JP2003089521A - Fine oxide particle which suppresses generation of harmful substance in combustion and decomposes the substance, method for producing the fine particle, organic matter containing the fine particle, and method for disposing of organic matter using the fine particle - Google Patents
Fine oxide particle which suppresses generation of harmful substance in combustion and decomposes the substance, method for producing the fine particle, organic matter containing the fine particle, and method for disposing of organic matter using the fine particleInfo
- Publication number
- JP2003089521A JP2003089521A JP2001279152A JP2001279152A JP2003089521A JP 2003089521 A JP2003089521 A JP 2003089521A JP 2001279152 A JP2001279152 A JP 2001279152A JP 2001279152 A JP2001279152 A JP 2001279152A JP 2003089521 A JP2003089521 A JP 2003089521A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- organic substance
- combustion
- harmful substances
- organic
- 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.)
- Pending
Links
- 239000000126 substance Substances 0.000 title claims abstract description 102
- 239000010419 fine particle Substances 0.000 title claims abstract description 86
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000005416 organic matter Substances 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 title abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 140
- 150000002013 dioxins Chemical class 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 61
- 239000000843 powder Substances 0.000 claims description 51
- 230000001699 photocatalysis Effects 0.000 claims description 38
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 19
- 229920000573 polyethylene Polymers 0.000 claims description 19
- 239000011941 photocatalyst Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002956 ash Substances 0.000 claims 4
- 239000010881 fly ash Substances 0.000 claims 4
- 239000002861 polymer material Substances 0.000 claims 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 claims 1
- 229920000515 polycarbonate Polymers 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 claims 1
- 239000005020 polyethylene terephthalate Substances 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 229910001111 Fine metal Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 235000014413 iron hydroxide Nutrition 0.000 description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 239000003440 toxic substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、焼却時にダイオキシン
のような有害物質の生成を抑制し、かつ、焼却後にかか
る有害物質を分解除去する材料、並びに、その材料を用
いた有機物の処分方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material which suppresses the production of harmful substances such as dioxins during incineration, and decomposes and removes the harmful substances after incineration, and a method for disposing of organic substances using the material. .
【０００２】[0002]
【従来の技術】有機物質の焼却時には、塩化物が混在す
るとダイオキシンなどの有害物質が生成することから、
この有害物質の生成を抑制することが、社会的観点から
重要課題となっている。また、このために、例えば、特
開平７−２５７５９４、特開平７−３２２９１０、特開
平９−８９２２８に見られるように水酸化鉄微粒子を燃
焼炉に導入する、あるいは、水酸化鉄微粒子を含んだプ
ラスティックをゴミ袋として用いることが提案されてい
る。ここで、水酸化鉄は、プラスティックなどの助燃作
用を有し、これにより、燃焼温度を上昇させ、ダイオキ
シンなどの有害物質の生成が燃焼温度の増加と共に抑制
される事実に基づいて、有害物質の生成の抑制を図る目
的に用いられている。2. Description of the Related Art When organic substances are incinerated, harmful substances such as dioxins are produced when chlorides are mixed.
Suppressing the generation of this harmful substance has become an important issue from a social perspective. For this reason, for example, iron hydroxide fine particles are introduced into a combustion furnace as seen in JP-A-7-257594, JP-A-7-322910, or JP-A-9-89228, or iron hydroxide particles are included. It has been proposed to use plastic as a garbage bag. Here, iron hydroxide has an auxiliary combustion effect such as plastic, which raises the combustion temperature and suppresses the production of harmful substances such as dioxins with the increase of the combustion temperature. It is used for the purpose of suppressing generation.
【０００３】また、特開２０００−０８４３６１に見ら
れるように、光触媒を焼却すべき物質にあらかじめ添加
することにより有害物質を分解する方法が提案されてい
る。Further, as disclosed in Japanese Patent Laid-Open No. 2000-084361, there has been proposed a method of decomposing harmful substances by adding a photocatalyst to a substance to be incinerated in advance.
【０００４】[0004]
【発明が解決しようとする課題】上述したように、水酸
化鉄微粒子をプラスティックに含ませることにより、焼
却時の燃焼温度を上昇させ、有害物質の生成を抑制する
ことが可能であるが、実際にゴミが焼却される状況を完
全に管理することは社会的状況から困難であり、また、
よしんば、ゴミの焼却が、自治体などの公的機関などに
より管理されている焼却設備でおこなわれたとしても、
これにより有害物質の発生を抑制することが可能であり
さえすれ、完全に発生させないことは現在の燃焼技術で
は不可能とされている。As described above, it is possible to increase the combustion temperature during incineration and suppress the production of harmful substances by incorporating iron hydroxide fine particles into the plastic. It is difficult to manage the situation in which the garbage is incinerated completely due to social circumstances, and
Even if the waste is incinerated at the incineration facilities managed by public institutions such as local governments,
This makes it possible to suppress the generation of harmful substances, but it is impossible to prevent them from being completely generated by the present combustion technology.
【０００５】逆に、現在の社会的、技術的状況が有害物
質を発生させない状況になっていないことが、プラステ
ィックに水酸化鉄を含有させるといった有害物質の発生
を抑制する技術の開発を促しているということができ
る。On the contrary, the fact that the current social and technological conditions do not allow the generation of harmful substances encourages the development of technology for suppressing the generation of harmful substances, such as containing iron hydroxide in plastic. It can be said that
【０００６】一方、燃焼時の助燃効果をもつ水酸化鉄
は、黄褐色の透過色を持つことから、透明性、あるい
は、着色任意性を大きな特徴としてきたプラスティック
製品への本技術の適用に大きな障害となってきた。On the other hand, iron hydroxide, which has an auxiliary combustion effect at the time of combustion, has a yellowish-brown transmission color, so that the present technology is greatly applied to plastic products characterized by transparency or coloring arbitrariness. It has become an obstacle.
【０００７】また、光触媒を焼却すべき物質にあらかじ
め添加する技術は、上記のように、ゴミの焼却が有害物
を発生させない状況になっていないことから、生まれた
技術のひとつであり、焼却により不可避的に生成した有
害物質をかかる光触媒により分解することを目的として
いる。しかしながら、光触媒を十分選定し、かつ、場合
により、表面処理方法などを十分に検討しなければ、光
触媒の添加により、かえって燃焼阻害が生じ、これによ
り燃焼温度の低下、つまり、ダイオキシンなどの有害物
質の生成を促進してしまう恐れもある。Further, the technique of adding a photocatalyst to a substance to be incinerated in advance is one of the techniques born from the fact that the incineration of dust does not generate a harmful substance as described above, and The purpose is to decompose toxic substances that are inevitably generated by such a photocatalyst. However, if a photocatalyst is selected sufficiently and, in some cases, the surface treatment method is not thoroughly studied, the addition of the photocatalyst rather causes combustion inhibition, which lowers the combustion temperature, that is, harmful substances such as dioxins. There is also a risk of promoting the generation of.
【０００８】一方、光触媒は光の照射したにおいてはじ
めて目的とする有害物質の分解をおこなうが、光触媒を
含んだ有機物が焼却された後、生成した有害物質を含む
焼却灰が、十分な光の照射を受ける環境下に常に管理さ
れることに大きな期待を寄せることは現実的ではない。On the other hand, the photocatalyst decomposes the target harmful substance only when it is irradiated with light, but after the organic matter containing the photocatalyst is incinerated, the incinerated ash containing the generated harmful substance is sufficiently irradiated with light. It is unrealistic to place great expectations on being constantly managed in a receiving environment.
【０００９】つまり、有機物に添加剤を含ませることに
より有害物質の発生を抑制する方法においては、添加す
る物質は、その助燃作用により、ダイオキシンなどの有
害物質の生成を抑制するとともに、その光触媒作用によ
り、生成した有害物質の分解をおこなうことが必要とさ
れる。That is, in the method of suppressing the generation of harmful substances by including an additive in an organic substance, the added substance suppresses the generation of harmful substances such as dioxin due to its combustion supporting effect, and at the same time, its photocatalytic action. Therefore, it is necessary to decompose the generated harmful substances.
