JP2008285366A - Iron chloride solution, and method for producing iron oxide - Google Patents
Iron chloride solution, and method for producing iron oxide Download PDFInfo
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本発明は、塩化鉄溶液および酸化鉄の製造方法に関し、特に、色鮮やかな赤色顔料用酸化鉄を得ることができる塩化鉄溶液とその溶液から酸化鉄を製造する方法に関するものである。 The present invention relates to an iron chloride solution and a method for producing iron oxide, and more particularly to an iron chloride solution capable of obtaining a colorful red pigment iron oxide and a method for producing iron oxide from the solution.
酸化鉄は、人体に対する安全性が高く、また、耐候性や耐薬品性にも優れていることから、古くから無機顔料に用いられており、現在でも、コンクリートやアスファルト、ゴム、プラスチック、陶磁器等の様々な分野で着色剤として用いられている。 Iron oxide has long been used for inorganic pigments because of its high safety to the human body and excellent weather resistance and chemical resistance. Even today, concrete, asphalt, rubber, plastic, ceramics, etc. It is used as a colorant in various fields.
ところで、顔料の分野では、酸化鉄中にＭｎが多く含まれると、色調が黒ずんだものとなることが知られている。そのため、色鮮やかな赤色の顔料用酸化鉄を製造するには、Ｍｎ含有量の少ない原料溶液を用いる必要がある。 By the way, in the field of pigments, it is known that when Mn is contained in iron oxide, the color tone becomes dark. Therefore, it is necessary to use a raw material solution with a low Mn content in order to produce bright red iron oxide for pigment.
酸化鉄の製造方法としては、硫酸第一鉄溶液を原料とし、これを湿式合成して製造する方法、塩化第一鉄溶液を原料とし、これを噴霧焙焼して製造する方法等が一般に知られているが、顔料に用いられる酸化鉄の多くは、前者の湿式合成法で製造されたものであり、後者の噴霧焙焼法で製造されるものは少ない。 As a method for producing iron oxide, a method of producing a ferrous sulfate solution as a raw material by wet synthesis, a method of producing a ferrous chloride solution as a raw material by spray roasting, etc. are generally known. However, most of the iron oxides used for pigments are produced by the former wet synthesis method, and few are produced by the latter spray roasting method.
上記塩化第一鉄溶液を噴霧焙焼して酸化鉄を製造する方法は、鉄鋼の製造過程で発生する安価な酸洗廃液（塩化第一鉄溶液）を原料とすることができ、また、同時に生成する塩酸を酸洗工程で再使用できるという利点を有している。しかし、原料の塩化第一鉄溶液中には、鋼材を起源とするＭｎが不可避的に含まれており、それが噴霧焙焼によっても除去されずにそのまま酸化鉄中に取り込まれることになる。 The method of producing iron oxide by spray roasting the ferrous chloride solution can use an inexpensive pickling waste solution (ferrous chloride solution) generated in the steel production process as a raw material. It has the advantage that the hydrochloric acid produced can be reused in the pickling process. However, the ferrous chloride solution as a raw material inevitably contains Mn originating from steel, and it is directly taken into iron oxide without being removed by spray roasting.
そこで、塩化第一鉄溶液中の不純物を除去、精製する方法について、種々の提案がなされている。例えば、特許文献１には、Ｓｉ，Ａｌ，Ｃｒ，Ｃｕ，Ｐを低減する方法が、また、特許文献２には、ＳｉＯ２，Ｃｒ，Ａｌ，Ｔｉ等の不純物を低減する方法が、特許文献３には、Ｓｉ，Ａｌ，Ｐ等の不純物を低減する方法が、特許文献４には、Ｓｉ，Ａｌ，Ｐ，Ｎａ，Ｃａ，Ｂ等の不純物を低減する方法が、さらに、特許文献５には、ＳｉＯ２，Ｐ，Ｃｌを低減する方法が提案されている。しかし、Ｍｎは、塩化第一鉄溶液中では安定に存在するため、上記特許文献１〜５に記載のいずれの技術を用いても、Ｍｎを低減することはできない。 Thus, various proposals have been made on methods for removing and purifying impurities in the ferrous chloride solution. For example, Patent Document 1 discloses a method for reducing Si, Al, Cr, Cu, and P, and Patent Document 2 discloses a method for reducing impurities such as SiO 2 , Cr, Al, and Ti. 3 is a method for reducing impurities such as Si, Al, P, and the like, and Patent Document 4 is a method for reducing impurities such as Si, Al, P, Na, Ca, B. A method for reducing SiO 2 , P, and Cl has been proposed. However, since Mn exists stably in the ferrous chloride solution, Mn cannot be reduced by using any of the techniques described in Patent Documents 1 to 5.
一方、特許文献６には、塩化第一鉄溶液に塩酸を添加して析出する塩化第一鉄の結晶を分離除去することにより、塩化第一鉄溶液を精製する方法が提案されている。この方法によれば、結晶化を介して塩化第一鉄溶液中のＭｎをある程度まで低減することは可能である。
しかしながら、特許文献６の方法では、生成する塩化第一鉄の結晶中にもＭｎが移行するため、一回の操作でＭｎを低減することは難しいという問題がある。また、結晶化を複数回繰り返すことにより、Ｍｎをある程度まで低減することができるが、コスト面からみて実用的ではない。 However, the method of Patent Document 6 has a problem that it is difficult to reduce Mn by a single operation because Mn migrates into the crystals of ferrous chloride to be produced. Further, Mn can be reduced to some extent by repeating crystallization a plurality of times, but it is not practical from the viewpoint of cost.
