JP2011219346A - Method for producing rutile-type titanium oxide having (001) crystal plane - Google Patents
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 200
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000013078 crystal Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 25
- 239000012736 aqueous medium Substances 0.000 claims abstract description 16
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 30
- 238000005374 membrane filtration Methods 0.000 claims description 28
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
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- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、光触媒、酸化触媒として有用な結晶面（００１）を有するルチル型酸化チタンの製造方法に関する。 The present invention relates to a method for producing a rutile-type titanium oxide having a crystal plane (001) useful as a photocatalyst or an oxidation catalyst.
光触媒反応とは、光触媒能を有する固体化合物に紫外線を照射すると励起電子と電子が出たあとの穴（正孔：ホール）が生成し、該励起電子が還元作用を、該ホールが強い酸化作用を有し、これらにより反応物を酸化、或いは還元する反応である。代表的な光触媒能を有する固体化合物としては酸化チタンが知られている。酸化チタンは紫外線を吸収すると、強い酸化作用を発揮することができ、例えば、大気浄化、水質浄化、汚染防止、脱臭、抗菌、院内感染防止、曇り防止など幅広い用途に応用されている。 Photocatalytic reaction means that when a solid compound having photocatalytic activity is irradiated with ultraviolet rays, excited electrons and holes after the electrons are emitted (holes: holes) are generated, the excited electrons perform a reducing action, and the holes have a strong oxidizing action. In this reaction, the reactant is oxidized or reduced. Titanium oxide is known as a typical solid compound having photocatalytic activity. Titanium oxide can exhibit a strong oxidizing action when it absorbs ultraviolet rays, and is applied to a wide range of applications such as air purification, water purification, pollution prevention, deodorization, antibacterial, hospital infection prevention, and fog prevention.
酸化チタンの主な結晶形としては、ルチル型とアナターゼ型が知られている。これらの結晶性酸化チタンは非晶性酸化チタン（アモルファス）に比べて高い化学的安定性を示し屈折率が大きい。そして、結晶化度が高い酸化チタン粒子は、結晶化度が低い酸化チタン粉末に比べて優れた光触媒能を発揮することができ、結晶のサイズが大きいほど、優れた光触媒能を発揮することが知られている。 Rutile type and anatase type are known as main crystal forms of titanium oxide. These crystalline titanium oxides exhibit higher chemical stability and a higher refractive index than amorphous titanium oxide (amorphous). Titanium oxide particles having a high degree of crystallinity can exhibit superior photocatalytic activity as compared with titanium oxide powder having a low degree of crystallinity. The larger the crystal size, the better the photocatalytic activity can be. Are known.
特許文献１には、酸化チタンにアルカリ性過酸化水素水処理、硫酸処理、又はフッ化水素酸処理を施して新規結晶面が発現した酸化チタン結晶を作る方法が記載されており、得られた新規結晶面が発現した酸化チタンからなる光触媒は高い酸化触媒性能を有することが記載されている。前記新規結晶面が発現した酸化チタンとしては、（１）ルチル型酸化チタンから得られる、新規に（１２１）面を発現させた酸化チタン結晶、（２）ルチル型酸化チタンから得られる、新規に（００１）（１２１）（０２１）（０１０）面を発現させた酸化チタン結晶、（３）ルチル型酸化チタンから得られる、新規に（０２１）面を発現させた酸化チタン結晶、（４）アナターゼ型酸化チタンから得られる、新規に（１２０）面を発現させた酸化チタン結晶、（５）アナターゼ型酸化チタンから得られる、新規に（１２２）面を発現させた酸化チタン結晶、（６）アナターゼ型酸化チタンから得られる、新規に（１１２）面を発現させた酸化チタン結晶が開示されている。 Patent Document 1 describes a method for producing a titanium oxide crystal in which a new crystal plane is expressed by subjecting titanium oxide to alkaline hydrogen peroxide treatment, sulfuric acid treatment, or hydrofluoric acid treatment. It is described that a photocatalyst composed of titanium oxide having a crystal plane developed has high oxidation catalyst performance. As the titanium oxide with the new crystal plane developed, (1) obtained from rutile type titanium oxide, titanium oxide crystal with newly developed (121) plane, (2) obtained from rutile type titanium oxide, (001) (121) (021) Titanium oxide crystal expressing (010) plane, (3) Titanium oxide crystal newly expressing (021) plane obtained from rutile-type titanium oxide, (4) Anatase Titanium oxide crystal newly developed from (120) plane obtained from type titanium oxide, (5) Titanium oxide crystal newly developed from (122) plane obtained from anatase type titanium oxide, (6) Anatase Disclosed is a titanium oxide crystal having a newly developed (112) plane obtained from type titanium oxide.
また、特許文献２には、チタン化合物を１５０℃以上の温度、その温度における飽和蒸気圧以上の圧力下で加水分解することにより、アナターゼ型とルチル型が混在する酸化チタンであって、結晶化度が高く、粒子径の揃った微粒子酸化チタンを得ることができること、さらに、チタン化合物の濃度を調整することによりアナターゼ型とルチル型の組成比率を容易に制御することができることが記載されている。 Patent Document 2 discloses a titanium oxide in which anatase type and rutile type are mixed by hydrolyzing a titanium compound at a temperature of 150 ° C. or higher and a pressure equal to or higher than a saturated vapor pressure at the temperature. It is described that fine titanium oxide having a high particle size and uniform particle diameter can be obtained, and that the composition ratio of anatase type and rutile type can be easily controlled by adjusting the concentration of the titanium compound. .
しかしながら、上記の製造方法により得られるルチル型酸化チタンは、光触媒能の点で十分に満足のできるものではなかった。すなわち、十分に満足のできる光触媒活性を有するルチル型酸化チタンの製造方法が未だ見出されていないのが現状である。 However, the rutile-type titanium oxide obtained by the above production method is not fully satisfactory in terms of photocatalytic activity. That is, the present condition is that the manufacturing method of the rutile type titanium oxide which has the photocatalytic activity which can fully be satisfied is not yet found.
従って、本発明の目的は、高い光触媒活性を有するルチル型酸化チタンの製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing rutile-type titanium oxide having high photocatalytic activity.
本発明者は、上記課題を解決するため鋭意検討した結果、通常、三塩化チタン等の３価のチタン化合物を水性媒体中で水熱処理すると、結晶面（１１０）（１１１）を有するロッド状ルチル型酸化チタンが得られるが、４価のチタン化合物に、特定の温度、圧力下で特定の時間水熱処理を施すと、結晶面（００１）（１１０）（１１１）を有するロッド状ルチル型酸化チタンを得ることができること（図１参照）、及び、得られた結晶面（００１）（１１０）（１１１）を有するロッド状ルチル型酸化チタンは、優れた光触媒能を発揮することができることを見出した。本発明はこれらの知見に基づいて完成させたものである。 As a result of intensive studies to solve the above-mentioned problems, the present inventor usually obtained a rod-shaped rutile having crystal planes (110) and (111) when hydrothermally treating a trivalent titanium compound such as titanium trichloride in an aqueous medium. -Type titanium oxide is obtained. When a tetravalent titanium compound is subjected to hydrothermal treatment for a specific time at a specific temperature and pressure, rod-shaped rutile titanium oxide having crystal planes (001) (110) (111) is obtained. (See FIG. 1), and the rod-shaped rutile titanium oxide having the obtained crystal planes (001), (110), and (111) has been found to exhibit excellent photocatalytic activity. . The present invention has been completed based on these findings.
