JP2008156167A - Spherical peroxotitanium hydrate and spherical titanium oxide and method for producing the same - Google Patents
Spherical peroxotitanium hydrate and spherical titanium oxide and method for producing the same Download PDFInfo
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本発明は、塗料、化粧料、有色顔料、触媒、光触媒、熱線反射材料、電磁遮蔽、導電材等に有用な金属元素を含有する球状ペルオキソチタン水和物及び該金属元素を含有する球状二酸化チタン並びにそれらの製造方法に関する。 The present invention relates to spherical peroxotitanium hydrate containing metal elements useful for paints, cosmetics, colored pigments, catalysts, photocatalysts, heat ray reflective materials, electromagnetic shielding, conductive materials, and the like, and spherical titanium dioxide containing the metal elements In addition, the present invention relates to a manufacturing method thereof.
二酸化チタンに金属元素を含有することで、有色顔料、光触媒、導電性等の用途で広く利用することができる。例えば、金属元素として、Ｆｅ、Ｃｕ、Ｍｏ、Ｎｂなどをドープする方法として、過酸化水素と混合してなるチタン含有水溶液と金属塩を７０〜３００℃で加熱処理する方法（特許文献１）、カルボン酸など有機物が配位した有機チタンペロキシ化合物と金属塩を水に溶解後、濃縮してゲル化したものを熱処理する方法（特許文献２）が知られている。また，金属元素としてＮｂ等をドープする方法として、チタン水溶液と金属塩を加え水熱処理する方法や、塩基性物質などの沈殿形成剤の添加による沈殿物やゲル化物を熱処理する方法が知られている（特許文献３）。 By containing a metal element in titanium dioxide, it can be widely used in applications such as colored pigments, photocatalysts, and conductivity. For example, as a method of doping Fe, Cu, Mo, Nb or the like as a metal element, a titanium-containing aqueous solution mixed with hydrogen peroxide and a metal salt are heated at 70 to 300 ° C. (Patent Document 1), A method (Patent Document 2) is known in which an organic titanium peroxy compound coordinated with an organic substance such as carboxylic acid and a metal salt are dissolved in water and then heat-treated after being concentrated and gelled. In addition, as a method of doping Nb or the like as a metal element, a method of hydrothermal treatment by adding a titanium aqueous solution and a metal salt, and a method of heat treatment of a precipitate or a gelled product by addition of a precipitation forming agent such as a basic substance are known. (Patent Document 3).
上記特許文献１〜３に開示されている金属ドープの酸化チタンの製造方法では、溶液の加熱処理、有機物含有物のゲル化、沈殿剤の添加による沈殿物やゲル化といった、溶液の加熱にエネルギーを消費する方法、沈殿物やゲル化物の濾過分別に長時間を要しエネルギーを消費する方法である。さらに、沈殿物やゲル化物では金属ドープ酸化チタンとするために、熱処理が必要で、焼結による固い凝集塊が生じ、これを粉砕するためにエネルギーを消費する。
In the method for producing metal-doped titanium oxide disclosed in
本発明者らは、より安価な金属ドープ酸化チタンの製造方法を見出すべく種々検討したところ、Ｎｂ、Ｚｒ、Ｔａ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｎ、Ｓｉ、Ａｌ、Ｍｏ、Ｖ、Ｓｂ、Ｗ及びＨｆから選ばれる少なくとも一種の金属元素を含有するペルオキソチタン酸溶液を２０℃以下の温度に保持すると平均粒子径で０．１〜５μｍの金属元素を含有する球状ペルオキソチタン水和物が生成すること、さらに得られた球状粒子を加熱処理すると金属元素を含有する二酸化チタンが得られることを見出し、本発明を完成した。 The inventors have made various studies to find a cheaper method for producing metal-doped titanium oxide. As a result, Nb, Zr, Ta, Fe, Co, Ni, Cu, Mn, Si, Al, Mo, V, Sb, When a peroxotitanic acid solution containing at least one metal element selected from W and Hf is kept at a temperature of 20 ° C. or less, spherical peroxotitanium hydrate containing a metal element having an average particle size of 0.1 to 5 μm is formed. In addition, the present inventors have found that titanium dioxide containing a metal element can be obtained by heat-treating the obtained spherical particles, and the present invention has been completed.
