JP2009196889A - Titanium oxide particle - Google Patents
Titanium oxide particle Download PDFInfo
- Publication number
- JP2009196889A JP2009196889A JP2009137268A JP2009137268A JP2009196889A JP 2009196889 A JP2009196889 A JP 2009196889A JP 2009137268 A JP2009137268 A JP 2009137268A JP 2009137268 A JP2009137268 A JP 2009137268A JP 2009196889 A JP2009196889 A JP 2009196889A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- oxide particles
- particle
- oxyhydrogen
- photocatalyst
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 190
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011941 photocatalyst Substances 0.000 claims abstract description 29
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000012798 spherical particle Substances 0.000 claims description 8
- 230000001954 sterilising effect Effects 0.000 claims description 6
- 238000004659 sterilization and disinfection Methods 0.000 claims description 6
- 238000004332 deodorization Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000009826 distribution Methods 0.000 abstract description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 18
- 229910001882 dioxygen Inorganic materials 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Abstract
Description
本発明は、光触媒として好適な酸化チタン粒子と、この酸化チタン粒子を光触媒として使用する方法に関するものである。 The present invention relates to titanium oxide particles suitable as a photocatalyst and a method of using the titanium oxide particles as a photocatalyst.
酸化チタン粒子（ＴｉＯ２）粒子は、ペイント、化粧品、および食品添加物等として広く使用されている。さらに、酸化チタン粒子は、これが保有する光触媒作用により、大気汚染の原因となるＮＯｘの分解や、水質汚濁を惹起せしめる有機溶剤を分解させるためなどに使用することの検討が行われている。 Titanium oxide particles (TiO 2 ) particles are widely used as paints, cosmetics, food additives and the like. Furthermore, studies are being made on the use of titanium oxide particles to decompose NOx that causes air pollution or to decompose organic solvents that cause water pollution due to the photocatalytic action possessed by the titanium oxide particles.
ところで、酸化チタン粒子の光触媒反応は、その表面で起こる反応であり、それ故、上記汚染物質の分解に当たっては、分解対象物質を酸化チタン粒子表面に吸着させることが望ましい。すなわち、分解をより効率よく行うには、吸着面積が広いこと好ましく、粒径が小さい酸化チタン粒子ほど高い分解力を有するものである。 By the way, the photocatalytic reaction of the titanium oxide particles is a reaction that occurs on the surface thereof. Therefore, it is desirable that the decomposition target substance is adsorbed on the surface of the titanium oxide particles when the contaminant is decomposed. That is, in order to perform decomposition more efficiently, it is preferable that the adsorption area is wide, and titanium oxide particles having a smaller particle size have higher decomposition power.
このため、特開平１１−２６７５１９号公報および特開平７−３０３８３５号公報では、数ｎｍオーダにまで微細化した酸化チタン粒子を提案している。しかし、数ｎｍオーダの粒子ではスラリー状とした時に、分散性に問題が生じることあり、粒径は１０ｎｍ以上にすることが望ましい。 For this reason, JP-A-11-267519 and JP-A-7-303835 propose titanium oxide particles refined to the order of several nm. However, when particles of the order of several nm are used in a slurry state, there may be a problem in dispersibility, and the particle size is desirably 10 nm or more.
また、光触媒として使用される酸化チタン粒子は、反応性、活性にばらつきが少なく、均一なものが好ましく、それゆえ、粒径分布が小さい粒子のものが望まれている。さらに、粒子合成装置、スラリー混合装置等からの分離、除去作業が容易である球状の粒子であることが望ましい。 Further, the titanium oxide particles used as the photocatalyst are preferably uniform with little variation in reactivity and activity, and therefore, particles having a small particle size distribution are desired. Furthermore, it is desirable that the particles are spherical particles that can be easily separated and removed from a particle synthesizer, a slurry mixer, or the like.
このようなことから、特開平５−１６３０２２号公報においては、球状で、真球度が高く、粒径分布が比較的小さい酸化チタン粒子が提案されている。
しかし、ここで提案されている酸化チタン粒子は、その粒径は０.１μｍ以上となり、分解を効果的に行うためには必要である、分解対象物を吸着するための比表面積が小さいという点で不利である。
For this reason, JP-A-5-163022 proposes titanium oxide particles that are spherical, have high sphericity, and have a relatively small particle size distribution.
However, the titanium oxide particles proposed here have a particle size of 0.1 μm or more, and the specific surface area for adsorbing the decomposition target is small, which is necessary for effective decomposition. It is disadvantageous.
一方、上記特開平５−１６３０２２号公報に開示されているように、光触媒活性を有するアナターゼ型酸化チタン粒子で、粒径が十分小さい粒子を得るには、一般に、焼成または凝集した酸化チタン粒子を粉砕等の手段をもって壊砕しなければならず、そのため、真球に近い形状の酸化チタン粒子粒子を得ることは困難である。 On the other hand, as disclosed in JP-A-5-163022, the anatase-type titanium oxide particles having photocatalytic activity are generally obtained by firing or agglomerated titanium oxide particles in order to obtain particles having a sufficiently small particle size. Therefore, it is difficult to obtain titanium oxide particles having a shape close to a true sphere.
また、粉砕工程用いないで粒子を得る方法として、四塩化チタンや硫酸チタン等を加水分解および熱酸化する製法があるが、この場合、粒径を小さくすると、粒子の真球度が低下して行くこととなる。
このように、比表面積が大きく、球状でかつ真球度が高いという要件を有し、光触媒として好適な酸化チタン粒子が未だ現出していないのが実情であり、その速やかな出現が望まれている。
In addition, as a method for obtaining particles without using a pulverization step, there is a production method in which titanium tetrachloride, titanium sulfate, etc. are hydrolyzed and thermally oxidized. In this case, if the particle size is reduced, the sphericity of the particles is lowered. Will go.
As described above, there is a requirement that titanium oxide particles suitable for a photocatalyst have not yet emerged with the requirement that the specific surface area is large, spherical and high in sphericity, and its rapid appearance is desired. Yes.
よって、本発明における課題は、光触媒として好適な酸化チタン粒子と該酸化チタン粒子を光触媒として使用して効率よく汚染物質を処理する方法や水を分解する方法を提供することにある。 Accordingly, an object of the present invention is to provide titanium oxide particles suitable as a photocatalyst and a method for efficiently treating contaminants and a method for decomposing water using the titanium oxide particles as a photocatalyst.