そこで、本発明の目的は、噴霧焙焼法でも色鮮やかな赤色顔料用の酸化鉄を得ることができる塩化鉄溶液とその酸化鉄の製造方法を提案することにある。 Therefore, an object of the present invention is to propose an iron chloride solution and a method for producing the iron oxide, which can obtain a colorful iron oxide for a red pigment even by spray roasting.
発明者らは、上記課題を解決するべく、鋭意検討を重ねた。
その結果、原料溶液となる塩化第一鉄溶液をｐＨ６以下で酸化して生成させた含水酸化鉄（ＦｅＯＯＨ）またはマグネタイト（Ｆｅ３Ｏ４）を塩酸に溶解させた塩化鉄は、Ｍｎ含有量が少なく、したがって、これを噴霧焙焼することにより色鮮やかな色調を呈する赤色顔料用の酸化鉄を得ることができることを見出し、本願発明を完成させた。
Inventors repeated earnest examination in order to solve the said subject.
As a result, iron chloride obtained by dissolving hydrous iron oxide (FeOOH) or magnetite (Fe 3 O 4 ) produced by oxidizing a ferrous chloride solution as a raw material solution at pH 6 or less has a Mn content. Therefore, it was found that iron oxide for a red pigment exhibiting a colorful color tone can be obtained by spray roasting, and the present invention has been completed.
すなわち、本発明は、溶質中のＦｅ含有量が酸化鉄（Ｆｅ２Ｏ３）に換算して９９．０ｍａｓｓ％以上である塩化第一鉄溶液を、ｐＨ６以下で酸化して含水酸化鉄（ＦｅＯＯＨ）またはマグネタイト（Ｆｅ３Ｏ４）を生成させ、その含水酸化鉄またはマグネタイトを洗浄・脱水したのち塩酸に溶解することを特徴とする塩化鉄溶液の製造方法である。 That is, in the present invention, a ferrous chloride solution in which the Fe content in the solute is 99.0 mass% or more in terms of iron oxide (Fe 2 O 3 ) is oxidized at a pH of 6 or less to contain iron hydroxide (FeOOH). ) Or magnetite (Fe 3 O 4 ), and the hydrous iron oxide or magnetite is washed and dehydrated, and then dissolved in hydrochloric acid.
本発明の塩化鉄溶液の製造方法は、上記塩化第一鉄溶液に、アルカリ溶液を添加することを特徴とする。 The method for producing an iron chloride solution of the present invention is characterized in that an alkaline solution is added to the ferrous chloride solution.
また、本発明の塩化鉄溶液の製造方法は、上記塩酸に溶解した塩化鉄溶液中のＦｅ含有量とＭｎ含有量の和に対するＭｎ含有量を７２０ｍａｓｓｐｐｍ以下とすることを特徴とする。 Moreover, the manufacturing method of the iron chloride solution of this invention is characterized by making Mn content with respect to the sum of Fe content and Mn content in the iron chloride solution melt | dissolved in the said hydrochloric acid into 720 massppm or less.
また、本発明は、上記の方法で得られる塩化鉄溶液を噴霧焙焼して酸化鉄とすることを特徴とする酸化鉄の製造方法である。 Moreover, this invention is a manufacturing method of iron oxide characterized by spray-baking the iron chloride solution obtained by said method, and making it an iron oxide.
本発明の酸化鉄の製造方法は、酸化鉄中のＭｎ含有量を５００ｍａｓｓｐｐｍ以下とすることを特徴とする。 The method for producing iron oxide of the present invention is characterized in that the Mn content in iron oxide is 500 massppm or less.
本発明によれば、酸化鉄の原料となる塩化鉄溶液中のＭｎ含有量を容易に低減できるので、その溶液を噴霧焙焼することで、色鮮やかな赤色顔料用の酸化鉄を容易かつ安価に製造することが可能となる。 According to the present invention, the Mn content in the iron chloride solution used as the raw material for iron oxide can be easily reduced. By spray-roasting the solution, iron oxide for colorful red pigments can be easily and inexpensively obtained. Can be manufactured.
本発明に係るＭｎ含有量の少ない赤色顔料用酸化鉄を製造する原料となる塩化鉄溶液の製造方法について説明する。
本発明では、塩化鉄溶液の原料として、酸洗廃液等の塩化第一鉄溶液をｐＨ６以下で酸化することにより生成する含水酸化鉄（ＦｅＯＯＨ）またはマグネタイト（Ｆｅ３Ｏ４）を用いることを特徴とする。その理由は、ｐＨ６以下の条件では、塩化第一鉄溶液中のＭｎは、含水酸化鉄やマグネタイト中にはほとんど取り込まれずに溶液中にＭｎ２＋イオンの形で安定に存在するため、この条件下で塩化第一鉄溶液中に生成する含水酸化鉄やマグネタイトなどの鉄酸化物中には、Ｍｎ含有量が少なくなるためである。
The manufacturing method of the iron chloride solution used as the raw material which manufactures the iron oxide for red pigments with little Mn content which concerns on this invention is demonstrated.