すなわち、本発明は反応温度１１０℃〜２２０℃、その反応温度における飽和蒸気圧以上の圧力下、水性媒体中で４価のチタン化合物に２時間以上水熱処理を施すことにより、結晶面（００１）（１１０）（１１１）を有するロッド状ルチル型酸化チタンを得ることを特徴とするルチル型酸化チタンの製造方法を提供する。 That is, in the present invention, a crystal surface (001) is obtained by subjecting a tetravalent titanium compound to hydrothermal treatment for 2 hours or more in an aqueous medium under a reaction temperature of 110 ° C. to 220 ° C. and a pressure equal to or higher than a saturated vapor pressure at the reaction temperature. A rod-shaped rutile type titanium oxide having (110) (111) is provided, and a method for producing a rutile type titanium oxide is provided.
４価のチタン化合物としては、四塩化チタンが好ましい。 As the tetravalent titanium compound, titanium tetrachloride is preferable.
また、水性媒体中の４価のチタン化合物濃度は、１．５〜１７．０重量％（チタン換算）の範囲内に調整することが好ましい。 Further, the concentration of the tetravalent titanium compound in the aqueous medium is preferably adjusted within the range of 1.5 to 17.0% by weight (in terms of titanium).
更に、上記得られたロッド状ルチル型酸化チタンをクロスフロー方式により膜濾過する操作に付すことが好ましく、特に、ロッド状ルチル型酸化チタン濃度が０．１〜４０重量％のロッド状ルチル型酸化チタン水分散液をクロスフロー方式により膜濾過し、イオン性不純物を透過液と共に分離除去して濃縮されたロッド状ルチル型酸化チタン水分散液を得、該濃縮されたロッド状ルチル型酸化チタン水分散液に水を加えて、ロッド状ルチル型酸化チタン濃度が上記範囲となるように希釈し、再びクロスフロー方式により膜濾過する操作を繰り返す循環膜濾過方式によりロッド状ルチル型酸化チタンを精製すると共に、定期的に濾過膜を逆洗浄することが好ましい。 Further, it is preferable to subject the obtained rod-shaped rutile titanium oxide to an operation of membrane filtration by a cross flow method, and in particular, rod-shaped rutile titanium oxide having a rod-shaped rutile titanium oxide concentration of 0.1 to 40% by weight. The titanium aqueous dispersion is subjected to membrane filtration by a cross-flow method, and ionic impurities are separated and removed together with the permeate to obtain a concentrated rod-shaped rutile-type titanium oxide aqueous dispersion. The concentrated rod-shaped rutile-type titanium oxide aqueous solution is obtained. Add water to the dispersion, dilute the rod-shaped rutile titanium oxide concentration to the above range, and then repeat the membrane filtration operation by the crossflow method again to purify the rod-shaped rutile titanium oxide. At the same time, it is preferable to periodically back-filter the filter membrane.
本発明に係るルチル型酸化チタンの製造方法によれば、４価のチタン化合物を特定の条件下、水性媒体中で水熱処理を施すことにより、結晶面（００１）を有するロッド状ルチル型酸化チタンを効率よく合成することができる。本発明に係るルチル型酸化チタンの製造方法によれば、四塩化チタンなどの安価な原料を使用することができるため、コストの大幅な削減が可能である。また、通常、ロッド状ルチル型酸化チタンは結晶面（１１０）と（１１１）からなり、結晶面（１１０）が還元サイト、結晶面（１１１）が酸化サイトとして作用するが、本発明に係るルチル型酸化チタンの製造方法により得られるロッド状ルチル型酸化チタンは、結晶面（１１０）（１１１）に加えて、結晶面（００１）を有し、結晶面（１１０）が還元サイト、結晶面（００１）と（１１１）が酸化サイトとして作用するため、紫外線を照射することにより生成する励起電子と活性化されたホールの分離性をより高める構造を有する。そのため、励起電子とホールの再結合や逆反応の進行をより低く抑制することができ、強い酸化作用を発揮することができる。本発明に係るルチル型酸化チタンの製造方法により得られたロッド状ルチル型酸化チタンを光触媒として使用すると、有機物質を効率よく酸化することができるため、大気の浄化、脱臭、浄水、抗菌、防汚などの目的に有用である。 According to the method for producing a rutile type titanium oxide according to the present invention, a rod-like rutile type titanium oxide having a crystal plane (001) is obtained by subjecting a tetravalent titanium compound to hydrothermal treatment in an aqueous medium under specific conditions. Can be synthesized efficiently. According to the method for producing a rutile type titanium oxide according to the present invention, since an inexpensive raw material such as titanium tetrachloride can be used, the cost can be significantly reduced. In general, rod-shaped rutile type titanium oxide is composed of crystal planes (110) and (111). The crystal plane (110) functions as a reduction site and the crystal plane (111) functions as an oxidation site. The rod-shaped rutile titanium oxide obtained by the method for producing type titanium oxide has a crystal plane (001) in addition to the crystal planes (110) and (111), and the crystal plane (110) is a reduction site and a crystal plane ( Since (001) and (111) act as oxidation sites, they have a structure that further increases the separation between excited electrons generated by irradiating ultraviolet rays and activated holes. Therefore, the recombination of excited electrons and holes and the progress of the reverse reaction can be further suppressed, and a strong oxidizing action can be exhibited. When the rod-shaped rutile type titanium oxide obtained by the method for producing rutile type titanium oxide according to the present invention is used as a photocatalyst, it is possible to efficiently oxidize an organic substance, so that air purification, deodorization, water purification, antibacterial, Useful for purposes such as dirt.
本発明に係るルチル型酸化チタンの製造方法は、反応温度１１０℃〜２２０℃、その反応温度における飽和蒸気圧以上の圧力下、水性媒体中で４価のチタン化合物に２時間以上水熱処理を施すことにより、結晶面（００１）（１１０）（１１１）を有するロッド状ルチル型酸化チタンを得ることを特徴とする。 The method for producing a rutile type titanium oxide according to the present invention comprises subjecting a tetravalent titanium compound to hydrothermal treatment for 2 hours or more in an aqueous medium under a reaction temperature of 110 ° C. to 220 ° C. and a pressure equal to or higher than a saturated vapor pressure at the reaction temperature. Thus, rod-shaped rutile type titanium oxide having crystal planes (001) (110) (111) is obtained.
（４価のチタン化合物）
本発明における４価のチタン化合物は、例えば、下記式（１）で表される化合物等を挙げることができる。
Ｔｉ（ＯＲ）tＸ4-t （１）
（式中、Ｒは炭化水素基を示し、Ｘはハロゲン原子を示す。ｔは０〜３の整数を示す）
(Tetravalent titanium compound)
Examples of the tetravalent titanium compound in the present invention include a compound represented by the following formula (1).
Ti (OR) t X 4-t (1)
(In the formula, R represents a hydrocarbon group, X represents a halogen atom, and t represents an integer of 0 to 3).
Ｒにおける炭化水素基としては、例えば、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、sec−ブチル、tert−ブチル等のＣ1-4脂肪族炭化水素基等を挙げることができる。 Examples of the hydrocarbon group for R include C 1-4 aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.
Ｘにおけるハロゲン原子としては、塩素、臭素、ヨウ素等を挙げることができる。 Examples of the halogen atom for X include chlorine, bromine, iodine and the like.
このような４価のチタン化合物としては、例えば、ＴｉＣｌ4、ＴｉＢｒ4、ＴｉＩ4などのテトラハロゲン化チタン；Ｔｉ（ＯＣＨ3）Ｃｌ3、Ｔｉ（ＯＣ2Ｈ5）Ｃｌ3、Ｔｉ（ＯＣ4Ｈ9）Ｃｌ3、Ｔｉ（ＯＣ2Ｈ5）Ｂｒ3、Ｔｉ（ＯＣ4Ｈ9）Ｂｒ3などのトリハロゲン化アルコキシチタン；Ｔｉ（ＯＣＨ3）2Ｃｌ2、Ｔｉ（ＯＣ2Ｈ5）2Ｃｌ2、Ｔｉ（ＯＣ4Ｈ9）2Ｃｌ2、Ｔｉ（ＯＣ2Ｈ5）2Ｂｒ2などのジハロゲン化ジアルコキシチタン；Ｔｉ（ＯＣＨ3）3Ｃｌ、Ｔｉ（ＯＣ2Ｈ5）3Ｃｌ、Ｔｉ（ＯＣ4Ｈ9）3Ｃｌ、Ｔｉ（ＯＣ2Ｈ5）3Ｂｒなどのモノハロゲン化トリアルコキシチタン等を挙げることができる。本発明においては、なかでも安価で、入手が容易な点で、テトラハロゲン化チタンが好ましく、特に四塩化チタン（ＴｉＣｌ4）が好ましい。 Examples of such tetravalent titanium compounds include titanium tetrahalides such as TiCl 4 , TiBr 4 , and TiI 4 ; Ti (OCH 3 ) Cl 3 , Ti (OC 2 H 5 ) Cl 3 , and Ti (OC 4). Trihalogenated alkoxytitanium such as H 9 ) Cl 3 , Ti (OC 2 H 5 ) Br 3 , Ti (OC 4 H 9 ) Br 3 ; Ti (OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Dihalogenated dialkoxytitanium such as Cl 2 , Ti (OC 4 H 9 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Br 2 ; Ti (OCH 3 ) 3 Cl, Ti (OC 2 H 5 ) 3 Cl, Examples thereof include monohalogenated trialkoxytitanium such as Ti (OC 4 H 9 ) 3 Cl and Ti (OC 2 H 5 ) 3 Br. In the present invention, titanium tetrahalide is preferable, and titanium tetrachloride (TiCl 4 ) is particularly preferable because it is inexpensive and easily available.
（水性媒体）
本発明において、水熱処理の際に用いる水性媒体としては、例えば、水又は水と水溶性有機溶媒との混合液等を挙げることができる。前記水溶性有機溶媒としては、例えば、メタノール、エタノール等のアルコール；エチレングリコールジメチルエーテル等のエーテル；アセトン等のケトン；アセトニトリル等のニトリル；酢酸等のカルボン酸等を挙げることができる。
(Aqueous medium)
In the present invention, examples of the aqueous medium used in the hydrothermal treatment include water or a mixed solution of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols such as methanol and ethanol; ethers such as ethylene glycol dimethyl ether; ketones such as acetone; nitriles such as acetonitrile; and carboxylic acids such as acetic acid.
水と水溶性有機溶媒との混合液を用いる場合の水と水溶性有機溶媒の比率は、前者／後者（重量比）＝１０／９０〜９９．９／０．０１、好ましくは５０／５０〜９９／１程度である。本発明においては、なかでも有機溶媒の回収作業が不要な点で水を使用することが好ましい。 The ratio of water and water-soluble organic solvent when using a mixed solution of water and water-soluble organic solvent is the former / the latter (weight ratio) = 10/90 to 99.9 / 0.01, preferably 50/50 to It is about 99/1. In the present invention, it is preferable to use water because it does not require an organic solvent recovery operation.
また、水性媒体にはハロゲン化物（例えば、塩化ナトリウム、塩化カリウム、塩化リチウム、臭化ナトリウム、臭化カリウム、臭化リチウム等のアルカリ金属ハロゲン化物など）を添加してもよい。しかし、本発明においては、特にハロゲン化物を添加しなくとも、結晶化度が高く、粒子径の揃ったロッド状ルチル型酸化チタンを得ることができる。 In addition, halides (for example, alkali metal halides such as sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, and lithium bromide) may be added to the aqueous medium. However, in the present invention, rod-shaped rutile titanium oxide having a high crystallinity and a uniform particle diameter can be obtained without adding a halide.
水性媒体中の４価のチタン化合物濃度（チタン換算）としては、１．５〜１７．０重量％（好ましくは２．５〜１５．０重量％、特に好ましくは２．５〜８．０重量％）となる濃度であることが好ましい。水性媒体中の４価のチタン化合物濃度（チタン換算）が上記範囲を上回ると、副生する塩素により反応器が腐食し易くなる傾向があり、一方、水性媒体中の４価のチタン化合物濃度（チタン換算）が上記範囲を下回ると、反応により得られる酸化チタンに結晶型の異なるものが混在して、結晶型の均一性が低下する傾向がある。 The concentration of the tetravalent titanium compound in the aqueous medium (in terms of titanium) is 1.5 to 17.0% by weight (preferably 2.5 to 15.0% by weight, particularly preferably 2.5 to 8.0% by weight). %) Is preferred. If the tetravalent titanium compound concentration (in terms of titanium) in the aqueous medium exceeds the above range, the reactor tends to be corroded by chlorine as a by-product, while the tetravalent titanium compound concentration in the aqueous medium ( If the titanium conversion is less than the above range, titanium oxides obtained by the reaction tend to have different crystal types, and the crystal type uniformity tends to decrease.
水熱処理時の反応温度は１１０℃〜２２０℃、好ましくは１４０℃〜２２０℃、特に好ましくは１５０℃〜２２０℃である。水熱処理時の反応温度が上記範囲を上回ると、副生する塩素により反応器が腐食し易くなる。一方、水熱処理時の反応温度が上記範囲を下回ると結晶面（００１）が形成されない。 The reaction temperature during hydrothermal treatment is 110 ° C to 220 ° C, preferably 140 ° C to 220 ° C, and particularly preferably 150 ° C to 220 ° C. If the reaction temperature during the hydrothermal treatment exceeds the above range, the reactor is easily corroded by by-produced chlorine. On the other hand, if the reaction temperature during hydrothermal treatment is below the above range, the crystal plane (001) is not formed.
水熱処理は反応温度における飽和蒸気圧以上の圧力下（すなわち、密閉系で）行われる。水熱処理時の反応圧力（絶対圧）は、例えば、０．１４ＭＰａ〜１．６ＭＰａ、好ましくは０．３６ＭＰａ〜１．６ＭＰａ、特に好ましくは０．４８ＭＰａ〜１．６ＭＰａである。 Hydrothermal treatment is performed under a pressure equal to or higher than the saturated vapor pressure at the reaction temperature (that is, in a closed system). The reaction pressure (absolute pressure) at the time of hydrothermal treatment is, for example, 0.14 MPa to 1.6 MPa, preferably 0.36 MPa to 1.6 MPa, particularly preferably 0.48 MPa to 1.6 MPa.
また、水熱処理を施す時間は２時間以上（例えば、２時間〜２４時間、好ましくは２時間〜１５時間、特に好ましくは５時間〜１５時間）である。水熱処理を施す時間が長すぎると生産性が低下する傾向がある。一方、水熱処理を施す時間が上記範囲を下回ると結晶面（００１）が形成されない。 The hydrothermal treatment time is 2 hours or longer (for example, 2 hours to 24 hours, preferably 2 hours to 15 hours, particularly preferably 5 hours to 15 hours). If the hydrothermal treatment time is too long, productivity tends to decrease. On the other hand, when the time for performing the hydrothermal treatment is less than the above range, the crystal plane (001) is not formed.
本発明における水熱処理は、回分式、半回分式、連続式などの慣用の方法により行うことができ、例えば、オートクレーブ等の密閉系反応容器を使用して、反応温度、反応圧力、反応時間、及び必要に応じて水性媒体中の４価のチタン化合物濃度（チタン換算）を上記範囲に調整することにより行うことができる。 Hydrothermal treatment in the present invention can be performed by a conventional method such as batch, semi-batch, continuous, etc., for example, using a closed reaction vessel such as an autoclave, reaction temperature, reaction pressure, reaction time, And it can carry out by adjusting the tetravalent titanium compound density | concentration (in titanium conversion) in an aqueous medium to the said range as needed.
上記方法により得られたロッド状ルチル型酸化チタンは、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段や、これらを組み合わせた分離手段により分離精製できる。 The rod-shaped rutile-type titanium oxide obtained by the above method can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.
本発明においては、なかでも、ロッド状ルチル型酸化チタンを圧密化することなくイオン性不純物を分離・除去することができる点で、ロッド状ルチル型酸化チタン水分散液にクロスフロー方式による膜濾過する操作を施すことが好ましい。クロスフロー方式により膜濾過する操作とは、濾過膜面に平行に供給液を流し、濾滓の沈着による濾過膜汚染を防ぎながら供給液の一部を、供給液の流れの側方で透過水として分離・除去し、濃縮液を得る方法である。ロッド状ルチル型酸化チタン水分散液をクロスフロー方式により膜濾過すると、イオン性不純物の含有量が低減され、且つ、高分散性を有するロッド状ルチル型酸化チタンを簡便且つ効率よく得ることができる。 In the present invention, in particular, ionic impurities can be separated and removed without densifying the rod-shaped rutile titanium oxide. It is preferable to perform the operation to do. The operation of membrane filtration by the cross-flow method is to feed the feed liquid parallel to the filtration membrane surface, and to prevent a filter membrane contamination due to the deposition of filter cake while preventing a part of the feed liquid from passing through the side of the feed liquid flow. Is separated and removed to obtain a concentrated solution. When a rod-shaped rutile-type titanium oxide aqueous dispersion is subjected to membrane filtration by a cross-flow method, the content of ionic impurities is reduced, and a rod-shaped rutile-type titanium oxide having high dispersibility can be obtained simply and efficiently. .
クロスフロー方式による膜濾過における濃縮倍率としては、１〜４００倍程度（なかでも１〜２０倍、特に１〜１０倍）が好ましい。濃縮倍率が上記範囲を上回ると、膜面への付着物質の堆積抑制が困難となり、濾過速度及び膜寿命が低下し易くなる傾向がある。一方、濃縮倍率が上記範囲を下回ると、イオン性不純物の分離効率が低下し、洗浄水の使用量が増加する傾向がある。 The concentration ratio in membrane filtration by the crossflow method is preferably about 1 to 400 times (in particular, 1 to 20 times, particularly 1 to 10 times). When the concentration ratio exceeds the above range, it is difficult to suppress the deposition of substances adhering to the film surface, and the filtration rate and the film life tend to decrease. On the other hand, when the concentration factor is below the above range, the separation efficiency of ionic impurities tends to decrease and the amount of washing water used tends to increase.
クロスフロー方式による膜濾過における濃縮倍率は、ロッド状ルチル型酸化チタン水分散液の膜面線速（クロスフロー速度）により調整することができる。ロッド状ルチル型酸化チタン水分散液を含む供給液の膜面線速が大きいほど膜面への付着物質の堆積が抑制されるので高い濾過流束（フラックス）が得られ、例えば、膜面線速（クロスフロー速度）は、例えば０．０２ｍ／ｓ以上、３ｍ／ｓ未満であり、好ましくは０．０５ｍ／ｓ以上、１．５ｍ／ｓ未満である。 The concentration rate in membrane filtration by the crossflow method can be adjusted by the membrane surface linear velocity (crossflow velocity) of the rod-shaped rutile-type titanium oxide aqueous dispersion. The higher the film surface linear velocity of the feed liquid containing the rod-shaped rutile-type titanium oxide aqueous dispersion, the more the deposition of adhering substances on the film surface is suppressed, so that a higher filtration flux (flux) is obtained. The speed (cross flow speed) is, for example, 0.02 m / s or more and less than 3 m / s, and preferably 0.05 m / s or more and less than 1.5 m / s.
クロスフロー方式により膜濾過する操作に付すロッド状ルチル型酸化チタン水分散液としては、ロッド状ルチル型酸化チタン含有量が、例えば、０．１〜４０重量％程度、好ましくは０．１〜２０重量％程度となるように、水（例えば、精製水、蒸留水、純水、イオン交換水等）で希釈したものを使用することが好ましい。ロッド状ルチル型酸化チタン含有量が上記範囲を外れると、イオン性不純物の除去効率が低下する傾向がある。また、ロッド状ルチル型酸化チタン含有量が上記範囲を上回る場合は、粘度が高くなりすぎ、ファウリング（目詰まり）し易くなる傾向もある。そして膜濾過処理により、水がイオン性不純物と共に透過液として分離されるため、例えば、１〜４００倍程度（なかでも１〜２０倍、特に１〜１０倍）に濃縮されたロッド状ルチル型酸化チタン水分散液が得られる。 The rod-shaped rutile-type titanium oxide aqueous dispersion subjected to the operation of membrane filtration by the crossflow method has a rod-like rutile-type titanium oxide content of, for example, about 0.1 to 40% by weight, preferably 0.1 to 20%. It is preferable to use one diluted with water (for example, purified water, distilled water, pure water, ion-exchanged water, etc.) so as to be about% by weight. If the rod-shaped rutile-type titanium oxide content is out of the above range, the removal efficiency of ionic impurities tends to decrease. Moreover, when the rod-shaped rutile-type titanium oxide content exceeds the above range, the viscosity becomes too high, and there is a tendency that fouling (clogging) is likely to occur. And since water is separated as a permeate together with ionic impurities by membrane filtration, for example, rod-shaped rutile oxidation concentrated to about 1 to 400 times (in particular, 1 to 20 times, especially 1 to 10 times). A titanium aqueous dispersion is obtained.
本発明においては、上記クロスフロー方式により膜濾過する操作を繰り返し行うことが、イオン性不純物を十分に分離・除去できる点で好ましく、クロスフロー方式による膜濾過で得られた濃縮されたロッド状ルチル型酸化チタン水分散液を、水（例えば、精製水、蒸留水、純水、イオン交換水等）で希釈することにより、ロッド状ルチル型酸化チタン水分散液の濃度を上記範囲に調整し、その後、再び膜濾過処理に付すことが好ましい。それにより、イオン性不純物の分離効率を向上させることができ、その上、ファウリング（目詰まり）等による濾過膜の負荷を軽減し、濾過膜の寿命を向上させることができる。 In the present invention, it is preferable to repeatedly perform the membrane filtration operation by the crossflow method from the viewpoint that ionic impurities can be sufficiently separated and removed, and the concentrated rod-shaped rutile obtained by the membrane filtration by the crossflow method. The concentration of the rod-shaped rutile titanium oxide aqueous dispersion is adjusted to the above range by diluting the titanium oxide aqueous dispersion with water (for example, purified water, distilled water, pure water, ion exchange water, etc.), Thereafter, it is preferable that the membrane filtration treatment is performed again. Thereby, the separation efficiency of ionic impurities can be improved, and furthermore, the load on the filtration membrane due to fouling (clogging) or the like can be reduced, and the life of the filtration membrane can be improved.
従って、本発明においては、特に、ロッド状ルチル型酸化チタン濃度が０．１〜４０重量％程度、好ましくは０．１〜２０重量％程度のロッド状ルチル型酸化チタン水分散液をクロスフロー方式により膜濾過し、イオン性不純物を透過液と共に分離除去して濃縮されたロッド状ルチル型酸化チタン水分散液を得、該濃縮されたロッド状ルチル型酸化チタン水分散液に水を加えて、ロッド状ルチル型酸化チタン濃度が上記範囲となるように希釈し、再びクロスフロー方式により膜濾過する操作を繰り返す循環膜濾過方式によりロッド状ルチル型酸化チタンを精製すると共に、定期的に濾過膜を逆洗浄することが、イオン性不純物の分離効率を向上し、それと同時に膜面への付着物質の堆積を抑制し、膜寿命を向上することができる点で好ましい。 Therefore, in the present invention, a rod-shaped rutile type titanium oxide aqueous dispersion having a rod-like rutile type titanium oxide concentration of about 0.1 to 40% by weight, preferably about 0.1 to 20% by weight, is cross-flow type. Filtration through a membrane, separating and removing ionic impurities together with the permeate to obtain a concentrated rod-shaped rutile-type titanium oxide aqueous dispersion, adding water to the concentrated rod-shaped rutile-type titanium oxide aqueous dispersion, The rod-shaped rutile titanium oxide is diluted so that the concentration of the rod-shaped rutile titanium oxide is within the above range, and the membrane filtration method is repeated again through the cross-flow method. Back washing is preferable in that it can improve the separation efficiency of ionic impurities, and at the same time, suppress the deposition of adhering substances on the film surface and improve the film life.
図２はロッド状ルチル型酸化チタンの循環膜濾過方式による精製方法の一例を示す概略図である。仕込みタンクに仕込まれたロッド状ルチル型酸化チタン水分散液を含む供給液は、クロスフロー濾過方式で膜濾過され、濃縮されたロッド状ルチル型酸化チタン水分散液（濃縮液）が得られる。濃縮されたロッド状ルチル型酸化チタン水分散液は、再度、仕込みタンクへ循環し、希釈用の水（希釈用水）で希釈され、再びクロスフロー濾過方式で膜濾過される。 FIG. 2 is a schematic view showing an example of a purification method using a circulating membrane filtration system for rod-shaped rutile titanium oxide. The feed liquid containing the rod-shaped rutile-type titanium oxide aqueous dispersion charged in the charging tank is subjected to membrane filtration by a cross-flow filtration method to obtain a concentrated rod-shaped rutile-type titanium oxide aqueous dispersion (concentrated liquid). The concentrated rod-shaped rutile-type titanium oxide aqueous dispersion is circulated again to the charging tank, diluted with dilution water (dilution water), and membrane-filtered again by the crossflow filtration method.
上記イオン性不純物としては、例えば、原料となる４価のチタン化合物に由来するチタンイオン、ハロゲンイオン（例えば、塩素イオン、臭素イオン、ヨウ素イオン）等を挙げることができる。 As said ionic impurity, the titanium ion derived from the tetravalent titanium compound used as a raw material, a halogen ion (for example, chlorine ion, bromine ion, iodine ion) etc. can be mentioned, for example.
本発明においては、ロッド状ルチル型酸化チタン中に含まれるイオン性不純物量を、例えば、１０〜３０００ｐｐｍ程度（好ましくは１０〜２０００ｐｐｍ程度）まで低減することが好ましい。ロッド状ルチル型酸化チタン中に含まれるイオン性不純物の含有量を上記範囲に低減すると、ロッド状ルチル型酸化チタンの光に対する応答性を向上することができる。 In the present invention, it is preferable to reduce the amount of ionic impurities contained in the rod-shaped rutile type titanium oxide to, for example, about 10 to 3000 ppm (preferably about 10 to 2000 ppm). When the content of the ionic impurities contained in the rod-shaped rutile titanium oxide is reduced to the above range, the response of the rod-shaped rutile titanium oxide to light can be improved.
上記濾過膜としては、例えば、限外濾過膜、精密濾過膜、ナノフィルター、逆浸透膜等を挙げることができる。本発明においては、なかでも、分画分子量の点で限外濾過膜を使用することが好ましい。 Examples of the filtration membrane include an ultrafiltration membrane, a microfiltration membrane, a nanofilter, and a reverse osmosis membrane. In the present invention, it is particularly preferable to use an ultrafiltration membrane in terms of the molecular weight cut-off.
限外濾過膜は、孔サイズが１〜１０ｎｍ（好ましくは、１〜５ｎｍ）であり、分子量１０００〜３０００００の物質（分子サイズとして、０．００１〜０．０１μｍ程度）［好ましくは、分子量１０００〜３００００（分子サイズとして、１〜５ｎｍ）］を分離対象とする分離膜である。 The ultrafiltration membrane has a pore size of 1 to 10 nm (preferably 1 to 5 nm) and a molecular weight of 1000 to 300,000 (molecular size is about 0.001 to 0.01 μm) [preferably a molecular weight of 1000 to 1000 μm. 30000 (1-5 nm as molecular size)] is a separation membrane.
限外濾過膜の膜形状としては、例えば、中空糸型濾過膜、チューブラー膜、スパイラル膜、平膜等の何れであっても良いが、逆洗浄が比較的容易に行える点から、中空糸型濾過膜、又はチューブラー膜を使用することが好ましい。 The membrane shape of the ultrafiltration membrane may be, for example, any of a hollow fiber type filtration membrane, a tubular membrane, a spiral membrane, a flat membrane, etc. It is preferable to use a mold filtration membrane or a tubular membrane.
中空糸型濾過膜における中空糸膜の内径は、汚染物質の閉塞の防止、膜モジュールへの中空糸充填率の向上という観点から、０．１〜２．０ｍｍ程度の範囲が好ましく、０．５〜１．０ｍｍの範囲がさらに好ましい。 The inner diameter of the hollow fiber membrane in the hollow fiber membrane is preferably in the range of about 0.1 to 2.0 mm from the viewpoint of preventing the blocking of contaminants and improving the hollow fiber filling rate of the membrane module. The range of -1.0 mm is more preferable.
濾過膜の材質としては、一般的なもの、例えば、酢酸セルロース、ポリアクリロニトリル、ポリスルホン、ポリエーテルスルホン、ポリアクリロニトリル、芳香族ポリアミド、ポリフッ化ビニリデン、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、ポリイミド、セラミックなどを使用できる。これらの中でも、濾過膜の材質としては酢酸セルロース、ポリスルホン、ポリエーテルスルホン（ＰＥＳ）、ポリアクリロニトリル、芳香族ポリアミドが好ましい。 As the material of the filtration membrane, general materials such as cellulose acetate, polyacrylonitrile, polysulfone, polyethersulfone, polyacrylonitrile, aromatic polyamide, polyvinylidene fluoride, polyvinyl chloride, polyethylene, polypropylene, polyimide, ceramic, etc. Can be used. Among these, cellulose acetate, polysulfone, polyethersulfone (PES), polyacrylonitrile, and aromatic polyamide are preferable as the material for the filtration membrane.
中空糸膜としては、酢酸セルロース系中空糸膜、ポリスルホン系中空糸膜、ポリアクリロニトリル系中空糸膜、ポリフッ化ビニリデン中空糸膜等を挙げることができるが、これらの中でも、酸に対する耐性が高いことからポリスルホン系中空糸膜が好ましい。 Examples of the hollow fiber membrane include cellulose acetate-based hollow fiber membranes, polysulfone-based hollow fiber membranes, polyacrylonitrile-based hollow fiber membranes, polyvinylidene fluoride hollow fiber membranes, etc. Among them, they have high resistance to acids. To polysulfone-based hollow fiber membranes are preferred.
中空糸型濾過膜を使用する場合、ロッド状ルチル型酸化チタン水分散液を流す方法（濾過方式）としては、内側（中空糸膜の内側）にロッド状ルチル型酸化チタン水分散液を含む供給液を流し、外側（中空糸膜の外側）に透過水を流す方式（内圧濾過方式）と、その逆に外側にロッド状ルチル型酸化チタン水分散液を含む供給液を流し、内側に向けて透過水が流れる方式（外圧濾過方式）が挙げられる。本発明においては、なかでも、膜面流速を高く維持できる点で内圧濾過方式が好ましい。 When a hollow fiber membrane is used, the rod-shaped rutile titanium oxide aqueous dispersion is flowed (filtration method) by supplying the rod-shaped rutile titanium oxide aqueous dispersion inside (inside the hollow fiber membrane). Flow the liquid and flow the permeate to the outside (the outside of the hollow fiber membrane) (internal pressure filtration system), and conversely flow the feed liquid containing the rod-shaped rutile-type titanium oxide aqueous dispersion to the outside and face the inside. A method in which permeate flows (external pressure filtration method) can be mentioned. In the present invention, the internal pressure filtration method is preferable because the membrane surface flow rate can be kept high.
クロスフロー方式により膜濾過する操作を施す際は、濾過膜面への付着物質の堆積を防止し、濾過膜への負担を軽減し、長期間膜濾過運転を行うため、濾過膜に対し、洗浄水により間欠的な逆洗浄を施すことが好ましい。逆洗浄は、圧力を制御しつつ、予め定められた周期で行うのが好ましく、例えば、０．５〜３時間に１回程度行うことが好ましい。逆洗浄の時間は０．５〜２分程度が好ましい。この際、濾過回収率は９０％以上、より好ましくは９５％以上に設定すると良い。濾過回収率は、下記式（２）で表される。
濾過回収率（％）＝１００×（膜濾過流量−逆洗浄水量）／膜濾過流量 （２）
When performing membrane filtration using the cross-flow method, the filter membrane is washed in order to prevent deposition of adhering substances on the membrane surface, reduce the burden on the membrane, and perform membrane filtration for a long period of time. It is preferable to perform intermittent backwashing with water. The reverse cleaning is preferably performed at a predetermined cycle while controlling the pressure, and is preferably performed about once every 0.5 to 3 hours, for example. The back washing time is preferably about 0.5 to 2 minutes. At this time, the filtration recovery rate may be set to 90% or more, more preferably 95% or more. The filtration recovery rate is represented by the following formula (2).
Filtration recovery rate (%) = 100 × (membrane filtration flow rate−backwash water amount) / membrane filtration flow rate (2)
なお、逆洗浄に用いる洗浄水としては、水（例えば、精製水、蒸留水、純水、イオン交換水等）を使用することが好ましい。また、逆洗浄により膜通過した洗浄水は、濃縮されたロッド状ルチル型酸化チタン水分散液の希釈用の水として再利用することが好ましい（図３参照）。 In addition, it is preferable to use water (For example, purified water, distilled water, pure water, ion-exchange water, etc.) as washing water used for back washing. Moreover, it is preferable to reuse the wash water that has passed through the membrane by back washing as water for diluting the concentrated rod-shaped rutile-type titanium oxide aqueous dispersion (see FIG. 3).
クロスフロー方式により膜濾過する操作では、透過液のｐＨを監視することにより容易にイオン性不純物の除去処理の進行度を確認することができ、例えば、透過液のｐＨが２〜７（好ましくは、２〜５）となるまでクロスフロー方式により膜濾過する操作を繰り返すことが好ましい。透過液のｐＨが上記範囲を外れる場合は、イオン性不純物の除去処理が不十分である場合がある。 In the operation of membrane filtration by the cross flow method, the progress of the ionic impurity removal treatment can be easily confirmed by monitoring the pH of the permeate. For example, the pH of the permeate is preferably 2 to 7 (preferably 2-5) It is preferable to repeat the operation of membrane filtration by the cross flow method until it becomes 2-5). When the pH of the permeate is outside the above range, the removal treatment of ionic impurities may be insufficient.
本発明に係るルチル型酸化チタンの製造方法により得られたロッド状ルチル型酸化チタンは、結晶面（００１）（１１０）（１１１）を有するため、励起電子とホールとの再結合を抑制することができ、且つ、逆反応の進行をより一層抑制することができる。それにより高い光触媒活性を発揮することができるため、種々の化学反応（例えば、酸化反応、有害物質の分解反応等）や殺菌などに光触媒として利用することができる。 Since the rod-shaped rutile type titanium oxide obtained by the method for producing rutile type titanium oxide according to the present invention has a crystal plane (001) (110) (111), it suppresses recombination of excited electrons and holes. And the progress of the reverse reaction can be further suppressed. As a result, a high photocatalytic activity can be exhibited, so that it can be used as a photocatalyst for various chemical reactions (for example, oxidation reaction, decomposition reaction of harmful substances, etc.) and sterilization.
本発明に係るルチル型酸化チタンの製造方法により得られたロッド状ルチル型酸化チタンは、３８０ｎｍ未満の紫外線を照射することにより（ロッド状ルチル型酸化チタンの種類によっては、紫外線域から６５０ｎｍ程度までの長波長の可視光線域までの広い波長範囲内の光を照射することにより）、高い触媒活性を発揮することができる。 The rod-shaped rutile titanium oxide obtained by the method for producing rutile titanium oxide according to the present invention is irradiated with ultraviolet rays of less than 380 nm (depending on the type of rod-shaped rutile titanium oxide, from the ultraviolet region to about 650 nm). High catalytic activity can be exhibited by irradiating light within a wide wavelength range up to the visible wavelength region of long wavelengths.
本発明に係るルチル型酸化チタンの製造方法により得られたロッド状ルチル型酸化チタンは、上記光の照射によって有害化学物質を水や二酸化炭素にまで分解することが可能であるため、抗菌防かび、脱臭、大気浄化、水質浄化、防汚などさまざまに応用することができ、室内の壁紙や家具をはじめ家庭内や病院、学校などの公共施設内での環境浄化、家電製品の高機能化など、広範囲への応用が可能である。 The rod-shaped rutile type titanium oxide obtained by the method for producing rutile type titanium oxide according to the present invention can decompose harmful chemical substances into water and carbon dioxide by irradiation with the light, so that it is antibacterial and antifungal. , Deodorization, air purification, water purification, antifouling, indoor wallpaper, furniture, environmental purification in homes, hospitals, schools, and other public facilities, and higher functionality of home appliances, etc. Application to a wide range is possible.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.
実施例１
室温（２５℃）にて、市販のＴｉＣｌ4水溶液（和光純薬社製試薬化学用、約１６．５％Ｔｉ含有希塩酸溶液）を、Ｔｉ濃度が５．４重量％になるようにイオン交換水で希釈した。この希釈後のＴｉＣｌ4水溶液 ５６ｇをテフロン（登録商標）塗装された容量１００ｍｌのオートクレーブに入れ密閉した。上記オートクレーブをオイルバスに投入し、３０分間かけて、オートクレーブ内におけるＴｉＣｌ4水溶液の温度を１８０℃まで昇温した。その後、反応温度１８０℃、反応圧力 １．０ＭＰａの条件で、１０時間保持した後、オートクレーブを氷水につけて冷却した。３分後、オートクレーブ内の温度が３０℃以下になったことを確認した後、オートクレーブを開封し、反応物（１）を取り出した。１０℃にて、得られた反応物（１）を遠心分離し、脱イオン水でリンスし、内温６５℃の真空乾燥機（バキュームオーブン）で１２時間減圧乾燥して、５．２ｇの酸化チタン粒子を得た。得られた酸化チタン粒子を透過型電子顕微鏡（ＴＥＭ）で確認したところ、結晶面（００１）（１１０）（１１１）を有するロッド状ルチル型酸化チタン粒子であった（図４）。
Example 1
At room temperature (25 ° C.), a commercially available TiCl 4 aqueous solution (for reagent chemistry manufactured by Wako Pure Chemical Industries, Ltd., dilute hydrochloric acid solution containing about 16.5% Ti) is ion-exchanged water so that the Ti concentration becomes 5.4% by weight. Diluted with 56 g of this diluted TiCl 4 aqueous solution was placed in a 100 ml autoclave coated with Teflon (registered trademark) and sealed. The autoclave was put into an oil bath, and the temperature of the TiCl 4 aqueous solution in the autoclave was raised to 180 ° C. over 30 minutes. Then, after maintaining for 10 hours under conditions of a reaction temperature of 180 ° C. and a reaction pressure of 1.0 MPa, the autoclave was cooled in ice water. Three minutes later, after confirming that the temperature in the autoclave was 30 ° C. or lower, the autoclave was opened, and the reaction product (1) was taken out. The obtained reaction product (1) is centrifuged at 10 ° C., rinsed with deionized water, and dried under reduced pressure for 12 hours in a vacuum dryer (vacuum oven) with an internal temperature of 65 ° C. Titanium particles were obtained. When the obtained titanium oxide particle was confirmed with the transmission electron microscope (TEM), it was a rod-shaped rutile type titanium oxide particle which has a crystal plane (001) (110) (111) (FIG. 4).
実施例２
反応時間を１０時間から３時間に変更した以外は実施例１と同様にして、４．７ｇの酸化チタン粒子を得た。
Example 2
4.7 g of titanium oxide particles were obtained in the same manner as in Example 1 except that the reaction time was changed from 10 hours to 3 hours.
実施例３
反応時間を１０時間から１４時間に変更した以外は実施例１と同様にして、５．２ｇの酸化チタン粒子を得た。
Example 3
Except that the reaction time was changed from 10 hours to 14 hours, 5.2 g of titanium oxide particles were obtained in the same manner as in Example 1.
実施例４
反応温度を１８０℃から１４０℃に変更した以外は実施例１と同様にして、４．９ｇの酸化チタン粒子を得た。
Example 4
4.9 g of titanium oxide particles were obtained in the same manner as in Example 1 except that the reaction temperature was changed from 180 ° C to 140 ° C.
実施例５
反応温度を１８０℃から２００℃に変更した以外は実施例１と同様にして、５．２ｇの酸化チタン粒子を得た。
Example 5
5.2 g of titanium oxide particles were obtained in the same manner as in Example 1 except that the reaction temperature was changed from 180 ° C. to 200 ° C.
実施例６
反応温度を１８０℃から２２０℃に変更した以外は実施例１と同様にして、５．２ｇの酸化チタン粒子を得た。
Example 6
5.2 g of titanium oxide particles were obtained in the same manner as in Example 1 except that the reaction temperature was changed from 180 ° C. to 220 ° C.
実施例７
上記実施例１で得られた反応物（１）５６ｇを純水で１０倍に希釈した後、限外ろ過膜（商品名「ＦＢ１０−ＨＶＣ−ＦＵＳ０３Ｃ１」、材質：ＰＥＳ、公称分画分子量：３万、ダイセン・メンブレン・システムズ（株）製）を用いて、室温（２５℃）、ろ過圧力０．０５ＭＰａにて、クロスフロー方式により膜濾過する操作を行い、イオン性不純物と酸化チタン粒子を分離し、イオン性不純物を系外に排出して、精製された酸化チタン粒子水分散液 ５６ｇを得た。精製された酸化チタン粒子水分散液を６０℃の真空乾燥機で１２時間乾燥して、５．２ｇの酸化チタン粒子を得た。
Example 7
After diluting 56 g of the reaction product (1) obtained in Example 1 with pure water 10 times, ultrafiltration membrane (trade name “FB10-HVC-FUS03C1”, material: PES, nominal molecular weight cut-off: 3 Tensile, manufactured by Daisen Membrane Systems Co., Ltd.) is used to perform membrane filtration by cross-flow method at room temperature (25 ° C) and filtration pressure 0.05 MPa to separate ionic impurities and titanium oxide particles. Then, ionic impurities were discharged out of the system to obtain 56 g of purified titanium oxide particle aqueous dispersion. The purified titanium oxide particle aqueous dispersion was dried with a vacuum dryer at 60 ° C. for 12 hours to obtain 5.2 g of titanium oxide particles.
比較例１
反応時間を１０時間から１時間とし、反応温度を１８０℃から２００℃に変更した以外は実施例１と同様にして、４．５ｇの酸化チタン粒子を得た。得られた酸化チタン粒子を透過型電子顕微鏡（ＴＥＭ）で確認したところ、結晶面（１１０）（１１１）を有するロッド状ルチル型酸化チタン粒子であり、結晶面（００１）は同定できなかった（図５）。
Comparative Example 1
4.5 g of titanium oxide particles were obtained in the same manner as in Example 1 except that the reaction time was changed from 10 hours to 1 hour and the reaction temperature was changed from 180 ° C. to 200 ° C. When the obtained titanium oxide particles were confirmed with a transmission electron microscope (TEM), they were rod-shaped rutile titanium oxide particles having crystal faces (110) and (111), and the crystal face (001) could not be identified ( FIG. 5).
比較例２
反応温度を１８０℃から１００℃に変更した以外は実施例１と同様にして、４．３ｇの酸化チタン粒子を得た。得られた酸化チタン粒子を透過型電子顕微鏡（ＴＥＭ）で確認したところ、結晶面（１１０）（１１１）を有するロッド状ルチル型酸化チタン粒子であり、結晶面（００１）は同定できなかった。
Comparative Example 2
4.3 g of titanium oxide particles were obtained in the same manner as in Example 1 except that the reaction temperature was changed from 180 ° C. to 100 ° C. When the obtained titanium oxide particles were confirmed with a transmission electron microscope (TEM), they were rod-shaped rutile titanium oxide particles having crystal faces (110) and (111), and the crystal face (001) could not be identified.
＜光触媒活性評価＞
実施例１〜７及び比較例１、２で得られた酸化チタン粒子の光触媒能を、気相にてアセトアルデヒドを酸化し、生成するＣＯ2量を測定することにより評価した。
テドラーバッグ（アズワン（株）製）を反応容器として使用した。実施例１〜６及び比較例１、２で得られた酸化チタン粒子 １００ｍｇをそれぞれガラス製皿に広げ、反応容器の中に入れ、５００ｐｐｍのアセトアルデヒド飽和ガスを反応容器に吹き込んだ。ガスとアセトアルデヒドが平衡に達した後、室温（２５℃）で光照射を行った。光源には５００Ｗのキセノンランプ用光源装置（商品名「ＳＸ−ＵＩ５０１ＸＱ」、ウシオ電機（株）製）を使用し、ＵＶ−３５フィルターを使用して３５０ｎｍより短い波長の光線を遮断した。さらに、ファインステンレス製のメッシュを光量調節用フィルターとして使用して光量を３０ｍＷ／ｃｍ2に調整した。
光照射開始から１５０分後のＣＯ2の生成量（反応容器内のＣＯ2濃度）をメタナイザーが付属した水素炎イオン化検出器付きガスクロマトグラフ（商品名「ＧＣ−８Ａ」、「ＧＣ−１４Ａ」、島津製作所製）を使用して測定した。
<Photocatalytic activity evaluation>
The photocatalytic ability of the titanium oxide particles obtained in Examples 1 to 7 and Comparative Examples 1 and 2 was evaluated by oxidizing acetaldehyde in the gas phase and measuring the amount of CO 2 produced.
A Tedlar bag (manufactured by As One Co., Ltd.) was used as a reaction vessel. 100 mg of the titanium oxide particles obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were spread on a glass dish, placed in a reaction vessel, and 500 ppm of acetaldehyde saturated gas was blown into the reaction vessel. After the gas and acetaldehyde reached equilibrium, light irradiation was performed at room temperature (25 ° C.). A 500 W xenon lamp light source device (trade name “SX-UI501XQ”, manufactured by USHIO INC.) Was used as a light source, and a UV-35 filter was used to block light having a wavelength shorter than 350 nm. Furthermore, the light amount was adjusted to 30 mW / cm 2 using a fine stainless steel mesh as a light amount adjusting filter.
The gas chromatograph with a flame ionization detector (trade names “GC-8A”, “GC-14A”), the amount of CO 2 produced 150 minutes after the start of light irradiation (CO 2 concentration in the reaction vessel) with a methanizer. (Manufactured by Shimadzu Corporation).
上記光触媒活性評価結果を下記表にまとめて示す。
以上より、本発明にかかるルチル型酸化チタンの製造方法により得られたルチル型酸化チタンは、結晶面（００１）（１１０）（１１１）を有するロッド状ルチル型酸化チタンであり、優れた光触媒能を発揮することができ、有機化合物の優れた酸化、分解作用を発揮することができることがわかる。 As described above, the rutile type titanium oxide obtained by the method for producing rutile type titanium oxide according to the present invention is a rod-like rutile type titanium oxide having crystal faces (001) (110) (111), and has excellent photocatalytic ability. It can be seen that an excellent oxidation and decomposition action of the organic compound can be exhibited.
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