かかる課題を解決するため、
請求項１にかかる発明は、多重管構造の酸水素バーナにより形成された酸水素炎に対してこの酸水素炎の側方からチタン化合物蒸気を送り込み、酸水素バーナに供給する酸素−水素の供給量比を３／４以上として酸素量を過剰にし、酸水素炎中で加水分解反応と熱酸化反応とを同時に引き起こして酸化チタン粒子を製造する方法によって製造された酸化チタン粒子であって、
粒子表面に網目模様を有し、平均粒子径が１０〜１００ｎｍであり、粒子の真球度が０.１以下の球状粒子であり、粒子集合物全体の８５容量％を占める粒子の径が１０ｎｍ〜４０ｎｍであることを特徴とする酸化チタン粒子である。
To solve this problem,
The invention according to claim 1 is the supply of oxygen-hydrogen supplied to the oxyhydrogen burner by feeding titanium compound vapor from the side of the oxyhydrogen flame to the oxyhydrogen flame formed by the oxyhydrogen burner having a multi-tube structure. Titanium oxide particles produced by a method of producing a titanium oxide particle by causing a hydrolysis reaction and a thermal oxidation reaction at the same time in an oxyhydrogen flame by increasing the oxygen amount with a quantitative ratio of 3/4 or more,
The particle surface has a mesh pattern, the average particle size is 10 to 100 nm, the sphericity of the particle is 0.1 or less, and the particle size occupying 85% by volume of the entire particle aggregate is 10 nm. Titanium oxide particles having a diameter of ˜40 nm.
請求項２にかかる発明は、多重管構造の酸水素バーナにより形成された酸水素炎に対してこの酸水素炎の側方からチタン化合物蒸気を送り込み、酸水素バーナに供給する酸素−水素の供給量比を３／４以上として酸素量を過剰にし、酸水素炎中で加水分解反応と熱酸化反応とを同時に引き起こして酸化チタン粒子を製造する方法によって製造された酸化チタン粒子であって、
粒子表面に網目模様を有し、平均粒子径が１０ｎｍ〜３０ｎｍであり、粒子の真球度が０.１以下の球状粒子であり、粒子集合物全体の８５容量％を占める粒子の径が１０ｎｍ〜２５ｎｍであることを特徴とする酸化チタン粒子である。
The invention according to claim 2 is the supply of oxygen-hydrogen supplied to the oxyhydrogen burner by feeding titanium compound vapor from the side of the oxyhydrogen flame to the oxyhydrogen flame formed by the oxyhydrogen burner having a multi-tube structure. Titanium oxide particles produced by a method of producing a titanium oxide particle by causing a hydrolysis reaction and a thermal oxidation reaction at the same time in an oxyhydrogen flame by increasing the oxygen amount with a quantitative ratio of 3/4 or more,
A spherical particle having a mesh pattern on the particle surface, an average particle diameter of 10 nm to 30 nm, a sphericity of the particle of 0.1 or less, and a particle diameter occupying 85% by volume of the entire particle aggregate is 10 nm. Titanium oxide particles having a diameter of ˜25 nm.
請求項３にかかる発明は、前記球状粒子の７０％以上がアナターゼ型の酸化チタン粒子であることを特徴とする請求項１または２記載の酸化チタン粒子である。
請求項４にかかる発明は、請求項１ないし請求項３のいずれかに記載の酸化チタン粒子からなることを特徴とする光触媒である。
The invention according to claim 3 is the titanium oxide particles according to claim 1 or 2, wherein 70% or more of the spherical particles are anatase type titanium oxide particles.
The invention according to claim 4 is a photocatalyst comprising the titanium oxide particles according to any one of claims 1 to 3.
請求項５にかかる発明は、請求項４に記載の光触媒を汚染物質と接触せしめて、該汚染物質を分解処理、脱臭処理、および殺菌処理の少なくととも１つの処理をすることを特徴とする汚染物質の処理方法である。
請求項６にかかる発明は、請求項４に記載の光触媒を水と接触せしめて、水を分解することを特徴とする水の分解方法である。
The invention according to claim 5 is characterized in that the photocatalyst according to claim 4 is brought into contact with a pollutant, and the pollutant is subjected to at least one of decomposition treatment, deodorization treatment, and sterilization treatment. This is a method for treating pollutants.
The invention according to claim 6 is a method for decomposing water, wherein the photocatalyst according to claim 4 is brought into contact with water to decompose water.
本発明によれば、
（ｉ）本発明の酸化チタン粒子は、酸素量過剰の条件で形成された酸水素炎の側方からこの酸水素炎にチタン化合物蒸気を供給する方法によって得られたものであり、粒子径が小さく、真球度が高く、粒度分布が狭いものとなり、粒子表面に網目模様があることから結晶性が高いものとなって、光触媒活性が高く、分散性に優れ、光触媒として好適である。
According to the present invention,
(I) The titanium oxide particles of the present invention are obtained by a method in which a titanium compound vapor is supplied to the oxyhydrogen flame from the side of the oxyhydrogen flame formed under an excessive oxygen amount condition, and the particle diameter is It is small, has high sphericity, has a narrow particle size distribution, and has a network pattern on the particle surface, so that it has high crystallinity, high photocatalytic activity, excellent dispersibility, and is suitable as a photocatalyst.
（ｉｉ）本発明の酸化チタン粒子は、粒子全体の７０％以上がアナターゼ型の酸化チタン粒子からなっているものであり、汚染物を分解する光触媒として効果的に機能する。
（ｉｉｉ）本発明の酸化チタン粒子を適宜の手段で基材上に塗布して付着せしめることで光触媒作用を発揮する。例えば、酸化チタン粒子を有機溶媒などの分散媒に分散せしめてペーストとし、このペーストをガラス、セラミックス、金属、木材、プラスチック、または塗膜等の基材上に塗布し、これに紫外光などの光を照射することで光触媒として機能する。
(Ii) The titanium oxide particles of the present invention are those in which 70% or more of the total particles are made of anatase-type titanium oxide particles, and effectively function as a photocatalyst for decomposing contaminants.
(Iii) The photocatalytic action is exhibited by applying and attaching the titanium oxide particles of the present invention on a substrate by an appropriate means. For example, titanium oxide particles are dispersed in a dispersion medium such as an organic solvent to form a paste, and this paste is applied onto a substrate such as glass, ceramics, metal, wood, plastic, or a coating film, and ultraviolet light or the like is applied thereto. It functions as a photocatalyst when irradiated with light.
（ｉｖ）さらに本発明の酸化チタン粒子の粒子よりなる光触媒は、汚染物質の分解除去、異臭物質の分解除去、殺菌、滅菌等や、超親水性被膜の形成用、表面の防汚、水の分解等に極めて効率よく効果的に機能する。 (Iv) Further, the photocatalyst comprising the titanium oxide particles according to the present invention is used for decomposition and removal of contaminants, decomposition and removal of off-flavor substances, sterilization, sterilization, etc., for the formation of superhydrophilic coatings, antifouling of surfaces, water It functions extremely efficiently and effectively for decomposition.
以下、本発明を詳しく説明する。
本発明の酸化チタン粒子は、その形状を真球度の高い球形粒子としたものである。その粒子の最大直径をＬ（ｍａｘ）、最小直径Ｌ（ｍｉｎ）とした時、平均粒子径Ｌを式（１）で定義する。
Ｌ＝［Ｌ（ｍａｘ）×Ｌ（ｍｉｎ）］１／２ …… （１）
The present invention will be described in detail below.
The titanium oxide particles of the present invention are spherical particles having a high sphericity. When the maximum diameter of the particles is L (max) and the minimum diameter L (min), the average particle diameter L is defined by equation (1).