In the present invention, as a raw material of the iron chloride solution, hydrous iron oxide (FeOOH) or magnetite (Fe 3 O 4 ) generated by oxidizing a ferrous chloride solution such as pickling waste liquid at pH 6 or less is used. And The reason for this is that Mn in the ferrous chloride solution is stably incorporated in the solution in the form of Mn 2+ ions in the solution of ferrous chloride and hardly contained in the hydrous iron oxide or magnetite under the condition of pH 6 or lower. This is because the Mn content is reduced in iron oxides such as hydrous iron oxide and magnetite produced in the ferrous chloride solution.
塩化第一鉄を酸化する方法としては、塩化第一鉄溶液中に空気などの酸素含有ガスや、オゾン含有ガスを吹き込む方法、過酸化水素水や硝酸ナトリウムなどの酸化剤を添加する方法などの公知の方法を用いることができる。酸化を行う際の溶液のｐＨは６以下とすることが必要である。ｐＨが６を超えると、生成する含水酸化鉄やマグネタイトの中にもＭｎが多く取り込まれるようになり、最終的に得られる酸化鉄が、色調のくすんだものとなってしまうからである。逆に、ｐＨが低過ぎると、空気酸化を行う場合には、含水酸化鉄やマグネタイトの生産性が低下するという別の問題が発生する。したがって、低Ｍｎの含水酸化鉄やマグネタイトを効率的に得ることができるｐＨは、より好ましくは２〜５．５、さらに好ましくは３〜５の範囲である。 As a method of oxidizing ferrous chloride, oxygen-containing gas such as air, ozone-containing gas is blown into ferrous chloride solution, and an oxidizing agent such as hydrogen peroxide or sodium nitrate is added. A known method can be used. The pH of the solution at the time of oxidation needs to be 6 or less. If the pH exceeds 6, much Mn will be taken into the hydrous iron oxide and magnetite to be produced, and the finally obtained iron oxide will be dull in color. On the other hand, if the pH is too low, another problem arises that the productivity of hydrous iron oxide and magnetite is reduced when air oxidation is performed. Therefore, the pH at which low Mn hydrous iron oxide and magnetite can be obtained efficiently is more preferably in the range of 2 to 5.5, and even more preferably in the range of 3 to 5.
ｐＨ６以下の塩化第一鉄溶液中で生成し得るＭｎ含有量の少ない含水酸化鉄には、空気などの酸素含有ガスやオゾン吹き込みにより生成するα−ＦｅＯＯＨ、β−ＦｅＯＯＨ、γ−ＦｅＯＯＨや、過酸化水素水で酸化した場合に生成するδ−ＦｅＯＯＨなどがあり、いずれも本発明の酸化鉄の製造に用いることができる。もちろん、これらの含水酸化鉄やマグネタイトは、複数種が混ざっているものであっても構わない。 Examples of the hydrous iron oxide having a low Mn content that can be produced in a ferrous chloride solution having a pH of 6 or less include oxygen-containing gases such as air, α-FeOOH, β-FeOOH, γ-FeOOH produced by ozone blowing, There are δ-FeOOH produced when oxidized with hydrogen oxide water, and any of them can be used for producing the iron oxide of the present invention. Of course, these hydrous iron oxides and magnetites may be a mixture of plural types.
次に、上記含水酸化鉄やマグネタイトを生成させる原料の塩化鉄第一鉄溶液について説明する。
塩化第一鉄溶液としては、溶液中に含まれる不純物を低減し、酸化鉄（Ｆｅ２Ｏ３）に換算した溶質中のＦｅの純度が９９．０ｍａｓｓ％以上である溶液を用いるのが好ましい。鉄鋼の製造過程で発生する酸洗廃液には、Ｍｎの他に、ＳｉＯ２やＰ，Ａｌ，Ｃｒ，Ｎｉなどの不純物を多量に含んでいる。そこで、酸洗廃液を一度精製して、溶質中のＦｅ純度を、酸化鉄に換算して９９．０％以上の塩化第一鉄溶液とし、これを本発明の原料溶液として用い、ｐＨ６以下で酸化することにより、Ｍｎだけでなく、ＳｉＯ２やＰ，Ａｌ，Ｃｒ，Ｎｉなどの不純物含有量の少ない含水酸化鉄やマグネタイトを生成することができ、ひいては、色鮮やかな酸化鉄を得ることができる。
Next, the ferrous chloride solution as a raw material for producing the hydrous iron oxide and magnetite will be described.
As the ferrous chloride solution, it is preferable to use a solution in which impurities contained in the solution are reduced and the purity of Fe in the solute converted to iron oxide (Fe 2 O 3 ) is 99.0 mass% or more. The pickling waste liquid generated in the manufacturing process of steel contains a large amount of impurities such as SiO 2 , P, Al, Cr, and Ni in addition to Mn. Therefore, the pickling waste liquor is purified once, and the Fe purity in the solute is converted to iron oxide to a ferrous chloride solution of 99.0% or more, which is used as the raw material solution of the present invention at a pH of 6 or less. Oxidation can produce not only Mn but also hydrous iron oxide and magnetite with low impurity content such as SiO 2 , P, Al, Cr, Ni, etc. As a result, colorful iron oxide can be obtained. it can.