すなわち、本発明は、ペルオキソチタン酸溶液を２０℃以下の温度に保持してＮｂ、Ｚｒ、Ｔａ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｎ、Ｓｉ、Ａｌ、Ｍｏ、Ｖ、Ｓｂ、Ｗ及びＨｆから選ばれる少なくとも一種の金属元素を含有する球状ペルオキソチタン水和物を生成させた後、固液分離することを特徴とする金属元素を含有する球状ペルオキソチタン水和物の製造方法である。また、前記球状ペルオキソチタン水和物を加熱処理することを特徴とする金属元素を含有する球状酸化チタンの製造方法である。
すなわち、本発明は、ペルオキソチタン酸溶液に金属元素化合物を添加し、塩基性物質を添加した後、溶液の凝固点以上で２０℃以下の温度で保持して球状粒子を生成させ、得られた球状粒子を固液分離し、焼成することを特徴とする金属元素を含有する球状酸化チタンの製造方法である。
That is, the present invention maintains a peroxotitanic acid solution at a temperature of 20 ° C. or lower, from Nb, Zr, Ta, Fe, Co, Ni, Cu, Mn, Si, Al, Mo, V, Sb, W, and Hf. A method for producing a spherical peroxotitanium hydrate containing a metal element, comprising producing a spherical peroxotitanium hydrate containing at least one selected metal element and then performing solid-liquid separation. The spherical peroxotitanium hydrate is heat-treated, and is a method for producing spherical titanium oxide containing a metal element.
That is, the present invention adds a metal element compound to a peroxotitanic acid solution, adds a basic substance, and then holds the solution at a temperature not lower than the freezing point of the solution and not higher than 20 ° C. to produce spherical particles. A method for producing spherical titanium oxide containing a metal element, characterized in that particles are solid-liquid separated and fired.
本発明の球状酸化チタンの製造方法は、製造時のエネルギー消費量が少なく、工業的に有利に金属元素を含有する球状酸化チタンを製造することが可能である。 The method for producing spherical titanium oxide of the present invention can produce spherical titanium oxide containing a metal element advantageously industrially with little energy consumption during production.
本発明は、金属元素を含有する球状ペルオキソチタン水和物の製造方法であって、Ｎｂ、Ｚｒ、Ｔａ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｎ、Ｓｉ、Ａｌ、Ｍｏ、Ｖ、Ｓｂ、Ｗ及びＨｆから選ばれる少なくとも一種の金属元素を含有するペルオキソチタン酸溶液を２０℃以下の温度に保持して球状粒子を生成させた後、固液分離することを特徴とする。 The present invention relates to a method for producing a spherical peroxotitanium hydrate containing a metal element, comprising Nb, Zr, Ta, Fe, Co, Ni, Cu, Mn, Si, Al, Mo, V, Sb, W and A peroxotitanic acid solution containing at least one metal element selected from Hf is maintained at a temperature of 20 ° C. or lower to produce spherical particles, and then solid-liquid separation is performed.
原料として用いるＮｂ、Ｚｒ、Ｔａ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｎ、Ｓｉ、Ａｌ、Ｍｏ、Ｖ、Ｓｂ、Ｗ及びＨｆから選ばれる少なくとも一種の金属元素を含有するペルオキソチタン酸溶液は、例えば、金属チタン、酸化チタン等のチタン原料を過酸化水素に溶解させた後、該金属元素の溶液を添加した後、塩基性物質を添加することで得ることができる。本発明においては、金属元素を含有するペルオキソチタン酸溶液の濃度は、Ｔｉのモル濃度で０．０１〜１ｍｏｌ／ｌの範囲が好ましい。金属元素としてはＴｉ原子に対して０．１から５０ａｔｍ％の範囲が望ましい。それより多いと球状粒子が生成し難くなる。添加する塩基性物質としては、アンモニア、モノエタンールアミン、水酸化ナトリウムなどのアルカリを用いることができるが、本発明においてはアンモニアが好ましい。塩基性物質の添加量は、０．１〜１０ｍｏｌ／ｌの範囲が好ましく、より好ましくは０．５〜５ｍｏｌ／ｌの範囲である。塩基性物質の添加温度は、５〜３０℃の範囲が好ましく、より好ましくは１０〜２５℃の範囲である。チタン原料を過酸化水素に溶解させた溶液に、金属元素の溶液を添加した後、塩基性物質を添加すると、溶液は透明溶液となり、この状態で、溶液の温度を２０℃以下に保持することで、溶液中に金属元素を含有する球状ペルオキソチタン水和物が析出する。保持する時間は、少なくとも２４時間は必要であり、好ましくは２４〜６０時間である。溶液を保持する温度が、上記範囲よりも高いと、粒子の析出が起こらず、ゲル化する。塩基性物質の添加量と析出温度を調整することにより、析出する金属元素を含有する球状ペルオキソチタン水和物の粒子径を制御することができるが、通常は０．２〜５μｍの範囲の金属元素を含有する球状ペルオキソチタン水和物を得ることができる。得られた金属元素を含有する球状ペルオキソチタン水和物は、金属イオンと共にペルオキソ基やＯＨ基を含む水和物で、Ｘ線回折測定からはアモルファス状態であり、示差熱−重量分析（ＴＧ−ＤＴＡ）から３００から３５０℃付近までＯＨ基等が存在しているものである。