L = [L (max) × L (min)] 1/2 (1)
そして、本発明の酸化チタン粒子の粒子は、平均粒子径Ｌが１０ｎｍ以上で１００ｎｍ以下であることを特徴としているものである。
また、粒子集合物全体の８５容量％を占める粒子の径が１０ｎｍ以上で４０ｎｍ以下という粒径分布を有しているものである。
And the particle | grains of the titanium oxide particle of this invention are characterized by the average particle diameter L being 10 nm or more and 100 nm or less.
In addition, the particle size distribution is such that the particle size occupying 85% by volume of the entire particle aggregate is 10 nm or more and 40 nm or less.
さらに、平均粒子径Ｌが１０ｎｍ〜３０ｎｍであり、粒子集合物全体の８５容量％を占める粒子の径が１０ｎｍ以上２５ｎｍの酸化チタン粒子粒子は、汚染物を分解するという面で光触媒活性が高く、優れた特性を有する。 Furthermore, the titanium oxide particle particles having an average particle diameter L of 10 nm to 30 nm and a particle diameter of 10 to 25 nm occupying 85% by volume of the entire particle aggregate have high photocatalytic activity in terms of decomposing contaminants, Has excellent properties.
また、粒子の真球度Ｄを式（２）で定義する。
Ｄ＝［｛Ｌ（ｍａｘ）−Ｌ（ｍｉｎ）｝／Ｌ］×１００ …… （２）
そして、本発明の酸化チタン粒子の粒子は、真球度Ｄが０.１以下で真球度が高いことにあることを特徴とするものである。真球度が高く、粒子径が揃っている酸化チタン粒子は、光触媒として高機能であるというだけでなく、従来使用されている顔料としても、展延性、分散性に優れているため、高特性機能を有するものである。
Further, the sphericity D of the particle is defined by equation (2).
D = [{L (max) −L (min)} / L] × 100 (2)
The titanium oxide particles of the present invention are characterized in that the sphericity D is 0.1 or less and the sphericity is high. Titanium oxide particles with high sphericity and uniform particle size are not only highly functional as photocatalysts, but also have excellent spreadability and dispersibility as conventional pigments. It has a function.
図１および図２は、本発明の酸化チタン粒子の走査型電気顕微鏡写真を示すもので、図２の写真は、図１の部分拡大したものである。図１において、目盛り１０個で５００ｎｍを表し、図２において、目盛り１０個で１００ｎｍを表している。
図１および図２の写真で明らかなように、本発明の酸化チタン粒子が、上記したような寸法要件を有する粒子をなしていることが確認される。
さらに、本発明の酸化チタン粒子粒子はその表面には、図２の写真で認められるように、網目模様を有することに特徴を有する。
1 and 2 show scanning electric micrographs of the titanium oxide particles of the present invention, and the photograph of FIG. 2 is a partially enlarged view of FIG. In FIG. 1, 10 scales represent 500 nm, and in FIG. 2, 10 scales represent 100 nm.
As is apparent from the photographs of FIGS. 1 and 2, it is confirmed that the titanium oxide particles of the present invention are particles having the dimensional requirements described above.
Furthermore, the titanium oxide particle particles of the present invention are characterized by having a mesh pattern on the surface thereof, as can be seen in the photograph of FIG.
また、本発明の酸化チタン粒子は、粒子集合物全体の７０％以上がアナターゼ型の酸化チタン粒子からなっていることに特徴を有するものであるが、汚染物を分解するという点では、９０％以上がアナターゼ型の酸化チタン粒子からなることが、より一層好ましい。そして、顔料として使用する上で、よりその効果を発揮せしめるには光学的に不活性なルチル型であることが望ましい。 The titanium oxide particles of the present invention are characterized in that 70% or more of the entire particle aggregate is made of anatase-type titanium oxide particles, but 90% in terms of decomposing contaminants. It is even more preferable that the above is made of anatase-type titanium oxide particles. And when using as a pigment, in order to exhibit the effect more, it is desirable that it is an optically inactive rutile type.
そして、本発明の酸化チタン粒子の粒子を７００℃以上の温度で熱処理することにより、ルチル型に変化せしめることができる特徴を有する。なお、この場合、熱処理時の焼結作用により比表面積が小さくなったり、または、粒子形状が変形することが懸念されるが、従来の球形の酸化チタン粒子に比べて、結晶性が高いため、焼結現象は抑制され、粒子径や形状の変化は起こり難い。 And it has the characteristics which can be changed into a rutile type by heat-processing the particle | grains of the titanium oxide particle of this invention at the temperature of 700 degreeC or more. In this case, there is a concern that the specific surface area is reduced by the sintering action during heat treatment, or the particle shape is deformed, but since the crystallinity is higher than the conventional spherical titanium oxide particles, Sintering is suppressed and changes in particle size and shape are unlikely to occur.
以上のような特徴を有する本発明の酸化チタン粒子は、光触媒として効果的に利用し得るものである。すなわち、本発明の酸化チタン粒子を適宜の手段で基材上に塗布して付着せしめることで光触媒作用を発揮する。例えば、酸化チタン粒子を有機溶媒などの分散媒に分散せしめてペーストとし、このペーストをガラス、セラミックス、金属、木材、プラスチック、または塗膜等の基材上に塗布し、これに紫外光などの光を照射することで光触媒として機能するものである。 The titanium oxide particles of the present invention having the above characteristics can be effectively used as a photocatalyst. That is, the photocatalytic action is exhibited by applying and adhering the titanium oxide particles of the present invention onto a substrate by an appropriate means. For example, titanium oxide particles are dispersed in a dispersion medium such as an organic solvent to form a paste, and this paste is applied onto a substrate such as glass, ceramics, metal, wood, plastic, or a coating film, and ultraviolet light or the like is applied thereto. It functions as a photocatalyst when irradiated with light.
また、この酸化チタン粒子からなる光触媒は、可視光応答型光触媒とすることができる。例えば、本発明の酸化チタン粒子を、アルゴンガスで所定の濃度に希釈したアンモニアガス雰囲気中で所定の時間加熱処理することにより、可視光応答型光触媒とすることが出来る。そして、この可視光応答型光触媒は、４００ｎｍ以上の波長領域の可視光でも光触媒活性を示し、室内等に配設された蛍光灯、白熱電灯などの人工光源からの可視光でもその光触媒作用を発揮することができ、極めて効果的に活用することができる。 Further, the photocatalyst composed of the titanium oxide particles can be a visible light responsive photocatalyst. For example, the visible light responsive photocatalyst can be obtained by heat-treating the titanium oxide particles of the present invention for a predetermined time in an ammonia gas atmosphere diluted to a predetermined concentration with argon gas. This visible light responsive photocatalyst exhibits photocatalytic activity even in visible light having a wavelength region of 400 nm or more, and exhibits its photocatalytic action even in visible light from an artificial light source such as a fluorescent lamp or an incandescent lamp installed in a room. Can be used very effectively.