しかし、酸化鉄（Ｆｅ２Ｏ３）に換算した溶質中のＦｅの純度が９９．０ｍａｓｓ％未満の不純物を多く含む塩化第一鉄溶液を原料溶液に用いると、ｐＨ６以下で酸化した際に、優先的にＳｉＯ２やＰ，Ａｌ，Ｃｒ，Ｎｉなどの不純物が含水酸化鉄やマグネタイトと共に析出するため、不純物の多い含水酸化鉄やマグネタイトが得られる。その結果、最終的に得られる酸化鉄は、不純物が多く、色のくすんだものしか得られず、好ましくない。なお、原料溶液である塩化第一鉄溶液の溶質中のＦｅ純度は、酸化鉄に換算した純度が９９．３ｍａｓｓ％以上であることが好ましく、さらに好ましくは９９．５ｍａｓｓ％以上である。 However, when a ferrous chloride solution containing a large amount of impurities with a purity of Fe of less than 99.0 mass% is used as a raw material solution in terms of iron oxide (Fe 2 O 3 ), when oxidized at a pH of 6 or less, Since impurities such as SiO 2 , P, Al, Cr, and Ni are preferentially precipitated together with hydrous iron oxide and magnetite, hydrous iron oxide and magnetite with a large amount of impurities can be obtained. As a result, the finally obtained iron oxide is not preferable because it has many impurities and only a dull color can be obtained. The Fe purity in the solute of the ferrous chloride solution that is the raw material solution is preferably 99.3 mass% or more, more preferably 99.5 mass% or more, in terms of iron oxide.
次いで、上記のようにして得られた低Ｍｎの含水酸化鉄またはマグネタイトを、洗浄・脱水する。上記洗浄工程は、Ｍｎを含む溶液を除去するために必須の工程である。というのは、洗浄が不十分であると、含水酸化鉄またはマグネタイトに付着しているＭｎ溶液の量が多くなるため、低Ｍｎの塩化鉄溶液を得るのが困難となるからである。 Next, the low Mn hydrous iron oxide or magnetite obtained as described above is washed and dehydrated. The cleaning step is an essential step for removing the solution containing Mn. This is because, if the cleaning is insufficient, the amount of the Mn solution adhering to the hydrous iron oxide or magnetite increases, and it becomes difficult to obtain a low Mn iron chloride solution.
次いで、洗浄・脱水して得た含水酸化鉄またはマグネタイトを塩酸に溶解させて、色鮮やかな赤色顔料の製造に用いる塩化鉄溶液とする。なお、上記塩化鉄溶液としては、含水酸化鉄を塩酸に溶解した場合には、塩化第二鉄溶液が得られ、また、マグネタイトが含まれる含水酸化鉄を塩酸に溶解した場合には、塩化第一鉄と塩化第二鉄の混合溶液が得られる。 Next, hydrous iron oxide or magnetite obtained by washing and dehydration is dissolved in hydrochloric acid to obtain an iron chloride solution used for producing a colorful red pigment. As the iron chloride solution, a ferric chloride solution is obtained when hydrous iron oxide is dissolved in hydrochloric acid, and a ferric chloride solution is obtained when hydrous iron oxide containing magnetite is dissolved in hydrochloric acid. A mixed solution of ferrous and ferric chloride is obtained.
上記塩化鉄溶液中に含まれるＭｎ含有量は、色鮮やかな色調の酸化鉄を得るためには、前記塩酸に溶解した後の塩化鉄中のＦｅ量とＭｎ量の和に対するＭｎ含有量（（Ｍｎ量／Ｍｎ量＋Ｆｅ量）×１０６）を７２０ｍａｓｓｐｐｍ以下とすることが好ましく、より好ましくは２９０ｍａｓｓｐｐｍ以下である。 The Mn content contained in the iron chloride solution is Mn content with respect to the sum of Fe amount and Mn amount in iron chloride after being dissolved in hydrochloric acid (( Mn amount / Mn amount + Fe amount) × 10 6 ) is preferably 720 massppm or less, more preferably 290 massppm or less.
なお、本発明の塩化鉄溶液を製造する方法においては、原料となる塩化第一鉄溶液に、アルカリ溶液を添加してｐＨを調整してから酸化を行ってもよい。添加するアルカリ溶液としては、水酸化物や炭酸塩のアルカリ溶液、アンモニア溶液など公知のものを用いることができる。アルカリ溶液を添加することで、溶液のｐＨを高めることで反応を早めて、含水酸化鉄やマグネタイトの生成量を増やすことができる。アルカリ溶液の添加は、特に空気酸化を行う場合に有効である。 In the method for producing an iron chloride solution of the present invention, oxidation may be performed after adjusting the pH by adding an alkaline solution to the ferrous chloride solution as a raw material. As the alkaline solution to be added, a known solution such as an alkali solution of hydroxide or carbonate, an ammonia solution, or the like can be used. By adding an alkaline solution, the reaction can be accelerated by increasing the pH of the solution, and the amount of hydrous iron oxide and magnetite produced can be increased. The addition of the alkaline solution is particularly effective when air oxidation is performed.