また、金属元素を含有する球状ペルオキソチタン水和物の固液分離は、炉過、水洗、乾燥により行うことができる。本発明の金属元素を含有する球状ペルオキソチタン水和物は、後記の球状酸化チタンを得るための前駆体としての用途のみならず、触媒、光触媒等の用途にも有用なものである。
A peroxotitanic acid solution containing at least one metal element selected from Nb, Zr, Ta, Fe, Co, Ni, Cu, Mn, Si, Al, Mo, V, Sb, W and Hf used as a raw material is, for example, It can be obtained by dissolving a titanium raw material such as metal titanium or titanium oxide in hydrogen peroxide, adding a solution of the metal element, and then adding a basic substance. In the present invention, the concentration of the peroxotitanic acid solution containing a metal element is preferably in the range of 0.01 to 1 mol / l in terms of the molar concentration of Ti. The metal element is preferably in the range of 0.1 to 50 atm% with respect to Ti atoms. When it is more than that, it becomes difficult to produce spherical particles. As the basic substance to be added, alkali such as ammonia, monoethaneamine, sodium hydroxide or the like can be used, but ammonia is preferred in the present invention. The addition amount of the basic substance is preferably in the range of 0.1 to 10 mol / l, more preferably in the range of 0.5 to 5 mol / l. The addition temperature of the basic substance is preferably in the range of 5 to 30 ° C, more preferably in the range of 10 to 25 ° C. When a basic substance is added after adding a metal element solution to a solution in which titanium raw material is dissolved in hydrogen peroxide, the solution becomes a transparent solution, and in this state, the temperature of the solution is maintained at 20 ° C. or lower. Thus, spherical peroxotitanium hydrate containing a metal element is precipitated in the solution. The holding time needs to be at least 24 hours, preferably 24 to 60 hours. When the temperature at which the solution is held is higher than the above range, precipitation of particles does not occur and gelation occurs. The particle diameter of spherical peroxotitanium hydrate containing the metal element to be precipitated can be controlled by adjusting the amount of the basic substance added and the precipitation temperature, but usually a metal in the range of 0.2 to 5 μm. Spherical peroxotitanium hydrate containing elements can be obtained. The obtained spherical peroxotitanium hydrate containing a metal element is a hydrate containing a peroxo group and an OH group together with a metal ion, and is in an amorphous state from X-ray diffraction measurement. Differential thermal-gravimetric analysis (TG-) OH groups and the like exist from 300 to 350 ° C. from DTA).
Further, the solid-liquid separation of the spherical peroxotitanium hydrate containing the metal element can be performed by furnace heating, washing with water, and drying. The spherical peroxotitanium hydrate containing the metal element of the present invention is useful not only as a precursor for obtaining spherical titanium oxide described later, but also for applications such as catalysts and photocatalysts.