本発明の酸化チタン粒子からなる光触媒は、酸化チタン粒子の結晶性が高いので触媒活性が極めて高く、汚染物質の分解除去、異臭物質の分解除去、殺菌、滅菌等や、超親水性被膜の形成用、表面の防汚等に極めて効率よく効果的に機能する。また、クリーンエネルギー源としての水素の供給のために水の分解にも適した光触媒としても、極めて有効に活用することが出来る。なお、その具体的な使用形態は、従来の酸化チタン粒子からなる光触媒と同様である。 The photocatalyst comprising the titanium oxide particles of the present invention has a very high catalytic activity because of the high crystallinity of the titanium oxide particles, decomposition removal of pollutants, decomposition removal of off-flavors, sterilization, sterilization, etc. It functions extremely efficiently and effectively for anti-fouling and surface contamination. Moreover, it can be used very effectively as a photocatalyst suitable for the decomposition of water for supplying hydrogen as a clean energy source. In addition, the specific usage form is the same as that of the photocatalyst which consists of a conventional titanium oxide particle.
次に本発明の酸化チタン粒子の製造方法について説明する。本発明の酸化チタン粒子は、酸水素火炎中にチタン化合物蒸気を供給して、加水分解反応と熱酸化反応とを同時に惹起せしめることによって製造する。
これを図３を参照して説明する。図３は本発明の酸化チタン粒子を製造する方法に使用する製造装置の一例を説明する概略図である。
Next, the manufacturing method of the titanium oxide particle of this invention is demonstrated. The titanium oxide particles of the present invention are produced by supplying a titanium compound vapor into an oxyhydrogen flame and simultaneously inducing a hydrolysis reaction and a thermal oxidation reaction.
This will be described with reference to FIG. FIG. 3 is a schematic diagram illustrating an example of a production apparatus used in the method for producing titanium oxide particles of the present invention.
図３において、チャンバー１内に設置された酸水素バーナ２に、管路３より酸素ガスＯ２が、また管路４より水素ガスＨ２が供給される。そして、酸水素バーナ２で発生せしめた酸水素火炎５中にチタン化合物蒸気９を管路８より供給をするようにする。この際図示のように、酸水素炎５の側方から酸水素炎５内にチタン化合物蒸気９を送り込む。 In Figure 3, the oxyhydrogen burner 2 placed in the chamber 1, the oxygen gas O 2 from the conduit 3 is also hydrogen gas H 2 is supplied from the pipe 4. Then, the titanium compound vapor 9 is supplied from the pipe 8 into the oxyhydrogen flame 5 generated by the oxyhydrogen burner 2. At this time, as shown in the figure, a titanium compound vapor 9 is fed into the oxyhydrogen flame 5 from the side of the oxyhydrogen flame 5.
なお、該チタン化合物蒸気１０は、貯槽６に貯留されていて、アルゴンガスＡｒ、窒素ガスＮ２のような不活性ガスＧを管路７により貯槽６内に供給して貯槽６内に吹き込み、貯槽６内のチタン化合物９を蒸気として同伴して送出し、管路８でチャンバー１に供給するものである。 The titanium compound vapor 10 is stored in the storage tank 6, and an inert gas G such as argon gas Ar and nitrogen gas N 2 is supplied into the storage tank 6 through the conduit 7 and blown into the storage tank 6. The titanium compound 9 in the storage tank 6 is sent along with steam and supplied to the chamber 1 through the pipe line 8.
そして、チャンバー１内で生成された酸化チタン粒子１０は、管路１１を介してバグフィルター１２に吸引され、該バグフィルタ１２に貯留される。なお、吸引排気は管路１３により図示しない吸引ポンプで行われる。 The titanium oxide particles 10 generated in the chamber 1 are sucked into the bag filter 12 through the pipe line 11 and stored in the bag filter 12. The suction exhaust is performed by a suction pump (not shown) through the pipe line 13.
そして、酸水素バーナ２では、通常は、酸素ガスＯ２と水素ガスＨ２は容量比で１：２の割合で反応して水を生成する。これを、本発明では酸水素バーナ２に供給する酸素ガスＯ２と水素ガスＨ２の容量を、酸素ガスＯ２を過剰として供給することを特徴とするものである。 In the oxyhydrogen burner 2, the oxygen gas O 2 and the hydrogen gas H 2 usually react at a volume ratio of 1: 2 to generate water. This is the volume of oxygen gas O2 and hydrogen gas H 2 is supplied to the oxyhydrogen burner 2 in the present invention, it is characterized in that supplying oxygen gas O 2 as excessive.
すなわち、本発明では、酸水素容量比＝酸素ガス流量／水素ガス流量と定義すると、酸水素容量比を０.７５以上とすることを特徴とし、さらに好ましくは１.５以上とすることである。これにより、酸素ガスＯ２と水素ガスＨ２の燃焼反応で、水が生成され、供給されるチタン化合物蒸気９と反応して加水分解反応を起こす。同時に、過剰な酸素ガスＯ２と酸水素火炎５の熱とにより、チタン化合物９に熱酸化が生じる。この結果、チタン化合物９の加水分解と熱酸化との同時発生により、本発明の酸化チタン粒子１０が合成されるのである。 That is, in the present invention, when defined as oxyhydrogen capacity ratio = oxygen gas flow rate / hydrogen gas flow rate, the oxyhydrogen capacity ratio is characterized by being 0.75 or more, more preferably 1.5 or more. . Thus, the combustion reaction with oxygen gas O 2 and hydrogen gas H 2, water is generated, causing a hydrolysis reaction by reacting with the titanium compound vapor 9 to be supplied. At the same time, thermal oxidation occurs in the titanium compound 9 due to the excessive oxygen gas O 2 and the heat of the oxyhydrogen flame 5. As a result, the titanium oxide particles 10 of the present invention are synthesized by simultaneous generation of hydrolysis and thermal oxidation of the titanium compound 9.
この酸化チタン粒子チタンの生成に使用される酸水素バーナ２としては、図４に図示するような同心の内外二重管で外管２１ａに酸素ガスＯ２を流し、内管２１ｂに水素ガスＨ２を流すようにした石英ガラス製の同心２重管酸水素バーナ２１を使用することが出来、均一な熱分布を有する酸水素火炎５を形成することが出来るので、粒径分布が小さい酸化チタン粒子１０の粒子を合成するには極めて好適である。 As the oxyhydrogen burner 2 used for the production of the titanium oxide particles titanium, a concentric inner / outer double pipe as shown in FIG. 4 is used to flow oxygen gas O 2 through the outer pipe 21a, and hydrogen gas H through the inner pipe 21b. 2 can be used, and a concentric double tube oxyhydrogen burner 21 made of quartz glass can be used, and an oxyhydrogen flame 5 having a uniform heat distribution can be formed. It is extremely suitable for synthesizing the particles 10.