次に、上記のようにして得られた塩化鉄溶液を噴霧焙焼することで、Ｍｎ含有量が低くて赤色顔料に用いて好適な、色鮮やかな色調の酸化鉄を得ることができる。上記噴霧焙焼の方法は、一般的に行われている方法でよく、特に制限はない。また、得られた酸化鉄は、一般的に行われているように、水洗し、粉砕して、赤色顔料用酸化鉄（製品）とするのが好ましい。 Next, the iron chloride solution obtained as described above is spray roasted to obtain iron oxide with a colorful color tone that has a low Mn content and is suitable for use as a red pigment. The spray roasting method may be a generally performed method and is not particularly limited. The obtained iron oxide is preferably washed with water and pulverized to obtain iron oxide (product) for red pigment, as is generally done.
上記酸化鉄中に含まれるＭｎ含有量は、色鮮やかな色調の酸化鉄を得るためには、５００ｍａｓｓｐｐｍ以下とすることが好ましく、より好ましくは２００ｍａｓｓｐｐｍ以下である。 The Mn content contained in the iron oxide is preferably 500 massppm or less, and more preferably 200 massppm or less in order to obtain iron oxide having a colorful color tone.
（発明例１）
下記原料溶液（塩化第一鉄溶液）１リットルに、オゾン８ｖｏｌ％と残部が酸素からなる混合ガスを１Ｌ／ｍｉｎで４時間通気して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、その水酸化鉄を純水で沈降分離して洗浄し、ろ過して回収した。なお、上記オゾンは、酸素ガスをオゾン発生装置に通すことで発生させた。次いで、洗浄後の水酸化鉄は、濃塩酸１００ｍｌに溶解して塩化鉄溶液とし、ＦｅとＭｎの濃度をＩＣＰ発光分析装置で測定した。そして、この測定結果から、溶液中に含まれるＦｅが全て酸化鉄（Ｆｅ２Ｏ３）であるとした場合におけるＭｎ濃度を求め、Ｍｎの低減効果を調べた。
＜原料とした塩化第一鉄溶液＞
・Ｆｅ濃度：１８０ｇ／Ｌ
・Ｆｅ純度：９９．５ｍａｓｓ％
・Ｍｎ濃度：３０００ｍａｓｓｐｐｍ
・ｐＨ：０．８
ただし、上記Ｆｅ濃度およびＭｎ濃度は、溶質中に含まれるＦｅを全てヘマタイト（Ｆｅ２Ｏ３）に換算したときの値である（以降、同様とする）。
(Invention Example 1)
To 1 liter of the following raw material solution (ferrous chloride solution), a mixed gas consisting of 8 vol% ozone and the balance oxygen was aerated at 1 L / min for 4 hours to generate iron hydroxide, and then the solution was filtered. Iron hydroxide was obtained, and then the iron hydroxide was precipitated and separated with pure water, washed, and recovered by filtration. The ozone was generated by passing oxygen gas through an ozone generator. Subsequently, the washed iron hydroxide was dissolved in 100 ml of concentrated hydrochloric acid to obtain an iron chloride solution, and the concentrations of Fe and Mn were measured with an ICP emission spectrometer. Then, from this measurement result, the Mn concentration in the case where all Fe contained in the solution is iron oxide (Fe 2 O 3 ) was obtained, and the effect of reducing Mn was investigated.
<Ferrous chloride solution as raw material>
・ Fe concentration: 180 g / L
-Fe purity: 99.5 mass%
・ Mn concentration: 3000 massppm
・ PH: 0.8
However, the Fe concentration and the Mn concentration are values when all Fe contained in the solute is converted to hematite (Fe 2 O 3 ) (hereinafter the same).
（発明例２）
遊離酸量を変えてｐＨ１．５に調整したこと以外は発明例１と同じとした原料溶液（塩化第一鉄溶液）１リットルに、３０ｍａｓｓ％過酸化水素水２００ｍｌを添加して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、発明例１と同様の処理を施して、Ｍｎの低減効果を調べた。
(Invention Example 2)
Except that the amount of free acid was changed and adjusted to pH 1.5, 200 ml of 30 mass% hydrogen peroxide solution was added to 1 liter of a raw material solution (ferrous chloride solution) which was the same as that of Invention Example 1, and iron hydroxide was added. After the formation, the solution was filtered to obtain iron hydroxide, and then the same treatment as in Invention Example 1 was performed to examine the effect of reducing Mn.
（発明例３）
遊離酸量を変えてｐＨ３．０に調整したこと以外は発明例１と同じとした原料溶液（塩化第一鉄溶液）１リットルに、空気を１Ｌ／ｍｉｎで８時間通気して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、発明例１と同様の処理を施して、Ｍｎの低減効果を調べた。
(Invention Example 3)
Except that the amount of free acid was changed and adjusted to pH 3.0, 1 liter of a raw material solution (ferrous chloride solution) that was the same as that of Invention Example 1 was aerated with air at 1 L / min for 8 hours to give iron hydroxide. After the formation, the solution was filtered to obtain iron hydroxide, and then the same treatment as in Invention Example 1 was performed to examine the effect of reducing Mn.