【００１０】しかしながら、特開２０００−０８４３６
１に述べられているように、プラスティックなどの有機
物一般に光触媒作用のある物質を添加した場合、かかる
有機物の商品寿命がつきる前にその有機物を分解してし
まう恐れもあることから、焼却という熱処理により始め
て十分な光触媒活性を発現することが重要な要件とな
る。同時に、光触媒作用による有害物質の分解を効率よ
くおこなうためには、プラスティックに十分に分散した
形で添加する必要があることから、添加粒子の表面に存
在する反応基を適切な形にすることが重要な要件とな
る。これらの観点から見て、前述の従来の光触媒を添加
する技術は上記２つの要件を同時に満たすものとはほど
遠く、満足のいくものではなかった。However, Japanese Unexamined Patent Publication No. 2000-08436.
As described in 1, when an organic substance such as plastics, which generally has a photocatalytic action, is added, there is a risk that the organic substance will be decomposed before the product life is reached. It is an important requirement to develop sufficient photocatalytic activity for the first time. At the same time, in order to efficiently decompose harmful substances by photocatalysis, it is necessary to add them in a sufficiently dispersed form in plastic, so it is necessary to make the reactive groups present on the surface of the added particles into an appropriate form. It becomes an important requirement. From these viewpoints, the technique of adding the above-mentioned conventional photocatalyst is far from the one satisfying the above two requirements at the same time and is not satisfactory.
【００１１】本発明は、プラスティックなどの有機物へ
の分散添加が容易であり、かつ、ほとんど無色透明であ
ることから既存及び新規商品への適用性に優れ、さら
に、焼却時に助燃作用を持つことによりダイオキシンな
どの有害物質の生成を抑制し、なおかつ、焼却時の加熱
により光触媒活性が発現することにより、商品寿命に影
響を与えることなく、焼却後に有害物質を分解する作用
を発現する添加物、もしくは、添加物を含んだ有機物を
提供することを技術的課題とする。INDUSTRIAL APPLICABILITY The present invention has excellent applicability to existing and new products because it can be easily dispersed and added to organic substances such as plastics, and is almost colorless and transparent. Further, it has an auxiliary combustion effect when incinerated. An additive that suppresses the production of toxic substances such as dioxins, and that exerts a photocatalytic activity by heating during incineration to exert a function of decomposing harmful substances after incineration without affecting the product life, or The technical problem is to provide an organic substance containing an additive.
【００１２】[0012]
【課題を解決するための手段】本発明は、過酸化チタン
の微粒子、もしくは、過酸化チタンで被覆した金属酸化
物を製造し、これらのいずれかの粒子を有機物に含ませ
たものを用いて製品とすることにある。According to the present invention, fine particles of titanium peroxide or a metal oxide coated with titanium peroxide are produced, and any one of these particles is contained in an organic substance. It is to be a product.
【００１３】これらの粒子の表面が光触媒活性を持たな
いことから、通常の使用条件においてかかる有機物の分
解を促進することがないために、製品の寿命が短くなる
ことはない。Since the surfaces of these particles do not have photocatalytic activity, they do not accelerate the decomposition of such organic substances under normal use conditions, so that the life of the product is not shortened.
【００１４】また、本発明は、これらの微粒子をあらか
じめ有機物に含ませておくほか燃焼前、もしくは、燃焼
時に有機物に混ぜることによっても達成される。The present invention can also be achieved by preliminarily including these fine particles in an organic substance and mixing them with the organic substance before or during combustion.
【００１５】すなわち、これらの微粒子が助燃作用を有
することから、燃焼温度を上昇させ、これにより燃焼時
におけるダイオキシンなどの有害物質の生成を抑制す
る。さらに、また、かかる過酸化チタンの微粒子、もし
くは、過酸化チタンにより被覆された金属酸化物の微粒
子は、燃焼時に、その少なくとも表面層がアナターゼ型
酸化チタンに変化し、光触媒能を持つことになる。燃焼
時に生じるダイオキシンなどの有害物質を含む燃焼灰な
どは、上述のように、少なくともその表面がアナターゼ
型酸化チタンとなった微粒子も含むことになるため、紫
外線の照射される環境に置かれるだけで、有害物質は分
解され、無毒化される。That is, since these fine particles have an auxiliary combustion effect, the combustion temperature is raised, thereby suppressing the production of harmful substances such as dioxins during combustion. Furthermore, the fine particles of titanium peroxide or the fine particles of metal oxide coated with titanium peroxide have a photocatalytic activity when at least the surface layer thereof is changed to anatase-type titanium oxide during combustion. . Combustion ash containing toxic substances such as dioxins generated during combustion, as described above, will also contain fine particles whose surface is at least anatase-type titanium oxide. , Harmful substances are decomposed and detoxified.
【００１６】上記のごとく、過酸化チタン微粒子、もし
くは、過酸化チタンで被覆した金属酸化物は、有機物に
含ませても商品寿命に影響を与えることがなく、また、
これを含んだ有機物を焼却する、あるいは、これらの微
粒子を混ぜて有機物を焼却することにより有害物質の生
成を抑制し、さらに、生成した有害物質と共存すること
から、紫外線照射によりかかる有害物質を分解し、ま
た、意図せず、環境中に流出した際も、環境中の紫外線
照射により環境を汚染することなく有害物質を分解する
作用を有する。As described above, the titanium peroxide fine particles or the metal oxide coated with titanium peroxide does not affect the life of the product even if it is included in the organic substance, and
Incineration of organic substances containing this, or by mixing these fine particles to incinerate organic substances suppresses the production of harmful substances, and because it coexists with the produced harmful substances, it is possible to remove harmful substances by UV irradiation. It decomposes, and even when it unintentionally flows out into the environment, it has a function of decomposing harmful substances without polluting the environment by ultraviolet irradiation in the environment.
【００１７】本発明は、上述の作用に基づき、燃焼時に
生じる有害物質を分解する酸化物微粒子およびその製造
方法および有害物質を分解する方法を提供する。The present invention provides oxide fine particles for decomposing harmful substances generated during combustion, a method for producing the same and a method for decomposing harmful substances, based on the above-mentioned effects.
【００１８】[0018]
【作用】過酸化チタン粒子を、例えば、以下の方法によ
り得ることができる。特許第２９３８３７６、特許第２
８７５９９３に与えられた技術により作成された過酸化
チタン溶液に、酸、もしくは、アルカリを加えることに
より、あるいは、単に水分を蒸発させることにより、過
酸化チタン微粒子ゲルよりなる沈殿物を生じさせる。次
に、これが凝結し、巨大粒子になったり、あるいは、薄
膜のような連続体となることのないように注意しながら
１２０℃で乾燥させ、粉体固形物を得、これを粉砕し、
過酸化チタン微粒子を得る。The titanium peroxide particles can be obtained, for example, by the following method. Patent No. 2938376, Patent No. 2
A titanium peroxide fine particle gel precipitate is formed by adding an acid or an alkali to the titanium peroxide solution prepared by the technique given in 875993 or by simply evaporating water. Next, it is dried at 120 ° C. while being careful not to condense into huge particles or become a continuous body such as a thin film, to obtain a powder solid matter, which is crushed,
Titanium peroxide fine particles are obtained.
【００１９】過酸化チタンで被覆した金属酸化物は、例
えば、以下の方法で得ることができる。特許２９３８３
７６，特許２８７６９９３に与えられた技術により作成
された過酸化チタン溶液に、金属酸化物微粒子を投入
し、水分を蒸発させる。これにより、過酸化チタンで被
覆された金属酸化物を得る。The metal oxide coated with titanium peroxide can be obtained, for example, by the following method. Patent 29383
76, Japanese Patent No. 2876993, metal oxide fine particles are added to a titanium peroxide solution prepared by the technique given, and water is evaporated. As a result, a metal oxide coated with titanium peroxide is obtained.