また、多重管構造の酸水素バーナとしては、図５に図示するような、最内側管路２２ｄより、外側管に向け順次管路２２ｃ，２２ｂ、２２ａを配した同心４重管からなる同心４重管酸水素バーナ２２等、種々の多重管が適宜その製造条件に応じて使用することが出来る。なお、この場合、前記管路２２ｄ、２２ｃ、２２ｂ、２２ａに、例えば酸素ガスＯ２と水素ガスＨ２とを交互に流すようにして酸水素火炎を発生するようにして使用することが出来る。 Further, as shown in FIG. 5, the oxyhydrogen burner having a multi-tube structure is a concentric 4 consisting of concentric quadruple tubes in which pipelines 22c, 22b and 22a are sequentially arranged from the innermost pipeline 22d toward the outer tube. Various multiple pipes such as the double pipe oxyhydrogen burner 22 can be appropriately used according to the production conditions. In this case, for example, oxygen gas O 2 and hydrogen gas H 2 can be alternately flowed through the conduits 22d, 22c, 22b, and 22a to generate an oxyhydrogen flame.
本発明で使用する上記チタン化合物９としては、四塩化チタン（ＴｉＣｌ４）、硫酸チタン（Ｔｉ（ＳＯ４）２）等を好適に用いることが出来る。例えば四塩化チタンを使用した場合、図３に図示するように、貯槽６に四塩化チタンを貯留し、アルゴンガスＡｒ等の不活性ガスＧを四塩化チタン液に吹き込んでバブリングして四塩化チタンを気化せしめて同伴して管路８よりチャンバー１に供給する。 As the titanium compound 9 used in the present invention, titanium tetrachloride (TiCl 4 ), titanium sulfate (Ti (SO 4 ) 2 ) and the like can be suitably used. For example, when titanium tetrachloride is used, as shown in FIG. 3, titanium tetrachloride is stored in the storage tank 6, and an inert gas G such as argon gas Ar is blown into the titanium tetrachloride solution and bubbled to form titanium tetrachloride. Is supplied to the chamber 1 through the pipe line 8.
この場合、四塩化チタンは、その蒸気圧の大きさから貯槽６を６０℃以上の温度とすることが望ましい。さらに管路８も、気化した四塩化チタンが液化しないように、貯槽６の温度以上の温度、好ましくは１００℃以上に保温するようにして、気化状態を保って、酸水素火炎５に供給するようにすると良い。 In this case, the titanium tetrachloride desirably has a temperature of 60 ° C. or higher in the storage tank 6 because of its vapor pressure. Further, the pipe 8 is also supplied to the oxyhydrogen flame 5 while keeping the vaporized state by keeping the temperature above the temperature of the storage tank 6, preferably at 100 ° C. or higher, so that the vaporized titanium tetrachloride is not liquefied. It is good to do so.
なお、合成される酸化チタン粒子１０に、例えばリン、窒素、ケイ素、ホウ素等のドーパントを添加する場合には、ドーパントとなる化合物の蒸気をチタン化合物９の蒸気に混合して、チャンバー１または酸水素バーナ２に供給するようにすれば良い。 When a dopant such as phosphorus, nitrogen, silicon, or boron is added to the titanium oxide particle 10 to be synthesized, the vapor of the compound serving as the dopant is mixed with the vapor of the titanium compound 9, and the chamber 1 or acid What is necessary is just to make it supply to the hydrogen burner 2. FIG.
ドーパント化合物を蒸気にして混合するにあたっては、例えばケイ素の場合は、原料として四塩化ケイ素を用いることが出来る。この場合、四塩化ケイ素を別途貯槽に貯留しておき、これにアルゴンガスＡｒ等のガスでバブリングして蒸気としてチャンバー１に送っても良いし、酸水素バーナ２に酸素ガスＯ２、水素ガスＨ２とは別にして導入しても良く、そして多重管構造のバーナを用いて酸水素火炎５とは別の管路より、酸水素火炎５に向けて噴出するようにすると良い。 In mixing the dopant compound in vapor, for example, in the case of silicon, silicon tetrachloride can be used as a raw material. In this case, silicon tetrachloride may be separately stored in a storage tank, bubbled with a gas such as argon gas Ar, and sent to the chamber 1 as vapor, or oxygen gas O 2 , hydrogen gas may be supplied to the oxyhydrogen burner 2. It may be introduced separately from H 2 and may be ejected toward the oxyhydrogen flame 5 from a pipe other than the oxyhydrogen flame 5 using a burner having a multi-tube structure.
次に、チャンバー１で合成された酸化チタン粒子１０は、排気ポンプ（図示せず）が管路１３で連結されているバグフィルター１２に管路１１を経て吸引され、このバグフィルタ１２に捕集される。そして、このバグフィルター１２には、例えば空気、窒素ガス等の圧縮ガスでバグフィルター１２に衝撃を付与して、目詰まりした酸化チタン粒子１０を払い落とす機構や、機械的に衝撃を与えて目詰まりを叩き落とす機構を設備しておくことによって、バグフィルター１２に捕集された酸化チタン粒子１０の粒子を効率よく回収することが出来る。 Next, the titanium oxide particles 10 synthesized in the chamber 1 are sucked through the pipe 11 to the bag filter 12 to which an exhaust pump (not shown) is connected by the pipe 13 and collected by the bag filter 12. Is done. The bag filter 12 is applied with an impact to the bag filter 12 with a compressed gas such as air or nitrogen gas, for example, and a mechanism for removing the clogged titanium oxide particles 10 or a mechanical shock is applied to the bag filter 12. By providing a mechanism for knocking off clogs, the titanium oxide particles 10 collected by the bag filter 12 can be efficiently recovered.
このようにして製造された酸化チタン粒子１０は、本発明の酸化チタン粒子としての特有の特徴、すなわち、粒子表面に網目模様を有し、平均粒子径が１０〜１００ｎｍで、粒子の真球度が０.１以下である球状粒子であり、該球状粒子の７０％以上がアナターゼ型の酸化チタン粒子である特徴を有するものとなる。 The titanium oxide particles 10 produced in this way are characteristic of the titanium oxide particles of the present invention, that is, having a mesh pattern on the particle surface, an average particle diameter of 10 to 100 nm, and the sphericity of the particles. Is a spherical particle having a particle size of 0.1 or less, and 70% or more of the spherical particle has an anatase-type titanium oxide particle.
以下に参考例を挙げる。 Reference examples are given below.