（発明例４）
発明例３と同じ原料溶液（塩化第一鉄溶液）１リットルに、２ｍｏｌ／Ｌの炭酸ナトリウム溶液を添加してｐＨ４．２に調整しながら、空気を１Ｌ／ｍｉｎで３時間通気して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、発明例１と同様の処理を施して、Ｍｎの低減効果を調べた。
(Invention Example 4)
While adding 2 mol / L sodium carbonate solution to 1 liter of the same raw material solution (ferrous chloride solution) as in Invention Example 3 to adjust the pH to 4.2, air was ventilated at 1 L / min for 3 hours for hydroxylation. After producing iron, the solution was filtered to obtain iron hydroxide, and then the same treatment as in Invention Example 1 was performed to examine the effect of reducing Mn.
（発明例５）
発明例３と同じ原料溶液（塩化第一鉄溶液）１リットルに、２ｍｏｌ／Ｌの水酸化カリウム溶液を添加してｐＨ５．０に調整し、３０％過酸化水素水２００ｍｌを添加して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、発明例１と同様の処理を施して、Ｍｎの低減効果を調べた。
(Invention Example 5)
To 1 liter of the same raw material solution (ferrous chloride solution) as in Invention Example 3, a 2 mol / L potassium hydroxide solution was added to adjust the pH to 5.0, and 200 ml of 30% hydrogen peroxide water was added for hydroxylation. After producing iron, the solution was filtered to obtain iron hydroxide, and then the same treatment as in Invention Example 1 was performed to examine the effect of reducing Mn.
（発明例６）
発明例３と同じ原料溶液（塩化第一鉄溶液）１リットルに、２８ｍａｓｓ％アンモニア水を添加してｐＨ５．８に調整しながら、上記溶液を７０℃に昇温して空気を１Ｌ／ｍｉｎで１時間通気して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、発明例１と同様の処理を施して、Ｍｎの低減効果を調べた。
(Invention Example 6)
While adding 28 mass% ammonia water to 1 liter of the same raw material solution (Ferrous Chloride Solution) as in Invention Example 3 and adjusting the pH to 5.8, the temperature of the solution was raised to 70 ° C. and air was supplied at 1 L / min. After aeration for 1 hour to produce iron hydroxide, the solution was filtered to obtain iron hydroxide, and then the same treatment as in Invention Example 1 was performed to examine the effect of reducing Mn.
（比較例１）
発明例３と同じ原料溶液（塩化第一鉄溶液）１リットルに、８ｍｏｌ／Ｌの水酸化ナトリウム溶液を添加してｐＨ６．６に調整しながら、空気を１Ｌ／ｍｉｎで１時間通気して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、発明例１と同様の処理を施して、Ｍｎの低減効果を調べた。
(Comparative Example 1)
While adding 8 mol / L sodium hydroxide solution to 1 liter of the same raw material solution (ferrous chloride solution) as in Invention Example 3 to adjust the pH to 6.6, air was aerated at 1 L / min for 1 hour to form water. After producing iron oxide, the solution was filtered to obtain iron hydroxide, and then the same treatment as in Invention Example 1 was performed to examine the effect of reducing Mn.
（比較例２）
発明例３と同じ原料溶液（塩化第一鉄溶液）１リットルに、２８ｍａｓｓ％アンモニア水を添加してｐＨ７．５に調整しながら、上記溶液に空気を１Ｌ／ｍｉｎで１時間通気して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、発明例１と同様の処理を施して、Ｍｎの低減効果を調べた。
(Comparative Example 2)
While adding 28 mass% ammonia water to 1 liter of the same raw material solution (ferrous chloride solution) as in Invention Example 3 to adjust the pH to 7.5, air was bubbled through the solution at 1 L / min for 1 hour for hydroxylation. After producing iron, the solution was filtered to obtain iron hydroxide, and then the same treatment as in Invention Example 1 was performed to examine the effect of reducing Mn.
上記発明例１〜６、比較例１および２の試験条件および結果を纏めて表１に示した。表１から、ｐＨ６以下の条件下で酸化を行えば、Ｍｎ含有量が５００ｍａｓｓｐｐｍ未満の高純度の塩化鉄溶液が得られることがわかる。 The test conditions and results of Invention Examples 1 to 6 and Comparative Examples 1 and 2 are summarized in Table 1. From Table 1, it can be seen that a high-purity iron chloride solution having a Mn content of less than 500 massppm can be obtained by oxidation under conditions of pH 6 or less.