【００２０】また、過酸化チタンで被覆した酸化チタン
は、上記の過酸化チタン溶液を用いる方法において、金
属酸化物として酸化チタン微粒子を用いることで得るこ
とができる。また、過酸化水素水溶液に酸化チタン微粒
子を投入し、適当な時間の撹拌を継続した後、水分を蒸
発させることにより、酸化チタン微粒子の表面を過酸化
チタンとすることにより、過酸化チタンで被覆した酸化
チタンを得る。ただし、過酸化チタン微粒子、及び、過
酸化チタンを被覆した金属酸化物を得る方法は上記の方
法に限定されるものではない。The titanium oxide coated with titanium peroxide can be obtained by using fine particles of titanium oxide as the metal oxide in the method using the titanium peroxide solution. In addition, by adding titanium oxide fine particles to an aqueous hydrogen peroxide solution and continuing stirring for an appropriate time, evaporating water to form titanium peroxide fine particles on the surface of the titanium oxide fine particles, thereby coating with titanium peroxide. To obtain titanium oxide. However, the method for obtaining the titanium peroxide fine particles and the metal oxide coated with titanium peroxide is not limited to the above method.
【００２１】これらの微粒子の大きさは、期待される助
燃効果と光触媒効果が微粒子の表面積と共に増大するこ
とから小さい方が望ましいが、粒径が小さすぎると自己
凝集を生じ、微粒子そのものの大きさを小さくした効果
が失われてしまう。このため、粒子の大きさは、最大外
形で、５ｎｍ以上であることが望ましい。さらに、有機
物、特に、高分子に混練する際は、例えば、酸化チタン
を用いると、その最大外形が５ｎｍであると混練を均一
におこなうことは不可能であるが、過酸化チタン微粒
子、もしくは、過酸化チタンで被覆された金属酸化物
は、その最大外形が５ｎｍであっても、混練を均一にお
こなうことができる。この機構は未だ明らかではない
が、少なくとも本発明において供せられる微粒子であれ
ば、十分な触媒作用を持ち、かつ、自己凝集することな
く、さらに、高分子への均一な混練が可能となることか
ら、微粒子の最大外形が５ｎｍ以上であることが望まし
い。The size of these fine particles is preferably small because the expected combustion-inhibiting effect and photocatalytic effect increase with the surface area of the fine particles, but if the particle size is too small, self-aggregation occurs and the size of the fine particles themselves. The effect of reducing is lost. Therefore, it is desirable that the maximum size of the particles be 5 nm or more. Furthermore, when kneading with an organic substance, especially a polymer, for example, when titanium oxide is used, it is impossible to perform kneading uniformly when the maximum outer shape is 5 nm, but titanium peroxide fine particles, or The metal oxide coated with titanium peroxide can be uniformly kneaded even if its maximum outer shape is 5 nm. Although this mechanism is not yet clear, at least the fine particles provided in the present invention have a sufficient catalytic action and do not cause self-aggregation, and further, uniform kneading into a polymer is possible. Therefore, it is desirable that the maximum outer shape of the fine particles is 5 nm or more.
【００２２】また、かかる微粒子を有機物、特に、高分
子に混練する際は、かかる高分子の成形体の強度が低下
することを避けるためには、微粒子の最大外形を概１ｍ
ｍ以下にすることが必要である。ただし、かかる高分子
をフィルム上に成形する際には、微粒子の最大外形をフ
ィルム厚に比べ十分に小さくすることも必要となる。When the fine particles are kneaded with an organic substance, particularly a polymer, the maximum outer shape of the fine particles should be about 1 m in order to prevent the strength of the molded body of the polymer from decreasing.
It is necessary to make it m or less. However, when molding such a polymer on a film, it is also necessary to make the maximum outer shape of the fine particles sufficiently smaller than the film thickness.
【００２３】過酸化チタンは光触媒活性を持たないた
め、過酸化チタン微粒子、もしくは、過酸化チタンを被
覆した金属酸化物を有機物に混練しても、通常の使用条
件下では、有機物の分解を促進することはなく、商品寿
命を短くすることはない。しかしながら、発明者らは、
非晶質酸化チタンを３００℃で９０分間加熱するとアナ
ターゼ型酸化チタンになることを確認しており、この事
実から類推して、過酸化チタン微粒子、あるいは、過酸
化チタンで被覆した金属酸化物微粒子を製造する際の乾
燥工程などでの加熱を３００℃未満にすることが望まし
い。加熱温度を低下させると乾燥などに要する時間が大
きくなり、製造タクトが延びることから、加熱温度を上
げることが要求されるが、上記の理由から、加熱温度を
３００℃未満にすることが望ましい。Since titanium peroxide does not have photocatalytic activity, even if fine particles of titanium peroxide or a metal oxide coated with titanium peroxide are kneaded with an organic substance, the decomposition of the organic substance is promoted under normal use conditions. It does not shorten the product life. However, the inventors
It has been confirmed that when an amorphous titanium oxide is heated at 300 ° C. for 90 minutes, it becomes anatase type titanium oxide. By analogy with this fact, titanium peroxide fine particles or metal oxide fine particles coated with titanium peroxide are confirmed. It is desirable that the heating in the drying step or the like when manufacturing the is less than 300 ° C. When the heating temperature is lowered, the time required for drying and the like becomes longer and the production tact is extended, so that it is required to raise the heating temperature.
【００２４】アナターゼ型酸化チタンが紫外線照射下
で、ダイオキシンを分解しうることは一般に知られてお
り、例えば、Ｅ． Ｐｅｌｉｚｚｅｔｔｉ， Ｍ． Ｂ
ｏｒｇａｒｅｌｌｏ， Ｅ． Ｂｏｒｇａｒｅｌｌｏ
ａｎｄ Ｎ． Ｓｅｒｐｏｎｅ， Ｃｈｅｍｏｓｈｅｒ
ｅ， １７ （１９８８） ４９９．に記述がある。ま
た、発明者らは、過酸化チタンで被覆した酸化チタンを
６００℃で１５分間加熱して得られた微粒子の光触媒活
性能を、被覆されていない酸化チタンのそれと比較した
結果、加熱後の過酸化チタン被覆酸化チタンの光触媒活
性能はアナターゼ型酸化チタンの５０−７０％程度であ
るが、ダイオキシンを分解するには十分な光触媒活性能
を持つことを確認した。It is generally known that anatase type titanium oxide can decompose dioxin under irradiation of ultraviolet rays. Pelizzzetti, M .; B
orgarello, E .; Borgarello
and N.M. Serpone, Chemoher
e, 17 (1988) 499. There is a description in. The inventors have also compared the photocatalytic activity of fine particles obtained by heating titanium oxide coated with titanium peroxide at 600 ° C. for 15 minutes with that of uncoated titanium oxide. The photocatalytic activity of titanium oxide coated with titanium oxide is about 50-70% of that of anatase-type titanium oxide, but it was confirmed that the photocatalytic activity has sufficient photocatalytic activity to decompose dioxin.
【００２５】過酸化チタン微粒子を高分子粉体と混合
し、燃焼させた結果、燃焼開始温度の低下と燃焼時の発
熱量増加に伴うと考えられる温度上昇が確認された。ま
た、過酸化チタンを被覆した酸化チタン微粒子を高分子
粉体と混合し、燃焼させた結果、同様に、燃焼開始温度
の低下と温度上昇が確認された。これらの結果より、過
酸化チタン微粒子、及び、過酸化チタンで被覆された金
属酸化物微粒子は、助燃効果を有すると結論できる。As a result of mixing the fine particles of titanium peroxide with the polymer powder and burning them, it was confirmed that the temperature at the start of combustion was lowered and the temperature was considered to be increased due to the increase in the amount of heat generated during combustion. Further, as a result of mixing the titanium oxide fine particles coated with titanium peroxide with the polymer powder and burning the mixture, it was similarly confirmed that the combustion start temperature was lowered and the temperature was increased. From these results, it can be concluded that the titanium peroxide fine particles and the metal oxide fine particles coated with titanium peroxide have an auxiliary combustion effect.