次の本発明はＮｂ、Ｚｒ、Ｔａ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｎ、Ｓｉ、Ａｌ、Ｍｏ、Ｖ、Ｓｂ、Ｗ及びＨｆから選ばれる少なくとも一種の金属元素を含有する球状酸化チタンの製造方法であって、前記の金属元素を含有する球状ペルオキソチタン水和物を加熱処理することを特徴とする。加熱の温度は、少なくとも１５０℃の温度があればよく、２００〜１０００℃の範囲が好ましい。金属元素を含有するペルオキソチタン水和物は非晶質の粒子であるが、このものを１５０〜４００℃の範囲の温度で加熱処理することで該水和物に含まれる結晶水が一部残存したアナタース型の球状酸化チタンが得られる。また、４００〜８００℃の範囲の温度で加熱処理することでアナタース型の球状酸化チタン、８００〜１０００℃の範囲の温度で加熱処理することで、ルチル型、或いは、ルチル型とアナタース型の混在した金属元素を含有する球状酸化チタンが得られる。アナタース型の構造を含む球状酸化チタンは触媒、光触媒、導電材に特に有用である。また、ルチル型の構造を含む球状酸化チタンは、塗料、有色顔料、熱線反射材料に特に有用である。本発明においては、上記温度範囲で加熱しても、加熱の前後で粒子形状の変化はほとんどなく、加熱前の球状粒子の形状が維持された金属元素を含有する酸化チタンを得ることができる。 Next, the present invention produces spherical titanium oxide containing at least one metal element selected from Nb, Zr, Ta, Fe, Co, Ni, Cu, Mn, Si, Al, Mo, V, Sb, W and Hf. A method is characterized in that the spherical peroxotitanium hydrate containing the metal element is heat-treated. The heating temperature may be at least 150 ° C., and is preferably in the range of 200 to 1000 ° C. Peroxotitanium hydrate containing a metal element is an amorphous particle, but by subjecting this to heat treatment at a temperature in the range of 150 to 400 ° C., part of the crystal water contained in the hydrate remains. Anatase type spherical titanium oxide is obtained. Also, anatase type spherical titanium oxide by heat treatment at a temperature in the range of 400 to 800 ° C., rutile type or a mixture of rutile type and anatase type by heat treatment at a temperature in the range of 800 to 1000 ° C. Spherical titanium oxide containing the obtained metal element is obtained. Spherical titanium oxide containing an anatase structure is particularly useful as a catalyst, a photocatalyst, and a conductive material. Spherical titanium oxide containing a rutile structure is particularly useful for paints, colored pigments, and heat ray reflective materials. In this invention, even if it heats in the said temperature range, there is almost no change of a particle shape before and behind heating, and the titanium oxide containing the metallic element with which the shape of the spherical particle before a heating was maintained can be obtained.
以下、本発明を実施例により説明するが、本発明はそれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
実施例１
（ペルオキソチタン酸溶液の作成）
酸化チタン４ｇ（ＰＴ−３０１：石原産業株式会社製高純度酸化チタン）に３０％の濃度のＨ２Ｏ２水溶液１００ｍｌを添加し、金属元素ＮｂとしてＮｂＯＣｌ３を０．２０ｇ含む水溶液を添加し、その後、２５％の濃度のＮＨ３水溶液２５ｍｌを添加してｐＨを１０．１に調整した後、１５℃温度で保持して酸化チタンを溶解させることで、ペルオキソチタン酸溶液を得た。
（ペルオキソチタン酸溶液の作成）
Example 1
(Preparation of peroxotitanic acid solution)
To 4 g of titanium oxide (PT-301: high-purity titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), 100 ml of 30% H 2 O 2 aqueous solution is added, and an aqueous solution containing 0.20 g of NbOCl 3 as the metal element Nb is added. Then, 25 ml of a 25% NH 3 aqueous solution was added to adjust the pH to 10.1, and the titanium oxide was dissolved at a temperature of 15 ° C. to obtain a peroxotitanic acid solution.
(Preparation of peroxotitanic acid solution)
（球状ペルオキソチタン水和物の生成）
得られたペルオキソチタン酸溶液を１０℃の温度で３６時間保持して球状ペルオキソチタン水和物を生成させた。次いで懸濁液をろ過、水洗、乾燥することで固液分離し本発明の金属元素（Ｎｂ）含有の球状ペルオキソチタン水和物（試料Ａ）を得た。（Ｎｂ／Ｔｉ＝０．０２）
(Formation of spherical peroxotitanium hydrate)
The obtained peroxotitanic acid solution was kept at a temperature of 10 ° C. for 36 hours to produce spherical peroxotitanium hydrate. Subsequently, the suspension was filtered, washed with water, and dried to obtain a solid-liquid separation to obtain a spherical peroxotitanium hydrate (sample A) containing the metal element (Nb) of the present invention. (Nb / Ti = 0.02)
（加熱処理）
得られた球状ペルオキソチタン水和物（試料Ａ）を大気中６００℃の温度で２時間加熱処理して本発明の球状酸化チタン（試料Ｂ）を得た。
(Heat treatment)
The obtained spherical peroxotitanium hydrate (sample A) was heat-treated in the atmosphere at a temperature of 600 ° C. for 2 hours to obtain the spherical titanium oxide (sample B) of the present invention.
実施例２
実施例１のペルオキソチタン酸溶液の作成において、金属元素ＮｂとしてＮｂＯＣｌ３を１．０２ｇ含む水溶液を添加すること以外は同様にして、ペルオキソチタン酸溶液を得た。（Ｎｂ／Ｔｉの原子比＝０．０２）。球状粒子の生成と焼成も実施例１と同様にして本発明の球状酸化チタン（試料Ｂ）を得た。
Example 2
In the preparation of the peroxotitanate solution of Example 1, a peroxotitanate solution was obtained in the same manner except that an aqueous solution containing 1.02 g of NbOCl3 as the metal element Nb was added. (Nb / Ti atomic ratio = 0.02). Spherical titanium oxide (sample B) of the present invention was obtained in the same manner as in Example 1 for the production and firing of spherical particles.