＜参考例１＞
四塩化チタン蒸気を原料として、これを図５で図示した４重管構造の酸水素バーナ２２を使用した酸水素火炎５中に、投入して熱酸化させ、酸化チタン粒子１０を合成した。４重管構造の酸水素バーナ２２の最内管２２ｄには四塩化チタン蒸気を２００ｓｃｃｍの流量で導入し、内側から２番目の管路２２ｃに水素ガスＨ２を２０００ｓｃｃｍの流量で、内側から３番目の管路２２ｂにアルゴンガスＡｒを２０００ｓｃｃｍの流量で、そして最外管の管路２２ａには酸素ガスＯ２を３５００ｓｃｃｍの流量で、それぞれ導入して、酸水素火炎により酸化チタン粒子１０を製造した。
<Reference Example 1>
Using titanium tetrachloride vapor as a raw material, this was put into the oxyhydrogen flame 5 using the oxyhydrogen burner 22 having the quadruple tube structure shown in FIG. 5 and thermally oxidized to synthesize titanium oxide particles 10. Titanium tetrachloride vapor is introduced into the innermost tube 22d of the oxyhydrogen burner 22 having a quadruple tube structure at a flow rate of 200 sccm, and hydrogen gas H 2 is introduced into the second pipe line 22c from the inside at a flow rate of 2000 sccm from the inner side. The argon gas Ar is introduced into the second pipe line 22b at a flow rate of 2000 sccm, and the oxygen gas O 2 is introduced into the pipe line 22a at the outermost pipe at a flow rate of 3500 sccm to produce titanium oxide particles 10 by an oxyhydrogen flame. did.
得られた酸化チタン粒子１０の粒子の形状は球形で、電子顕微鏡で観察した粒子像から測定した粒子の平均粒子径は４０ｎｍで、真球度は０.０６以下であった。また、粒径分布は粒子集合物全体の８５％を占める粒子の径が２０ｎｍ以上で、６０ｎｍ以下であり、粒径分布は小さかった。 The resulting titanium oxide particles 10 had a spherical shape, the average particle diameter of the particles measured from the particle image observed with an electron microscope was 40 nm, and the sphericity was 0.06 or less. The particle size distribution was such that the diameter of the particles occupying 85% of the entire particle aggregate was 20 nm or more and 60 nm or less, and the particle size distribution was small.
＜比較例１＞
参考例１の特性を検証するため、以下のような比較例１を行った。四塩化チタン蒸気を原料として使用した。そして、この四塩化チタン蒸気と加熱された酸素ガスＯ２と合成チャンバー内で混合し、熱酸化せしめて酸化チタン粒子を製造した。
<Comparative Example 1>
In order to verify the characteristics of Reference Example 1, the following Comparative Example 1 was performed. Titanium tetrachloride vapor was used as a raw material. Then, these four were mixed with titanium tetrachloride vapor heated oxygen gas O 2 in the synthesis chamber to produce titanium oxide particles allowed to thermal oxidation.
四塩化チタンの蒸気はバブリングで形成して供給し、バブリング温度は貯槽の温度を８５℃に加温、保持し、バブリングキャリアガスとしてアルゴンガスＡｒを２００ｓｃｃｍの流量で流した。反応酸素ガスＯ２は流量３５００ｓｃｃｍとし、その温度を１０００℃に加熱した。 Titanium tetrachloride vapor was formed and supplied by bubbling, and the bubbling temperature was maintained by heating and maintaining the temperature of the storage tank at 85 ° C., and argon gas Ar was flowed at a flow rate of 200 sccm as a bubbling carrier gas. The reactive oxygen gas O 2 was flowed at 3500 sccm and the temperature was heated to 1000 ° C.
得られた酸化チタン粒子の粒子の形状は表面に起伏のある不規則な粒状であり、真球度は測定不可能な形状であった。電子顕微鏡で観察した粒子像から測定した粒子の平均粒子径は９０ｎｍであり、粒径分布は、粒子全体の８５％を占める粒子の径が２０ｎｍ以上で、２００ｎｍ以下であり、粒径分布は大きかった。 The resulting titanium oxide particles had irregular shapes with undulating surfaces, and the sphericity was a shape that could not be measured. The average particle size of the particles measured from the particle image observed with an electron microscope is 90 nm, and the particle size distribution is 20 nm or more and 200 nm or less, and the particle size distribution is large. It was.
＜参考例１と比較例１との比較検証＞
上記参考例１の四塩化チタン蒸気を過剰酸素ガスＯ２の酸水素火炎中で合成して得られた酸化チタン粒子の粒子は、平均粒子径、真球度、粒径分布の点で、比較例１の単なる高温度酸素ガスＯ２雰囲気で四塩化チタン蒸気を熱酸化する方法で製造された酸化チタン粒子と格段の差異があることが明らかであり、参考例１の酸化チタン粒子が明白に優れていることが確認された。
<Comparison verification between Reference Example 1 and Comparative Example 1>
The titanium oxide particles obtained by synthesizing the titanium tetrachloride vapor of Reference Example 1 in an oxyhydrogen flame of excess oxygen gas O 2 are compared in terms of average particle size, sphericity, and particle size distribution. It is clear that there is a marked difference from the titanium oxide particles produced by thermal oxidation of titanium tetrachloride vapor in the simple high-temperature oxygen gas O 2 atmosphere of Example 1, and the titanium oxide particles of Reference Example 1 are clearly It was confirmed to be excellent.
＜参考例２＞
上記参考例１と同様に、四塩化チタン蒸気を原料として、図５で図示した４重管構造の酸水素バーナ２２を使用した酸水素火炎５中に、投入して熱酸化させ、酸化チタン粒子１０の粒子を合成した。４重管構造の酸水素バーナ２２の最内管２２ｄには四塩化チタン蒸気を２００ｓｃｃｍの流量で導入し、内側から２番目の管路２２ｃには水素ガスＨ２を２０００ｓｃｃｍの流量で、内側から３番目の管路２２ｂにはアルゴンガスＡｒを２０００ｓｃｃｍの流量で、そして最外管の管路２２ａには酸素ガスＯ２を３５００ｓｃｃｍの流量で、それぞれ導入して、酸化チタン粒子１０を製造した。
<Reference Example 2>
In the same manner as in Reference Example 1, titanium tetrachloride vapor is used as a raw material and is put into an oxyhydrogen flame 5 using the oxyhydrogen burner 22 shown in FIG. Ten particles were synthesized. Titanium tetrachloride vapor is introduced into the innermost tube 22d of the oxyhydrogen burner 22 having a quadruple tube structure at a flow rate of 200 sccm, and hydrogen gas H 2 is introduced into the second conduit 22c from the inside at a flow rate of 2000 sccm from the inside. Titanium oxide particles 10 were produced by introducing argon gas Ar into the third pipe line 22b at a flow rate of 2000 sccm and oxygen gas O 2 into the pipe line 22a at the outermost pipe at a flow rate of 3500 sccm.
ここで得られた酸化チタン粒子の粒子を石英ガラス板上にコーティングし、紫外線照射による光触媒活性の評価を行った。評価は、アセトアルデヒドの分解能力で行い、分解されて発生する二酸化炭素（ＣＯ２）の濃度を測定することによって評価した。その結果を、図７に時間経過に伴う二酸化炭素濃度（ｐｐｍ）の変化として、グラフに示す。 The obtained titanium oxide particles were coated on a quartz glass plate, and the photocatalytic activity by ultraviolet irradiation was evaluated. Evaluation was performed by measuring the concentration of carbon dioxide (CO 2 ) generated by decomposing by the ability to decompose acetaldehyde. The results are shown in the graph in FIG. 7 as changes in carbon dioxide concentration (ppm) with time.