【００２６】上記の過酸化チタン微粒子、及び、過酸化
チタンで被覆された金属酸化物微粒子の持つ助燃効果、
及び、光触媒能活性の、混合される有機物への作用は、
かかる微粒子の有機物に対する量が多くなるにしたがい
大きくなる。一方、有機物に混入される微粒子の量が大
きくなりすぎると、有機物に期待される物理的、化学的
性能が損なわれる。このことから、混入される微粒子の
量は総量の０．５重量％から５０重量％の範囲にあるこ
とが望ましい。また、１重量％から３０重量％の範囲に
あることがさらに望ましい。また、１重量％から１５重
量％の範囲にあることが特に望ましい。[0026] The above-mentioned titanium peroxide fine particles and the metal oxide fine particles coated with titanium peroxide have an auxiliary combustion effect,
And, the action of photocatalytic activity on the mixed organic matter,
The larger the amount of such fine particles with respect to the organic substance, the larger. On the other hand, if the amount of the fine particles mixed in the organic substance becomes too large, the physical and chemical performance expected of the organic substance is impaired. From this, it is desirable that the amount of fine particles to be mixed is in the range of 0.5 wt% to 50 wt% of the total amount. Further, it is more desirable to be in the range of 1% by weight to 30% by weight. Further, it is particularly desirable to be in the range of 1% by weight to 15% by weight.
【００２７】過酸化チタン微粒子は若干の黄色透過色を
呈するが、過酸化チタンを被覆した酸化チタンの透過
色、及び、反射色は極めてニュートラルであり、無色で
ある。このことから、過酸化チタンで被覆した金属酸化
物は、かかる金属酸化物自身が無色透明である場合、無
色透明であるといえる。これにより、高分子にこれら微
粒子を混練しても、その外観に大きな変化がなく、審美
的に所望される無色透明性、もしくは、外観色を容易に
得ることができる。The titanium peroxide fine particles show a slight yellow transmission color, but the transmission color and reflection color of titanium oxide coated with titanium peroxide are extremely neutral and colorless. From this, it can be said that the metal oxide coated with titanium peroxide is colorless and transparent when the metal oxide itself is colorless and transparent. As a result, even if these fine particles are kneaded with the polymer, the appearance does not change significantly, and the colorless transparency or appearance color that is aesthetically desired can be easily obtained.
【００２８】上述のごとく、本発明は、焼却時にダイオ
キシンのような有害物質の生成を抑制し、かつ、焼却後
にかかる有害物質を分解除去するのに好適な材料とし
て、過酸化チタン、及び、過酸化チタンを被覆した金属
酸化物を与える。As described above, the present invention suppresses the production of harmful substances such as dioxins during incineration and, as a material suitable for decomposing and removing the harmful substances after incineration, titanium peroxide and peroxide are used. This gives a metal oxide coated with titanium oxide.
【００２９】[0029]
【実施例１】過酸化チタンゾルであるペルオキソチタン
酸溶液（株式会社エコート社製ＰＴＡ溶液、酸化チタン
換算で０．８５重量％を含む）２００ｃｃをフラスコに
入れ、油浸により温度を約６０℃に保った状態で、ロー
タリーポンプで４時間排気することにより、粉体固形物
を得た。この後、７０℃の大気雰囲気下で１２時間置
き、乾燥し、この後、乳鉢で粉体とし、過酸化チタン粉
体を得た。[Example 1] 200 cc of a peroxotitanic acid solution (PTA solution manufactured by Ekot Co., Ltd., containing 0.85 wt% in terms of titanium oxide), which is a titanium peroxide sol, was placed in a flask and the temperature was adjusted to about 60 ° C by oil immersion. While keeping this state, the powder was solid-evacuated by evacuation with a rotary pump for 4 hours. Then, it was placed in an atmosphere of 70 ° C. for 12 hours and dried, and then powdered in a mortar to obtain a titanium peroxide powder.
【００３０】[0030]
【実施例２】平均粒径７ｎｍのアナターゼ型酸化チタン
粉体（石原産業株式会社製光触媒酸化チタンＳＴ−０
１）１ｇを５ｇの１重量％過酸化水素水溶液中に分散
し、１時間、スターラーで撹拌し続けた。この後、これ
を１２０℃の大気雰囲気中で２時間置き、乾燥し、粉体
固形物を得た。この後、得られた粉体固形物を乳鉢で粉
体とし、過酸化チタンで被覆された酸化チタン粉体を得
た。Example 2 Anatase type titanium oxide powder having an average particle size of 7 nm (photocatalyst titanium oxide ST-0 manufactured by Ishihara Sangyo Co., Ltd.)
1) 1 g was dispersed in 5 g of a 1 wt% hydrogen peroxide aqueous solution, and the mixture was continuously stirred with a stirrer for 1 hour. Then, this was left in an air atmosphere at 120 ° C. for 2 hours and dried to obtain a powder solid. Then, the obtained powder solid matter was powdered in a mortar to obtain titanium oxide powder coated with titanium peroxide.
【００３１】[0031]
【実施例３】平均粒径７ｎｍのアナターゼ型酸化チタン
粉体（石原産業株式会社製光触媒酸化チタンＳＴ−０
１）１ｇを過酸化チタンゾルであるペルオキソチタン酸
溶液（株式会社エコート社製ＰＴＡ溶液、酸化チタン換
算で０．８５重量％を含む）１５ｇに投入、１時間、ス
ターラーで撹拌し続けた。この後、これを１２０℃の大
気雰囲気中で２時間置き、乾燥し、粉体固形物を得た。
この後、得られた粉体固形物を乳鉢で粉体とし、過酸化
チタンで被覆された酸化チタンを得た。Example 3 Anatase type titanium oxide powder having an average particle size of 7 nm (photocatalyst titanium oxide ST-0 manufactured by Ishihara Sangyo Co., Ltd.)
1) 1 g was added to 15 g of a peroxotitanic acid solution (PTA solution manufactured by Equat Co., Ltd., containing 0.85% by weight in terms of titanium oxide) which is a titanium peroxide sol, and stirring was continued with a stirrer for 1 hour. Then, this was left in an air atmosphere at 120 ° C. for 2 hours and dried to obtain a powder solid.
Then, the obtained powder solid matter was powdered in a mortar to obtain titanium oxide coated with titanium peroxide.
【００３２】[0032]
【比較例１】図１に示す燃焼装置内に置かれた石英ガラ
スのボートに、粒径が５０μｍのポリエチレン粉体を１
ｇ置き、石英ガラス燃焼管内の雰囲気温度を１分間に１
０度上昇するように加熱し、ポリエチレン近傍直上に設
置した熱電対により、ポリエチレンの温度を測定した。
得られた経過時間に対するポリエチレンの温度を図２に
与える。Comparative Example 1 A polyethylene glass powder having a particle size of 50 μm was placed in a quartz glass boat placed in the combustion apparatus shown in FIG.
g, and set the ambient temperature in the quartz glass combustion tube to 1 min.
The temperature of the polyethylene was measured with a thermocouple installed immediately above the polyethylene, which was heated so as to rise by 0 degree.
The temperature of polyethylene with respect to the elapsed time obtained is given in FIG.
【００３３】また、石英ガラスのボートに一切の物質を
置くことなく、上記と同様に、燃焼管内の雰囲気温度を
上昇させたときの、ボート近傍直上の温度もあわせて図
２に与える。Also, without placing any substance on the quartz glass boat, the temperature immediately above the vicinity of the boat when the atmospheric temperature in the combustion tube is raised is also given in FIG.