実施例３
実施例１のペルオキソチタン酸溶液の作成において、金属元素ＮｂとしてＮｂＯＣｌ３を１．５３ｇ含む水溶液を添加すること以外は同様にして、ペルオキソチタン酸溶液を得た。（Ｎｂ／Ｔｉの原子比＝０．１５）。球状粒子の生成と焼成も実施例１と同様にして本発明の球状酸化チタン（試料Ｃ）を得た。
Example 3
A peroxotitanic acid solution was obtained in the same manner as in Example 1 except that an aqueous solution containing 1.53 g of NbOCl3 as the metal element Nb was added. (Nb / Ti atomic ratio = 0.15). Spherical titanium oxide (sample C) of the present invention was obtained in the same manner as in Example 1 for the production and firing of spherical particles.
実施例４
実施例１の焼成において、得られた球状粒子を管状炉内に装入し、Ｎ２（２５容積％）−Ｈ２（７５容積％）の混合ガスを２リットル／分で流して、６００℃の温度で２時間焼成することで本発明の球状酸化チタン（試料Ｄ）を得た。
Example 4
In the firing of Example 1, the obtained spherical particles were charged into a tubular furnace, and a mixed gas of N2 (25% by volume) -H2 (75% by volume) was flowed at 2 liters / minute, and a temperature of 600 ° C. Was fired for 2 hours to obtain spherical titanium oxide (sample D) of the present invention.
実施例５
実施例３の焼成において、得られた球状粒子を、管状炉内に装入し、Ｎ２（２５容積％）−Ｈ２（７５容積％）の混合ガスを２リットル／分で流して、６００℃の温度で２時間焼成することで本発明の球状酸化チタン（試料Ｅ）を得た。
Example 5
In the calcination of Example 3, the obtained spherical particles were charged into a tubular furnace, and a mixed gas of N 2 (25% by volume) -H 2 (75% by volume) was flowed at 2 liters / minute, Spherical titanium oxide (sample E) of the present invention was obtained by firing at a temperature for 2 hours.
比較例１
実施例１の球状粒子の生成において、保持する温度及び時間を６０℃、８時間とした場合には、ゲル化して塊となることから、大気中６００℃で焼成後、これを乳鉢で粉砕して比較試料の酸化チタン（試料Ｆ）を得た。
Comparative Example 1
In the production of the spherical particles of Example 1, when the temperature and time to be maintained are 60 ° C. and 8 hours, they are gelled and become lumps. Thus, a comparative sample of titanium oxide (sample F) was obtained.
実施例１〜５及び比較例１で得られた金属元素（Ｎｂ）を含有する酸化チタン（試料Ａ、Ｂの走査型電子顕微鏡写真を撮影し、粒子形状及び平均粒子径を算出した。各試料の走査型電子顕微鏡写真をそれぞれ図１〜７に示した。図１及び２より、本発明の製造方法で得られる金属元素を含有する酸化チタンは、その粒子形状が球状であり、平均粒子径は試料Ａは１．５６μｍであることがわかった。試料Ｂ〜Ｆの平均粒子径は表１に示した。一方、図７として、比較試料（試料Ｆ）の酸化チタンでは、ゲル化した塊となることから、焼成後、これを乳鉢で粉砕したものを示した。
なお、試料Ｂ〜ＦとＧの結晶形を粉末Ｘ線回折により確認したところ、何れもアナターゼ型の構造を有していた。
Titanium oxide containing the metal element (Nb) obtained in Examples 1 to 5 and Comparative Example 1 (Scanning electron micrographs of samples A and B were taken, and the particle shape and average particle size were calculated. 1 to 7 show scanning electron micrographs of each of Fig. 1 and 2. From Figs.1 and 2, titanium oxide containing a metal element obtained by the production method of the present invention has a spherical particle shape and an average particle diameter. The sample A was found to be 1.56 μm, and the average particle diameters of the samples B to F are shown in Table 1. On the other hand, as shown in FIG. Therefore, after firing, this was crushed in a mortar.
When the crystal forms of Samples B to F and G were confirmed by powder X-ray diffraction, they all had an anatase type structure.
本発明は、塗料、化粧料、有色顔料、触媒、光触媒、熱線反射材料、電磁遮蔽、導電材等として有用なものである。 The present invention is useful as a paint, a cosmetic, a colored pigment, a catalyst, a photocatalyst, a heat ray reflective material, an electromagnetic shield, a conductive material, and the like.
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