（発明例７，８、比較例３）
下記のＦｅ純度が異なる３種類の原料溶液（塩化第一鉄溶液）１リットルに、８ｍｏｌ／Ｌの水酸化ナトリウム溶液を添加してｐＨ５．０に調整しながら、空気を１Ｌ／ｍｉｎで１時間通気して水酸化鉄を生成させたのち、その溶液をろ過して水酸化鉄を得、その後、その水酸化鉄を純水で沈降分離を行って洗浄し、ろ過して回収した。なお、上記オゾンは、酸素ガスをオゾン発生装置に通して発生させた。次いで、洗浄後の水酸化鉄は、濃塩酸１００ｍｌに溶解して塩化鉄溶液とし、ＩＣＰ発光分析装置を用いて、Ｆｅ，Ｍｎ濃度の他に、Ａｌ，Ｃｒ，Ｎｉ，Ｐ，ＳｉＯ２濃度を測定した。この測定結果から、溶液中に含まれるＦｅが全て酸化鉄（Ｆｅ２Ｏ３）であるとした場合におけるＦｅ，Ｍｎ，Ａｌ，Ｃｒ，Ｎｉ，Ｐ，ＳｉＯ２の含有量を求めた。
＜原料とした塩化第一鉄溶液＞
・Ｆｅ濃度：１６０ｇ／Ｌ
・Ｆｅ純度：９９．６ｍａｓｓ％（発明例７）、９９．２ｍａｓｓ％（発明例８）、９８．５ｍａｓｓ％（比較例３）
・Ｍｎ濃度：３０００ｍａｓｓｐｐｍ
・ｐＨ：１．６
(Invention Examples 7 and 8, Comparative Example 3)
While adjusting the pH to 5.0 by adding 8 mol / L sodium hydroxide solution to 1 liter of the following three raw material solutions (ferrous chloride solution) with different Fe purity, air was adjusted at 1 L / min for 1 hour. After aeration to produce iron hydroxide, the solution was filtered to obtain iron hydroxide, and then the iron hydroxide was washed by settling with pure water and collected by filtration. The ozone was generated by passing oxygen gas through an ozone generator. Next, the iron hydroxide after washing is dissolved in 100 ml of concentrated hydrochloric acid to form an iron chloride solution, and using an ICP emission analyzer, in addition to Fe and Mn concentrations, Al, Cr, Ni, P, and SiO 2 concentrations are adjusted. It was measured. From this measurement result, the content of Fe, Mn, Al, Cr, Ni, P, and SiO 2 when all the Fe contained in the solution was iron oxide (Fe 2 O 3 ) was determined.
<Ferrous chloride solution as raw material>
-Fe concentration: 160 g / L
Fe purity: 99.6 mass% (Invention Example 7), 99.2 mass% (Invention Example 8), 98.5 mass% (Comparative Example 3)
・ Mn concentration: 3000 massppm
・ PH: 1.6
上記発明例７，８および比較例３の測定結果を纏めて表２に示した。表２から、原料溶液（塩化第一鉄溶液）のＦｅ純度が高ければ、Ｍｎ以外に酸化鉄の色調に悪影響を及ぼすＣｒ，Ｎｉの他、Ａｌ，Ｐ，ＳｉＯ２などの不純物の含有量も少ない塩化鉄溶液が得られることがわかる。 The measurement results of Invention Examples 7 and 8 and Comparative Example 3 are summarized in Table 2. From Table 2, if the Fe purity of the raw material solution (ferrous chloride solution) is high, the contents of impurities such as Al, P, SiO 2 as well as Cr, Ni which adversely affect the color tone of iron oxide in addition to Mn It can be seen that less iron chloride solution is obtained.
（比較例４）
下記塩化第一鉄溶液を、温度８００℃で噴霧焙焼して酸化鉄とし、水洗・乾燥後、振動ミルを用いて乾式粉砕し、空気透過法で測定した平均粒径が０．４５μｍの酸化鉄粉とし、得られた酸化鉄粉について、蛍光Ｘ線分析装置を用いて不純物の含有量を測定した。
＜噴霧焙焼した塩化鉄溶液＞
・Ｆｅ濃度：１２０ｇ／Ｌ
・Ｆｅ純度：９９．５ｍａｓｓ％
・Ｍｎ濃度：２０００ｍａｓｓｐｐｍ
・ｐＨ：２．０
(Comparative Example 4)
The following ferrous chloride solution is spray roasted at a temperature of 800 ° C. to obtain iron oxide, washed with water, dried, then dry pulverized using a vibration mill, and an average particle diameter measured by an air permeation method is 0.45 μm. About the obtained iron oxide powder as an iron powder, the content of impurities was measured using a fluorescent X-ray analyzer.
<Spray-baked iron chloride solution>
-Fe concentration: 120 g / L
-Fe purity: 99.5 mass%
・ Mn concentration: 2000 massppm
-PH: 2.0
（発明例９）
容量が１０ｍ３の反応槽に、比較例４と同じ原料溶液（塩化第一鉄溶液）を７ｍ３入れ、この溶液中に４０ｍａｓｓ％の水酸化ナトリウム溶液を加えてｐＨ４〜５の範囲に調整しながら空気を吹き込んで水酸化鉄を生成させ、その水酸化鉄をフィルタープレスでろ過して回収したのち水洗し、塩酸に溶解して塩化鉄溶液とした。その後、この塩化鉄溶液を、Ｆｅ濃度が１２０ｇ／Ｌとなるよう調整したのち噴霧焙焼して酸化鉄とし、水洗・乾燥後、振動ミルを用いて乾式粉砕し、空気透過法で測定した平均粒径が０．４３μｍの酸化鉄粉とした。上記のようにして得た酸化鉄粉について、比較例４と同様にして、酸化鉄粉中の不純物量を測定した。
(Invention Example 9)
The reactor capacity is 10 m 3, the same starting solution as in Comparative Example 4 (solution of ferrous chloride) 7m 3 placed, is adjusted to a range of pH4~5 adding 40 mass% of sodium hydroxide solution to this solution Then, air was blown in to produce iron hydroxide, and the iron hydroxide was collected by filtration with a filter press, washed with water, dissolved in hydrochloric acid to obtain an iron chloride solution. Thereafter, this iron chloride solution was adjusted to have an Fe concentration of 120 g / L, then spray roasted to obtain iron oxide, washed with water, dried, then dry pulverized using a vibration mill, and measured by an air permeation method. An iron oxide powder having a particle size of 0.43 μm was used. About the iron oxide powder obtained as mentioned above, it carried out similarly to the comparative example 4, and measured the impurity amount in an iron oxide powder.
さらに、上記比較例４および発明例９で得た酸化鉄粉について、日本電色製の色差計を用いて色調（Ｌ値、ａ値、ｂ値）を測定した。色調の測定は、上記酸化鉄１ｇに、あまに油０．６ｇを加えてフーバー式マラーでペースト化し、得られたペーストに透明ラッカー１２ｇを加え、アプリケーターにて厚み０．２ｍｍの塗膜とし、この塗膜試料を測定することにより行った。なお、両酸化鉄粉の色調の違いは、比較例４の鉄粉のＬ値、ａ値、ｂ値を０（基準）として、発明例９の酸化鉄粉と比較例４の酸化鉄粉のＬ値、ａ値、ｂ値の差（ΔＬ、Δａ、Δｂ）で評価した。 Furthermore, the color tone (L value, a value, b value) of the iron oxide powder obtained in Comparative Example 4 and Invention Example 9 was measured using a color difference meter made by Nippon Denshoku. The color tone is measured by adding 0.6 g of oil to 1 g of the iron oxide and pasting with a Hoover type muller, adding 12 g of transparent lacquer to the obtained paste, and forming a coating film having a thickness of 0.2 mm with an applicator. This was done by measuring the coating sample. In addition, the difference in the color tone of both iron oxide powders is that the L value, a value, and b value of the iron powder of Comparative Example 4 are 0 (reference), and the iron oxide powder of Invention Example 9 and the iron oxide powder of Comparative Example 4 are compared. Evaluation was based on the difference (ΔL, Δa, Δb) between the L value, the a value, and the b value.
上記比較例４および発明例９の測定結果を表３に示した。表３から、Ｍｎ含有量の少ない発明例９の酸化鉄は、比較例４の酸化鉄と比較して、ΔＬが＋２．５、Δａが＋５．９、Δｂが＋１．９であり、鮮やかな色調であることがわかる。 The measurement results of Comparative Example 4 and Invention Example 9 are shown in Table 3. From Table 3, the iron oxide of Invention Example 9 with a low Mn content has a brighter ΔL of +2.5, Δa of +5.9, and Δb of +1.9 than the iron oxide of Comparative Example 4. It turns out that it is a color tone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012176884A (en) * | 2011-02-04 | 2012-09-13 | Jfe Chemical Corp | Method of manufacturing ferric chloride solution |
| CN110304661A (en) * | 2019-06-20 | 2019-10-08 | 李柏丛 | Soft magnetic ferrite high-performance iron oxide new preparation process |
| CN112875762A (en) * | 2021-01-30 | 2021-06-01 | 嘉诚环保工程有限公司 | Method for preparing iron oxide red by using iron-containing pickling waste liquid |
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| JPH06157043A (en) * | 1992-11-13 | 1994-06-03 | Daiso Co Ltd | Continuous production of ferric chloride solution |
| JPH06171953A (en) * | 1992-12-14 | 1994-06-21 | Daiso Co Ltd | Production of ferric chloride solution |
| JP2006265421A (en) * | 2005-03-25 | 2006-10-05 | Jfe Chemical Corp | Iron oxide for iron chloride-based red pigment and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157043A (en) * | 1992-11-13 | 1994-06-03 | Daiso Co Ltd | Continuous production of ferric chloride solution |
| JPH06171953A (en) * | 1992-12-14 | 1994-06-21 | Daiso Co Ltd | Production of ferric chloride solution |
| JP2006265421A (en) * | 2005-03-25 | 2006-10-05 | Jfe Chemical Corp | Iron oxide for iron chloride-based red pigment and method for producing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012176884A (en) * | 2011-02-04 | 2012-09-13 | Jfe Chemical Corp | Method of manufacturing ferric chloride solution |
| CN110304661A (en) * | 2019-06-20 | 2019-10-08 | 李柏丛 | Soft magnetic ferrite high-performance iron oxide new preparation process |
| CN112875762A (en) * | 2021-01-30 | 2021-06-01 | 嘉诚环保工程有限公司 | Method for preparing iron oxide red by using iron-containing pickling waste liquid |
| CN112875762B (en) * | 2021-01-30 | 2022-05-17 | 河北粤海水务集团有限公司 | Method for preparing iron oxide red by using iron-containing pickling waste liquid |
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