＜比較例２＞
上記参考例２の光触媒活性の評価を検証するため、比較例２として、上記比較例１で得られた酸化チタン粒子の粒子を、実施例２と同様に石英ガラス板上にコーティングし、紫外線照射による光触媒活性の評価を行った。評価は、アセトアルデヒドの分解能力で行い、分解されて発生する二酸化炭素（ＣＯ２）の濃度を測定することによって評価した。なお、粒子の平均粒径が同程度になるよう合成条件を調整した。その結果を、時間経過に伴う二酸化炭素濃度（ｐｐｍ）変化として、図７に実施例２のグラフと併記して図示する。
<Comparative Example 2>
In order to verify the evaluation of the photocatalytic activity of Reference Example 2, as Comparative Example 2, the titanium oxide particles obtained in Comparative Example 1 were coated on a quartz glass plate in the same manner as in Example 2, and then irradiated with ultraviolet rays. The photocatalytic activity was evaluated. Evaluation was performed by measuring the concentration of carbon dioxide (CO 2 ) generated by decomposing by the ability to decompose acetaldehyde. The synthesis conditions were adjusted so that the average particle size of the particles was approximately the same. The results are shown in FIG. 7 together with the graph of Example 2 as changes in carbon dioxide concentration (ppm) with time.
＜参考例２と比較例２とでの光触媒活性の比較検証＞
図６で明らかであるように、参考例２の酸化チタン粒子の方が、極めて高いアセトアルデヒド分解力を示しており、光触媒活性が優れていることが確認された。
<Comparison verification of photocatalytic activity in Reference Example 2 and Comparative Example 2>
As apparent from FIG. 6, the titanium oxide particles of Reference Example 2 showed an extremely high acetaldehyde decomposing power, and it was confirmed that the photocatalytic activity was excellent.
＜比較例３＞
比較例３として、ガラス管を合成管として用い、該ガラス管に四塩化チタン蒸気と酸素ガスＯ２を導入し、熱源を酸水素バーナとして、ガラス管の外部から加熱することにより、ガラス管内で四塩化チタンを熱酸化させるＣＶＤ法により箱型形状酸化チタン粒子を合成した。
得られたこの酸化チタン粒子の粒子を石英ガラス板上にコーティングし、これに大腸菌を塗布した。
そして、ブラックライトを照射し、大腸菌数の時間経過による変化を検証した。その結果、最初の大腸菌数の１％以下に達するまでの時間は３０分であった。
<Comparative Example 3>
As Comparative Example 3, a glass tube was used as a synthetic tube, titanium tetrachloride vapor and oxygen gas O 2 were introduced into the glass tube, and the heat source was an oxyhydrogen burner, and the glass tube was heated from outside the glass tube. Box-shaped titanium oxide particles were synthesized by a CVD method in which titanium tetrachloride was thermally oxidized.
The obtained titanium oxide particles were coated on a quartz glass plate, and E. coli was applied thereto.
Then, irradiation with black light was performed, and changes in the number of E. coli with time were verified. As a result, the time required to reach 1% or less of the initial number of E. coli was 30 minutes.
＜比較例４＞
比較例４として四塩化チタンの蒸気を原料として、酸素ガスＯ２と混合して、これを加熱して熱酸化させるＣＶＤ法により球状の酸化チタン粒子を合成した。
得られたこの酸化チタン粒子の粒子を石英ガラス板上にコーティングし、これに大腸菌を塗布した。
そして、ブラックライトを照射し、大腸菌数の時間経過による変化を検証した。その結果、最初の大腸菌数の１％以下に達するまでの時間は６０分であった。
<Comparative example 4>
As Comparative Example 4, spherical titanium oxide particles were synthesized by a CVD method in which titanium tetrachloride vapor was mixed with oxygen gas O 2 and heated to thermally oxidize.
The obtained titanium oxide particles were coated on a quartz glass plate, and E. coli was applied thereto.
Then, irradiation with black light was performed, and changes in the number of E. coli with time were verified. As a result, the time required to reach 1% or less of the initial number of E. coli was 60 minutes.
１０…酸化チタン粒子、 １…チャンバー、 ２…酸水素バーナ、 ３、４、７、８、１１、１３…管路、 ５…酸水素火炎、 ６…貯槽、 ９…チタン化合物、 １２…バグフィルター、 ２１…同心２重管酸水素バーナ、 ２２…同心４重管酸水素バーナ、２３…同心３重管酸水素バーナ DESCRIPTION OF SYMBOLS 10 ... Titanium oxide particle, 1 ... Chamber, 2 ... Oxyhydrogen burner, 3, 4, 7, 8, 11, 13 ... Pipe line, 5 ... Oxyhydrogen flame, 6 ... Storage tank, 9 ... Titanium compound, 12 ... Bag filter 21 ... Concentric double tube oxyhydrogen burner, 22 ... Concentric quadruple tube oxyhydrogen burner, 23 ... Concentric triple tube oxyhydrogen burner
Claims (6)
粒子表面に網目模様を有し、平均粒子径が１０〜１００ｎｍであり、粒子の真球度が０.１以下の球状粒子であり、粒子集合物全体の８５容量％を占める粒子の径が１０ｎｍ〜４０ｎｍであることを特徴とする酸化チタン粒子。 Titanium compound vapor is fed from the side of the oxyhydrogen flame to the oxyhydrogen flame formed by the multi-tube oxyhydrogen burner, and the oxygen-hydrogen supply ratio supplied to the oxyhydrogen burner is set to 3/4 or more. Titanium oxide particles produced by a method of producing titanium oxide particles by causing an excess of oxygen and simultaneously causing a hydrolysis reaction and a thermal oxidation reaction in an oxyhydrogen flame,
The particle surface has a mesh pattern, the average particle size is 10 to 100 nm, the sphericity of the particle is 0.1 or less, and the particle size occupying 85% by volume of the entire particle aggregate is 10 nm. Titanium oxide particles characterized by being ˜40 nm.