【００３４】また、粒径が５０μｍのポリエチレン粉体
を１ｇと平均粒径７ｎｍのアナターゼ型酸化チタン粉体
（石原産業株式会社製光触媒酸化チタンＳＴ−０１）を
０．１ｇが均一に混ざるように注意しながら金属さじで
混ぜ、これを石英ガラスのボートに置き、上記と同様
に、燃焼管内の温度を上昇させた。この際に得られた試
料近傍直上の温度もあわせて図２に与える。Further, 1 g of polyethylene powder having a particle size of 50 μm and 0.1 g of anatase type titanium oxide powder (photocatalytic titanium oxide ST-01 manufactured by Ishihara Sangyo Co., Ltd.) having an average particle size of 7 nm were mixed uniformly. Carefully mix with a metal spoon, place this in a quartz glass boat and raise the temperature in the combustion tube as above. The temperature immediately above the sample obtained at this time is also shown in FIG.
【００３５】図２において、試料を石英ガラスのボート
に入れることなく加熱したときのボート付近の温度曲線
に対し、ポリエチレン、もしくは、ポリエチレンと酸化
チタン微粒子を混合したものを試料としてボートに乗せ
て求めた温度曲線が、温度の高い側にある場合は、試料
が燃焼発熱し、これにより温度が高くなっているという
ことができる。また、空のボートを加熱したときに得ら
れる温度曲線からの温度の高い側への乖離の程度が大き
いほど発熱量が大きいということができる。In FIG. 2, the temperature curve near the boat when the sample was heated without putting it in a quartz glass boat was determined by placing polyethylene or a mixture of polyethylene and titanium oxide fine particles on the boat as a sample. If the temperature curve is on the higher temperature side, it can be said that the sample heats up due to combustion, which causes the temperature to rise. Further, it can be said that the larger the degree of deviation from the temperature curve obtained when an empty boat is heated to the higher temperature side, the larger the amount of heat generation.
【００３６】これら３つの昇温の結果から、ここで用い
たポリエチレンは３８０℃付近で着火することがわか
る。また、酸化チタン微粒子を混ぜた場合は、燃焼開始
温度が３３０℃付近まで低下しているが、発熱量はポリ
エチレンのみを加熱した場合に比べて極めて大きいとは
いえず、燃焼温度を上昇させることによるダイオキシン
などの有害物質の生成を抑制する効果は大きくないもの
といえるFrom the results of these three temperature rises, it can be seen that the polyethylene used here ignites at around 380 ° C. In addition, when titanium oxide fine particles are mixed, the combustion start temperature is lowered to around 330 ° C, but the calorific value is not extremely large as compared with the case where only polyethylene is heated, and the combustion temperature should be increased. It can be said that the effect of suppressing the generation of toxic substances such as dioxins due to water is not great.
【００３７】[0037]
【実施例４】粒径が５０μｍのポリエチレン粉体１ｇと
実施例１において得られた過酸化チタン微粒子からなる
粉体０．１ｇが均一に混ざるように注意しながら金属さ
じで混ぜ、加熱用試料とした。図１に示す燃焼装置内に
置かれた石英ガラスのボートに、作成した試料を置き、
石英ガラス燃焼管内の雰囲気温度を１分間に１０度上昇
するように加熱し、試料近傍直上に設置した熱電対によ
り、試料の温度を測定した。得られた経過時間に対する
試料の温度を図３に与える。図３には、比較例１で得ら
れた空のボートを加熱した際の温度曲線とポリエチレン
粉体を加熱した際の温度曲線をあわせて与える。[Example 4] A heating sample was prepared by mixing 1 g of polyethylene powder having a particle size of 50 µm and 0.1 g of the titanium peroxide fine particles obtained in Example 1 with a metal spoon while being careful to mix them uniformly. And The prepared sample was placed in a quartz glass boat placed in the combustion apparatus shown in FIG.
The atmosphere temperature in the quartz glass combustion tube was heated so as to increase by 10 degrees per minute, and the temperature of the sample was measured by a thermocouple installed immediately above the vicinity of the sample. The temperature of the sample with respect to the elapsed time obtained is given in FIG. In FIG. 3, the temperature curve when heating the empty boat obtained in Comparative Example 1 and the temperature curve when heating the polyethylene powder are given together.
【００３８】図３より、過酸化チタン微粒子を混ぜるこ
とにより、燃焼開始温度が１０度以上低下し、さらに、
発熱量も増加していることがわかる。これより、燃焼温
度の上昇によりダイオキシンなどの有害物質の生成が抑
制されるといえる。As shown in FIG. 3, by mixing the titanium peroxide fine particles, the combustion starting temperature was lowered by 10 degrees or more.
It can be seen that the calorific value is also increasing. From this, it can be said that the production of harmful substances such as dioxins is suppressed by the increase in the combustion temperature.
【００３９】[0039]
【実施例５】粒径が５０μｍのポリエチレン粉体１ｇと
実施例２において得られた過酸化チタンを被覆した酸化
チタン微粒子からなる粉体０．１ｇが均一に混ざるよう
に注意しながら金属さじで混ぜ、加熱用試料とした。試
料を変える以外は実施例４と同様にして、温度曲線を求
めた。得られた温度曲線を図３に与える。Example 5 1 g of polyethylene powder having a particle size of 50 μm and 0.1 g of fine particles of titanium oxide particles coated with titanium peroxide obtained in Example 2 were uniformly mixed with a metal spoon while being careful. The mixture was mixed and used as a heating sample. A temperature curve was obtained in the same manner as in Example 4 except that the sample was changed. The temperature curve obtained is given in FIG.
【００４０】図３より、過酸化チタンを被覆した酸化チ
タン微粒子を混ぜることにより、燃焼開始温度が１０度
近く低下し、さらに、発熱量も増加していることがわか
る。これより、燃焼温度の上昇によりダイオキシンなど
の有害物質の生成が抑制されるといえる。It can be seen from FIG. 3 that by mixing the titanium oxide fine particles coated with titanium peroxide, the combustion starting temperature is lowered by about 10 degrees and the calorific value is increased. From this, it can be said that the production of harmful substances such as dioxins is suppressed by the increase in the combustion temperature.
【００４１】[0041]
【実施例６】粒径が５０μｍのポリエチレン粉体１ｇと
実施例３において得られた過酸化チタンを被覆した酸化
チタン微粒子からなる粉体０．１ｇが均一に混ざるよう
に注意しながら金属さじで混ぜ、加熱用試料とした。試
料を変える以外は実施例４と同様にして、温度曲線を求
めた。得られた温度曲線を図３に与える。Example 6 1 g of polyethylene powder having a particle size of 50 μm and 0.1 g of fine particles of titanium oxide fine particles coated with titanium peroxide obtained in Example 3 were carefully mixed with a metal spoon. The mixture was mixed and used as a heating sample. A temperature curve was obtained in the same manner as in Example 4 except that the sample was changed. The temperature curve obtained is given in FIG.
【００４２】図３より、過酸化チタンを被覆した酸化チ
タン微粒子を混ぜることにより、燃焼開始温度が６０度
近く低下し、さらに、発熱量も増加していることがわか
る。これより、燃焼温度の上昇によりダイオキシンなど
の有害物質の生成が抑制されるといえる。It can be seen from FIG. 3 that the combustion start temperature is lowered by about 60 ° C. and the calorific value is increased by mixing the titanium oxide fine particles coated with titanium peroxide. From this, it can be said that the production of harmful substances such as dioxins is suppressed by the increase in the combustion temperature.
【００４３】[0043]
【実施例７】平均粒径７ｎｍのアナターゼ型酸化チタン
粉体（石原産業株式会社製光触媒酸化チタンＳＴ−０
１）の光触媒活性能を以下の方法で求めた。上記酸化チ
タン粉体１．０ｇを容積１Ｌのガラス容器にできるだけ
多くの粉体が紫外光に照射される状態にして広げ、ガラ
ス容器中の濃度が約２００００ｐｐｍになるようにアセ
トアルデヒド気体を注入した。この状態で、２０時間弱
静置してアセトアルデヒドの一部が粉体やガラス容器内
壁に吸着され、平衡状態になり、アセトアルデヒドのガ
ラス容器内の濃度に変化がなくなってから、該ガラス容
器を１ｍＷの紫外光照射下に置いた。紫外光照射を５時
間継続し、この間に数回、ガスシリンジにてガラス容器
内の気体を採取し、ガスクロマトグラフにより、アセト
アルデヒドの分解生成物である二酸化炭素の濃度を測定
した。Example 7 Anatase type titanium oxide powder having an average particle size of 7 nm (photocatalyst titanium oxide ST-0 manufactured by Ishihara Sangyo Co., Ltd.)
The photocatalytic activity of 1) was determined by the following method. 1.0 g of the above titanium oxide powder was spread in a glass container having a volume of 1 L in a state where as much powder as possible was irradiated with ultraviolet light, and acetaldehyde gas was injected so that the concentration in the glass container was about 20,000 ppm. In this state, the mixture was left standing for a little less than 20 hours, and a part of acetaldehyde was adsorbed on the powder or the inner wall of the glass container to reach an equilibrium state, and the concentration of acetaldehyde in the glass container remained unchanged. Under UV light irradiation. The irradiation with ultraviolet light was continued for 5 hours, during which the gas in the glass container was sampled several times with a gas syringe, and the concentration of carbon dioxide, which is a decomposition product of acetaldehyde, was measured by gas chromatography.
【００４４】酸化チタン粉体を、実施例１によって得ら
れた粉体に換えた以外は上記と同様にして、二酸化炭素
の濃度を調べた。The carbon dioxide concentration was examined in the same manner as above except that the titanium oxide powder was replaced with the powder obtained in Example 1.
【００４５】酸化チタン粉体、及び、実施例１で得られ
た過酸化チタン粉体は、５時間までおこなった紫外線照
射の範囲では、共通に、紫外線照射時間に比例した量の
二酸化炭素を生成した。二酸化炭素の濃度の時間に対す
る傾きから求めた過酸化チタンを被覆した酸化チタンの
光触媒活性能は、酸化チタンを１とすると０．３であっ
た。これから、実施例１によって得られた過酸化チタン
粉体は、混練される有機物を分解する速度が大きくな
く、混練された有機物を用いた製品の寿命を著しく短く
しないといえる。The titanium oxide powder and the titanium peroxide powder obtained in Example 1 commonly produce carbon dioxide in an amount proportional to the ultraviolet irradiation time in the range of ultraviolet irradiation up to 5 hours. did. The photocatalytic activity of titanium oxide coated with titanium peroxide, which was determined from the slope of the concentration of carbon dioxide with respect to time, was 0.3 assuming that titanium oxide was 1. From this, it can be said that the titanium peroxide powder obtained in Example 1 does not have a high rate of decomposing the kneaded organic matter and does not significantly shorten the life of the product using the kneaded organic matter.
【００４６】さらに、酸化チタン粉体を、実施例１で得
られた過酸化チタン粉体を６００℃で３０分間、大気中
で加熱したものに換えた以外は上記と同様にして、二酸
化炭素の濃度を調べた。かかる粉体の光触媒活性能は、
酸化チタンを１とすると０．８であった。これから、実
施例１で得られた過酸化チタン粉体は、６００℃、３０
分間の加熱後には、ダイオキシンなどの有害物質を分解
するのに十分な光触媒活性能を有することがわかる。Further, the same procedure as described above was repeated except that the titanium oxide powder was replaced with the titanium peroxide powder obtained in Example 1 heated at 600 ° C. for 30 minutes in the atmosphere. The concentration was checked. The photocatalytic activity of the powder is
When titanium oxide was set to 1, it was 0.8. From this, the titanium peroxide powder obtained in Example 1 is
It can be seen that after heating for a minute, it has a photocatalytic activity sufficient to decompose harmful substances such as dioxins.
【００４７】[0047]
【実施例８】実施例１で得られた過酸化チタン粉体を６
００℃で１５分間、大気中で加熱して得られる粉体の光
触媒活性能を実施例７と同様にして求めた。得られた光
触媒活性能は、酸化チタンを１とすると０．４であっ
た。この結果から、加熱温度が６００℃と低いときは、
その加熱時間が１５分間では、光触媒活性が発現すると
はいえ、極めて大きいとはいえず、かかる粉体を含んだ
有機物の処理においては、焼却時間の少なくとも３０分
までの延長、あるいは、燃焼温度の増加が必要であるこ
とがわかる。Example 8 The titanium peroxide powder obtained in Example 1 was
The photocatalytic activity of the powder obtained by heating in air at 00 ° C. for 15 minutes was determined in the same manner as in Example 7. The photocatalytic activity obtained was 0.4 assuming that titanium oxide was 1. From this result, when the heating temperature is as low as 600 ° C,
Although the photocatalytic activity is manifested when the heating time is 15 minutes, it cannot be said that it is extremely large, and in the treatment of the organic substance containing such powder, the incineration time is extended to at least 30 minutes or the combustion temperature is increased. It turns out that an increase is necessary.
【００４８】[0048]
【実施例９】実施例２で得られた過酸化チタンで被覆し
た酸化チタン粉体の光触媒活性能を実施例７と同様にし
て求めた。得られた光触媒活性能は、酸化チタンを１と
すると０．２であった。これから、実施例２によって得
られた過酸化チタンを被覆した酸化チタン粉体は、混練
される有機物を分解する速度が大きくなく、混練された
有機物を用いた製品の寿命を著しく短くしないとえる。Example 9 The photocatalytic activity of the titanium oxide powder coated with titanium peroxide obtained in Example 2 was determined in the same manner as in Example 7. The obtained photocatalytic activity was 0.2 assuming that titanium oxide was 1. From this, it can be said that the titanium oxide powder coated with titanium peroxide obtained in Example 2 does not have a high rate of decomposing the kneaded organic matter and does not significantly shorten the life of the product using the kneaded organic matter.
【００４９】さらに、実施例２で得られた過酸化チタン
で被覆した酸化チタン粉体を６００℃で１５分間、大気
中で加熱して得られる粉体の光触媒活性能を実施例７と
同様にして求めた。得られた光触媒活性能は、酸化チタ
ンを１とすると０．８であった。これから、実施例２で
得られた過酸化チタン粉体は、６００℃、１５分間の加
熱後には、ダイオキシンなどの有害物質を分解するのに
十分な光触媒活性能を有することがわかる。Further, the titanium oxide powder coated with titanium peroxide obtained in Example 2 was heated at 600 ° C. for 15 minutes in the atmosphere, and the photocatalytic activity of the powder obtained was the same as in Example 7. I asked. The obtained photocatalytic activity was 0.8 assuming that titanium oxide was 1. From this, it can be seen that the titanium peroxide powder obtained in Example 2 has a photocatalytic activity sufficient to decompose harmful substances such as dioxins after heating at 600 ° C. for 15 minutes.
【００５０】[0050]
【実施例１０】実施例３で得られた過酸化チタンで被覆
した酸化チタン粉体の光触媒活性能を実施例７と同様に
して求めた。得られた光触媒活性能は、酸化チタンを１
とすると０．３であった。これから、実施例２によって
得られた過酸化チタンを被覆した酸化チタン粉体は、混
練される有機物を分解する速度が大きくなく、混練され
た有機物を用いた製品寿命を著しく短くしないといえ
る。Example 10 The photocatalytic activity of the titanium oxide powder coated with titanium peroxide obtained in Example 3 was determined in the same manner as in Example 7. The obtained photocatalytic activity is 1
Then, it was 0.3. From this, it can be said that the titanium oxide powder coated with titanium peroxide obtained in Example 2 does not have a high rate of decomposing the kneaded organic matter, and does not significantly shorten the product life using the kneaded organic matter.
【００５１】さらに、実施例３で得られた過酸化チタン
で被覆した酸化チタン粉体を６００℃で１５分間、大気
中で加熱して得られる粉体の光触媒活性能を実施例７と
同様にして求めた。得られた光触媒活性能は、酸化チタ
ンを１とすると０．９であった。これから、実施例３で
得られた過酸化チタン粉体は、６００℃、１５分間の加
熱後には、ダイオキシンなどの有害物質を分解するのに
十分な光触媒活性能を有することがわかる。Further, the titanium oxide powder coated with titanium peroxide obtained in Example 3 was heated in the air at 600 ° C. for 15 minutes to obtain a powder having the same photocatalytic activity as in Example 7. I asked. The obtained photocatalytic activity was 0.9 assuming that titanium oxide was 1. From this, it is understood that the titanium peroxide powder obtained in Example 3 has sufficient photocatalytic activity to decompose harmful substances such as dioxins after heating at 600 ° C. for 15 minutes.
【００５２】[0052]
【実施例１１】実施例３において、用いるペルオキソチ
タン酸溶液を５ｇとした以外は同様にして、過酸化チタ
ンで被覆した酸化チタン粉体を得た。得られた粉体の光
触媒活性能を実施例７と同様にして求めた。得られた光
触媒活性能は、酸化チタンを１とすると０．６であっ
た。Example 11 A titanium oxide powder coated with titanium peroxide was obtained in the same manner as in Example 3 except that the peroxotitanic acid solution used was 5 g. The photocatalytic activity of the obtained powder was determined in the same manner as in Example 7. The obtained photocatalytic activity was 0.6 assuming that titanium oxide was 1.
【００５３】さらに、得られた粉体を６００℃で１５分
間、大気中で加熱し、この粉体の光触媒活性能を実施例
７と同様にして求めた。得られた光触媒活性能は、酸化
チタンを１とすると１であった。これらの結果から、過
酸化チタンの被覆が十分でないことが推測される。しか
しながら、得られた粉体を含ませた有機物を製品に用い
た場合、焼却処分後に生成したダイオキシンなどの有害
物質の分解には十分な光触媒活性能を有しており、製品
に求められる寿命が長くない製品に用いることが有用で
あると理解される。Further, the obtained powder was heated at 600 ° C. for 15 minutes in the atmosphere, and the photocatalytic activity of this powder was determined in the same manner as in Example 7. The obtained photocatalytic activity was 1 when titanium oxide was 1. From these results, it is assumed that the titanium peroxide coating is not sufficient. However, when an organic substance containing the obtained powder is used for a product, it has sufficient photocatalytic activity for decomposing harmful substances such as dioxins generated after incineration, and has a long life required for the product. It is understood to be useful for use in products that are not long.
【効果】有機物の焼却時に、ダイオキシンなどの有害物
質の生成を抑制し、かつ、生成した有害物を分解しう
る。[Effect] It is possible to suppress the production of harmful substances such as dioxins when incinerating organic substances, and to decompose the generated harmful substances.
【図１】有機物質、及び、有機物質と酸化物微粒子の混
合物を加熱するための装置の概略図。FIG. 1 is a schematic view of an apparatus for heating an organic substance and a mixture of the organic substance and oxide fine particles.
【図２】図１の加熱装置において求めた比較のための温
度曲線（試料用ボートが空の際のボートの温度曲線、試
料用ボートにポリエチレンを入れた際の温度曲線、及
び、試料用ボートにポリエチレンと酸化チタンの混合物
を入れた際の温度曲線）。2 is a temperature curve for comparison obtained by the heating device of FIG. 1 (a temperature curve of a boat when the sample boat is empty, a temperature curve when polyethylene is put in the sample boat, and a sample boat). Temperature curve when a mixture of polyethylene and titanium oxide was added to the.
【図３】図１の加熱装置において求めた本発明にかかる
温度曲線（試料用ボートにポリエチレンと過酸化チタン
の混合物を入れた際の温度曲線、試験用ボートにポリエ
チレンと過酸化チタンで被覆した酸化チタンの混合物を
入れた際の温度曲線）、および、比較のための温度曲線
（試料用ボートが空の際の温度曲線と、試料用ボートに
ポリエチレンのみを入れた際の温度曲線）。FIG. 3 shows a temperature curve according to the present invention obtained by the heating apparatus of FIG. 1 (a temperature curve when a mixture of polyethylene and titanium peroxide is put into a sample boat, and a test boat is coated with polyethylene and titanium peroxide). A temperature curve when a mixture of titanium oxide was added), and a temperature curve for comparison (a temperature curve when the sample boat was empty and a temperature curve when only polyethylene was put in the sample boat).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０９Ｂ 3/00 Ｃ０７Ｄ 319/24 ＺＡＢ Ｂ０９Ｂ 3/00 ３０３Ｆ Ｃ０１Ｇ 23/04 ＺＡＢ Ｃ０７Ｄ 319/24 ３０４Ｚ Ｂ０１Ｄ 53/36 Ｊ Ｇ (72)発明者 斎木 千恵子 東京都府中市本町４−15−８グランデルコ ートＡ棟２号室 (72)発明者 渡部 俊也 神奈川県藤沢市鵠沼海岸６−15−７ (72)発明者 橋本 和仁 神奈川県横浜市栄区飯島町2073−２−Ｄ 213 Ｆターム(参考） 2E191 BA12 BB00 BD13 BD17 4D004 AA07 AA36 AA37 AB07 CA28 CA34 CA43 CC09 4D048 AA11 AB03 BA07X BA13X BA41X BB01 BB17 EA01 4G047 CA02 CB08 CC03 CD02 4G069 AA03 AA08 BA04A BA04B BA48A BB04A BC50A BC50B CA04 CA10 CA19 EA01X EA01Y EA02X EB18X EB18Y EB19 EE01 FA01 FA03 FB06 FB15 FB16 FB57 FC07 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B09B 3/00 C07D 319/24 ZAB B09B 3/00 303F C01G 23/04 ZAB C07D 319/24 304Z B01D 53 / 36 J G (72) Inventor Chieko Saiki 4-15-8 Honmachi, Fuchu-shi, Tokyo Room 2 of Grand Del Coat A Building (72) Inventor Toshiya Watanabe 6-15-7 Kugenuma Kaigan, Fujisawa-shi, Kanagawa (72) Inventor Kazuhito Hashimoto 2073-2-D 213 F term, Iijima-cho, Sakae-ku, Yokohama-shi, Kanagawa 2E191 BA12 BB00 BD13 BD17 4D004 AA07 AA36 AA37 AB07 CA28 CA34 CA43 CC09 4D048 AA11 AB03 BA07X BA13X BA41X BB01 BB17 EA01 4G047 CA02 408 CC02 CA02 AA08 BA04A BA04B BA48A BB04A BC50A BC50B CA04 CA10 CA19 EA01X EA01Y EA02X EB18X EB18Y EB19 EE01 FA01 FA03 FB06 FB15 FB16 FB57 FC07
Claims (21)
粒子。1. Metal oxide fine particles coated with titanium peroxide.
を持つことを特徴とする請求項１に記載の微粒子。2. The fine particles according to claim 1, having a maximum outer diameter of 5 nm to 1 mm.
とする請求項１または２に記載の金属酸化物微粒子。3. The metal oxide fine particles according to claim 1, which are fine particles for adding an organic substance.
濁液中に分散させ、金属酸化物微粒子を過酸化チタンで
被覆し、この後、３００℃未満の雰囲気中で乾燥して得
られる請求項１から３のいずれか１項に記載の微粒子。4. The metal oxide fine particles are obtained by dispersing the metal oxide fine particles in a titanium peroxide sol suspension, coating the metal oxide fine particles with titanium peroxide, and then drying in an atmosphere of less than 300 ° C. 4. The fine particles according to any one of 1 to 3.
徴とする請求項１から４のいずれか１項に記載の微粒
子。5. The fine particles according to any one of claims 1 to 4, wherein the metal oxide is titanium oxide.
分散させ、表面に過酸化チタン層を形成した後、３００
℃未満の雰囲気中で乾燥して得られる請求項１から３の
いずれか１項に記載の微粒子。6. Titanium oxide fine particles are dispersed in an aqueous hydrogen peroxide solution to form a titanium peroxide layer on the surface, and then 300
The fine particles according to any one of claims 1 to 3, which are obtained by drying in an atmosphere of less than ° C.
で加熱することにより光触媒活性微粒子となることを特
徴とする請求項１から６のいずれか１項に記載の微粒
子。7. The fine particles according to any one of claims 1 to 6, which are photocatalytically active fine particles when heated in a temperature range of 300 ° C. or higher and 900 ° C. or lower.
子であって、３００℃以上、９００℃以下の温度範囲で
加熱することにより光触媒活性を生じることを特徴とす
る過酸化チタン微粒子。8. Fine particles of a photocatalyst precursor to which an organic substance is added, wherein the fine particles of titanium peroxide exhibit photocatalytic activity when heated in a temperature range of 300 ° C. or higher and 900 ° C. or lower.
を持った粉体であることを特徴とする請求項８に記載の
微粒子。9. The fine particle according to claim 8, which is a powder having a maximum outer diameter of 5 nm to 1 mm.
の微粒子、あるいは、請求項８または９に記載の微粒子
の、いずれか少なくとも一方を含む有機物。10. An organic substance containing at least one of the fine particles according to any one of claims 1 to 7 or the fine particles according to claim 8 or 9.
徴とする請求項１０に記載の有機物。11. The organic substance according to claim 10, wherein the organic substance is a polymer material.
レン、ポリスチレン、ポリプロピレン、ポリエチレンテ
レフタレート、ポリカーボネート、ポリ塩化ビニルを含
むことを特徴とした請求項１１に記載の有機物。12. The organic substance according to claim 11, wherein the polymer material contains at least polyethylene, polystyrene, polypropylene, polyethylene terephthalate, polycarbonate and polyvinyl chloride.
０．５重量％以上、５０重量％以下であることを特徴と
する請求項１０から１２のいずれか１項に記載の有機
物。13. The total content of fine particles with respect to the whole is
It is 0.5% by weight or more and 50% by weight or less, and the organic substance according to any one of claims 10 to 12, which is characterized in that.
する請求項１０から１３のいずれか１項に記載の有機
物。14. The organic substance according to claim 10, wherein the fine particles have an auxiliary combustion effect.
時におけるダイオキシンなどの有害物質の発生量が少な
いことを特徴とする請求項１０から１４のいずれか１項
に記載の有機物。15. The organic substance according to any one of claims 10 to 14, wherein the amount of harmful substances such as dioxins generated during combustion is smaller than that when no fine particles are present.
ら１５に記載した有機物を併せて燃焼させることを特徴
とする、ダイオキシンなどの有害物質の生成を抑制する
有機物の処分方法。16. A method of disposing an organic substance, which suppresses the production of harmful substances such as dioxins, which comprises burning the organic substance according to any one of claims 10 to 15 when disposing the organic substance.
記載した有機物を含む有機物を燃焼後、その焼却灰や飛
灰を紫外線の照射される環境に置くことにより、生成し
たダイオキシンなどの有害物質を分解する方法。17. A harmful substance such as dioxins produced by burning the organic matter containing the organic matter according to any one of claims 10 to 15 and then placing the incinerated ash or fly ash in an environment irradiated with ultraviolet rays. A method of decomposing substances.
記載した有機物を燃焼させることにより、ダイオキシン
などの有害物質の生成を抑制し、かつ、燃焼後にその焼
却灰や飛灰を紫外線の照射される環境に置くことによ
り、生成したダイオキシンなどの有害物質を分解する有
機物の処分方法。18. Combustion of the organic matter according to any one of claims 10 to 15 suppresses the production of harmful substances such as dioxins, and irradiates the incineration ash or fly ash with ultraviolet rays after combustion. A method of disposing of organic substances that decomposes harmful substances such as dioxins generated by placing them in an environment where
の微粒子、あるいは、請求項８または９に記載の微粒子
の、いずれか少なくとも一方を、燃焼前、あるいは、燃
焼中に有機物と混ぜることにより、ダイオキシンなどの
有害物質の生成を抑制する有機物の処分方法。19. The fine particles according to any one of claims 1 to 7 or at least one of the fine particles according to claim 8 or 9 is mixed with an organic substance before or during combustion. By doing so, a method of disposing of organic substances that suppresses the production of harmful substances such as dioxins.
の微粒子、あるいは、請求項８または９に記載の微粒子
の、いずれか少なくとも一方を、燃焼前、あるいは、燃
焼中に有機物と混ぜて燃焼させた後、その焼却灰や飛灰
を紫外線の照射される環境に置くことにより、生成した
ダイオキシンなどの有害物質を分解する有機物の処分方
法。20. At least one of the fine particles according to any one of claims 1 to 7 or the fine particles according to claim 8 or 9 is mixed with an organic substance before or during combustion. A method of disposing of organic matter that decomposes harmful substances such as dioxins generated by placing the incinerated ash or fly ash in an environment where it is exposed to ultraviolet rays after being burned by burning.
の微粒子、あるいは、請求項８または９に記載の微粒子
の、いずれか少なくとも一方を、燃焼前、あるいは、燃
焼中に有機物と混ぜることにより、ダイオキシンなどの
有害物質の生成を抑制し、かつ、燃焼後にその焼却灰や
飛灰を紫外線の照射される環境に置くことにより、生成
したダイオキシンなどの有害物質を分解する有機物の処
分方法。21. Mixing at least one of the fine particles according to any one of claims 1 to 7 or the fine particles according to claim 8 or 9 with an organic substance before or during combustion. By suppressing the generation of harmful substances such as dioxin, and by disposing the incinerated ash and fly ash in the environment where ultraviolet rays are irradiated after combustion, a method of disposing of organic substances that decomposes the generated dioxin and other harmful substances. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001279152A JP2003089521A (en) | 2001-09-14 | 2001-09-14 | Fine oxide particle which suppresses generation of harmful substance in combustion and decomposes the substance, method for producing the fine particle, organic matter containing the fine particle, and method for disposing of organic matter using the fine particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001279152A JP2003089521A (en) | 2001-09-14 | 2001-09-14 | Fine oxide particle which suppresses generation of harmful substance in combustion and decomposes the substance, method for producing the fine particle, organic matter containing the fine particle, and method for disposing of organic matter using the fine particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003089521A true JP2003089521A (en) | 2003-03-28 |
Family
ID=19103399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001279152A Pending JP2003089521A (en) | 2001-09-14 | 2001-09-14 | Fine oxide particle which suppresses generation of harmful substance in combustion and decomposes the substance, method for producing the fine particle, organic matter containing the fine particle, and method for disposing of organic matter using the fine particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003089521A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004069946A1 (en) * | 2003-02-10 | 2004-08-19 | Kansai Paint Co., Ltd. | Coating material for forming photocatalyst/titanium oxide composite film |
-
2001
- 2001-09-14 JP JP2001279152A patent/JP2003089521A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004069946A1 (en) * | 2003-02-10 | 2004-08-19 | Kansai Paint Co., Ltd. | Coating material for forming photocatalyst/titanium oxide composite film |
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