粒子表面に網目模様を有し、平均粒子径が１０ｎｍ〜３０ｎｍであり、粒子の真球度が０.１以下の球状粒子であり、粒子集合物全体の８５容量％を占める粒子の径が１０ｎｍ〜２５ｎｍであることを特徴とする酸化チタン粒子。 Titanium compound vapor is sent from the side of the oxyhydrogen flame to the oxyhydrogen flame formed by the multi-tube oxyhydrogen burner, and the oxygen-hydrogen supply ratio to the oxyhydrogen burner is set to 3/4 or more. Titanium oxide particles produced by a method of producing titanium oxide particles by causing an excess of oxygen and simultaneously causing a hydrolysis reaction and a thermal oxidation reaction in an oxyhydrogen flame,
A spherical particle having a mesh pattern on the particle surface, an average particle diameter of 10 nm to 30 nm, a sphericity of the particle of 0.1 or less, and a particle diameter occupying 85% by volume of the entire particle aggregate is 10 nm. Titanium oxide particles characterized by being ˜25 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009137268A JP5107304B2 (en) | 2009-06-08 | 2009-06-08 | Titanium oxide particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009137268A JP5107304B2 (en) | 2009-06-08 | 2009-06-08 | Titanium oxide particles |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003126333A Division JP4444582B2 (en) | 2003-05-01 | 2003-05-01 | Titanium oxide particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009196889A true JP2009196889A (en) | 2009-09-03 |
| JP5107304B2 JP5107304B2 (en) | 2012-12-26 |
Family
ID=41140825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009137268A Expired - Fee Related JP5107304B2 (en) | 2009-06-08 | 2009-06-08 | Titanium oxide particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5107304B2 (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03252315A (en) * | 1990-02-27 | 1991-11-11 | Osaka Titanium Co Ltd | Production of high-purity titanium oxide |
| JPH05221615A (en) * | 1991-03-15 | 1993-08-31 | Osaka Titanium Co Ltd | Production of ultra-fine powder of metal oxide |
| JPH07216536A (en) * | 1994-01-24 | 1995-08-15 | Ulvac Japan Ltd | Omnidirection simultaneous vapor-deposition polymerizer |
| JPH08217654A (en) * | 1995-02-08 | 1996-08-27 | Nippon Aerojiru Kk | Ultraviolet-shelding cosmetic using fine powder of titanium dioxide |
| JP2001039704A (en) * | 1998-06-25 | 2001-02-13 | Ishihara Sangyo Kaisha Ltd | Production of metal oxide |
| WO2001016027A1 (en) * | 1999-08-30 | 2001-03-08 | Showa Denko K.K. | Titanium oxide particles and method for production thereof |
| JP2001151509A (en) * | 1999-11-19 | 2001-06-05 | Toho Titanium Co Ltd | Spherical titanium oxide fine particle |
| JP2001151510A (en) * | 1999-11-19 | 2001-06-05 | Toho Titanium Co Ltd | Method of producing titanium oxide fine particle |
| JP2001276615A (en) * | 2000-04-03 | 2001-10-09 | Michio Matsumura | Titanium oxide powder for photocatalyst |
| JP2001287996A (en) * | 2000-04-03 | 2001-10-16 | Toho Titanium Co Ltd | Anatase-type titanium oxide single crystal |
| JP2001302242A (en) * | 2000-04-17 | 2001-10-31 | Toho Titanium Co Ltd | Method for producing titanium oxide fine particle |
-
2009
- 2009-06-08 JP JP2009137268A patent/JP5107304B2/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03252315A (en) * | 1990-02-27 | 1991-11-11 | Osaka Titanium Co Ltd | Production of high-purity titanium oxide |
| JPH05221615A (en) * | 1991-03-15 | 1993-08-31 | Osaka Titanium Co Ltd | Production of ultra-fine powder of metal oxide |
| JPH07216536A (en) * | 1994-01-24 | 1995-08-15 | Ulvac Japan Ltd | Omnidirection simultaneous vapor-deposition polymerizer |
| JPH08217654A (en) * | 1995-02-08 | 1996-08-27 | Nippon Aerojiru Kk | Ultraviolet-shelding cosmetic using fine powder of titanium dioxide |
| JP2001039704A (en) * | 1998-06-25 | 2001-02-13 | Ishihara Sangyo Kaisha Ltd | Production of metal oxide |
| WO2001016027A1 (en) * | 1999-08-30 | 2001-03-08 | Showa Denko K.K. | Titanium oxide particles and method for production thereof |
| JP2001151509A (en) * | 1999-11-19 | 2001-06-05 | Toho Titanium Co Ltd | Spherical titanium oxide fine particle |
| JP2001151510A (en) * | 1999-11-19 | 2001-06-05 | Toho Titanium Co Ltd | Method of producing titanium oxide fine particle |
| JP2001276615A (en) * | 2000-04-03 | 2001-10-09 | Michio Matsumura | Titanium oxide powder for photocatalyst |
| JP2001287996A (en) * | 2000-04-03 | 2001-10-16 | Toho Titanium Co Ltd | Anatase-type titanium oxide single crystal |
| JP2001302242A (en) * | 2000-04-17 | 2001-10-31 | Toho Titanium Co Ltd | Method for producing titanium oxide fine particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5107304B2 (en) | 2012-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI410275B (en) | Method of fabricating visible light absorbed tio/cnt photocatalysts and photocatalytic filters | |
| Kuo et al. | Carbon-containing nano-titania prepared by chemical vapor deposition and its visible-light-responsive photocatalytic activity | |
| Huang et al. | Aerosol-assisted flow synthesis of B-doped, Ni-doped and B–Ni-codoped TiO2 solid and hollow microspheres for photocatalytic removal of NO | |
| JP4145923B2 (en) | Titanium oxide particles, manufacturing method thereof, manufacturing apparatus, and processing method using the titanium oxide | |
| JP2007203223A (en) | Visible light-responsive titanium oxide-activated carbon composite photocatalyst and manufacturing method | |
| CN109174075A (en) | A kind of rare-earth element modified titanium dioxide nano photocatalysis material and preparation method thereof for photocatalytic degradation VOCs | |
| Xu et al. | Photocatalytic degradation of cooking fume on a TiO2-coated carbon nanotubes composite filter | |
| JP4444582B2 (en) | Titanium oxide particles | |
| Kassahun et al. | Effects of operational parameters on bacterial inactivation in Vis-LEDs illuminated N-doped TiO2 based photoreactor | |
| Ouzzine et al. | Carbon nanofibres as substrates for the preparation of TiO2 nanostructured photocatalysts | |
| JP3993956B2 (en) | Method for producing spherical titanium oxide fine particles | |
| KR102562529B1 (en) | Transition Metal Doped Complex Photocatalyst and Manufacturing Method thereof | |
| Hsieh et al. | Synthesis and visible‐light‐derived photocatalysis of titania nanosphere stacking layers prepared by chemical vapor deposition | |
| JP5107304B2 (en) | Titanium oxide particles | |
| JP4754197B2 (en) | Titanium oxide particles, production method thereof and use thereof | |
| JPS60186418A (en) | Production of ultrafine particle of titanium oxide | |
| JP3949143B2 (en) | Titanium dioxide nanophotocatalyst powder, production method and apparatus thereof | |
| US7662476B2 (en) | Metal surface-modified silica-titania composites and methods for forming the same | |
| JP3890403B2 (en) | Nitrogen-containing zinc oxide powder and method for producing the same | |
| JP4234298B2 (en) | Method for producing titanium oxide fine particles | |
| JP5259767B2 (en) | Method for evaluating crystallinity of titanium oxide particles, and method for measuring surface defect density of titanium oxide particles | |
| JP3787254B2 (en) | Method for producing titanium oxide fine particles | |
| JP2001276615A (en) | Titanium oxide powder for photocatalyst | |
| JP4625942B2 (en) | Visible light responsive titanium oxide powder photocatalyst and process for producing the same | |
| TWI428183B (en) | Preparation of Modified Titanium Dioxide with Better Degradation Efficiency |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090608 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20090609 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110512 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120925 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121003 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5107304 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151012 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |