JP2001302241A - Method for producing titanium oxide - Google Patents
Method for producing titanium oxideInfo
- Publication number
- JP2001302241A JP2001302241A JP2000122126A JP2000122126A JP2001302241A JP 2001302241 A JP2001302241 A JP 2001302241A JP 2000122126 A JP2000122126 A JP 2000122126A JP 2000122126 A JP2000122126 A JP 2000122126A JP 2001302241 A JP2001302241 A JP 2001302241A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- titanium
- weight
- hydroxide
- titanium hydroxide
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 6
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 239000013078 crystal Substances 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910001040 Beta-titanium Inorganic materials 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 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 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- LLQPHQFNMLZJMP-UHFFFAOYSA-N Fentrazamide Chemical compound N1=NN(C=2C(=CC=CC=2)Cl)C(=O)N1C(=O)N(CC)C1CCCCC1 LLQPHQFNMLZJMP-UHFFFAOYSA-N 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- VULAXXNFNMUCIP-UHFFFAOYSA-M [NH4+].[O-]S(=O)(=O)O[Ti] Chemical compound [NH4+].[O-]S(=O)(=O)O[Ti] VULAXXNFNMUCIP-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- OKCGHURFTRSMMX-UHFFFAOYSA-K titanium(3+);trihydroxide Chemical compound O[Ti](O)O OKCGHURFTRSMMX-UHFFFAOYSA-K 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は酸化チタンの製造方
法に関するものであり、詳細には、可視光線を照射する
ことによって優れた光触媒活性を示す酸化チタンの製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing titanium oxide, and more particularly, to a method for producing titanium oxide which exhibits excellent photocatalytic activity when irradiated with visible light.
【0002】[0002]
【従来の技術】半導体に光を照射すると強い還元作用を
持つ電子と強い酸化作用を持つ正孔が生成し、半導体に
接触した分子種を酸化還元作用により分解する。このよ
うな半導体を通常光触媒と呼び、この光触媒を利用する
ことによって、大気中のＮＯｘの分解、居住空間や作業
空間での悪臭物質やカビなどの分解除去、あるいは水中
の有機溶剤や農薬、界面活性剤などの環境汚染物質の分
解除去を行うことが可能となる。2. Description of the Related Art When a semiconductor is irradiated with light, electrons having a strong reducing action and holes having a strong oxidizing action are generated, and molecular species in contact with the semiconductor are decomposed by the redox action. Such a semiconductor is usually called a photocatalyst. By using this photocatalyst, it can decompose NOx in the atmosphere, decompose and remove odorous substances and mold in living and working spaces, or use organic solvents, pesticides, and It becomes possible to decompose and remove environmental pollutants such as activators.
【0003】可視光線を照射することによって触媒活性を示
す光触媒が発見され、この光触媒の製造方法として各種
提案がなされている。例えば、ＷＯ９８２３７４号公報
には、酸化チタンをマイクロ波低温プラズマ法により処
理しその表面に炭化チタンを形成することによって触媒
活性を示す酸化チタンからなる光触媒を得る方法が記載
されている。また、日本化学会第７６春季年会講演予稿
集Ｉ（４Ｆ４３２）には、マグネトロンスパッタ法によ
り基板上に酸化チタンを製膜することによって触媒活性
を示す酸化チタンからなる光触媒を得る方法が記載され
ている。[0003] Photocatalysts exhibiting catalytic activity upon irradiation with visible light have been discovered, and various proposals have been made as methods for producing such photocatalysts. For example, WO 982374 describes a method for obtaining a photocatalyst comprising titanium oxide having catalytic activity by treating titanium oxide by a microwave low-temperature plasma method and forming titanium carbide on the surface thereof. In addition, the proceedings of the 76th Annual Meeting of the Chemical Society of Japan, Spring Meeting I (4F432), describes a method for obtaining a photocatalyst composed of titanium oxide having catalytic activity by forming titanium oxide on a substrate by magnetron sputtering. ing.
【0004】しかし、ＷＯ９８２３７４号公報等に記載され
た方法では、酸化チタンを処理又は製膜するためにマイ
クロ波低温プラズマ発生装置等の真空容器を備えた特定
の装置が必要であり、操作が煩雑となる問題があった。[0004] However, in the method described in WO982374 or the like, a specific apparatus equipped with a vacuum vessel such as a microwave low-temperature plasma generator is required for treating or forming titanium oxide, and the operation is complicated. There was a problem.
【0005】[0005]
【発明が解決しようとする課題】本発明の目的は可視光
線を照射することによって優れた触媒活性を示す酸化チ
タンを真空容器を備えた特定の装置を用いることなく簡
易に製造する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for easily producing titanium oxide exhibiting excellent catalytic activity by irradiating visible light without using a specific apparatus equipped with a vacuum vessel. It is in.
【0006】[0006]
【課題を解決するための手段】本発明者等は優れた光触
媒活性を示す酸化チタンを水酸化チタンから製造するた
めの方法について検討を行った結果、本発明を完成する
に至った。Means for Solving the Problems The present inventors have studied methods for producing titanium oxide having excellent photocatalytic activity from titanium hydroxide, and as a result, the present invention has been completed.
【0007】すなわち、本発明は、水酸化チタンに、分解し
てアンモニアを発生する化合物を添加した後、焼成する
ことを特徴とする酸化チタンの製造方法を提供するもの
である。[0007] That is, the present invention provides a method for producing titanium oxide, comprising adding a compound capable of decomposing to generate ammonia to titanium hydroxide, followed by firing.
【0008】[0008]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明に用いられる水酸化チタンは、Ｔｉ（ＯＨ）2な
る組成式で表される水酸化チタン（II）、Ｔｉ（ＯＨ）
3なる組成式で表される水酸化チタン（III）、Ｔｉ（Ｏ
Ｈ）4なる組成式で表される水酸化チタン（IV）、Ｔｉ
Ｏ（ＯＨ）2なる組成式で表されるオキシ水酸化チタ
ン、Ｈ 4ＴｉＯ4なる組成式で表されるα−チタン酸（オ
ルトチタン酸と呼ばれることもある。）、Ｈ2ＴｉＯ3な
る組成式で表されるβ−チタン酸（メタチタン酸と呼ば
れることもある。）等が挙げられる。また、水酸化チタ
ンは非晶質相を含むものであることが好ましい。非晶質
相の割合が高いほど、得られる酸化チタンは可視光線の
照射によって高い光触媒作用を示す傾向がある。非晶質
相の割合はＸ線回折法により求めることができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The titanium hydroxide used in the present invention is Ti (OH)TwoWhat
(II) hydroxide and Ti (OH) represented by the following composition formula:
ThreeTitanium (III) hydroxide and Ti (O) represented by the following composition formula:
H)FourTitanium (IV) hydroxide represented by the following composition formula:
O (OH)TwoOxyhydroxide titer represented by the following formula:
N, H FourTiOFourΑ-titanic acid represented by the composition formula
Sometimes referred to as orthotitanic acid. ), HTwoTiOThreeWhat
Β-titanic acid (also called metatitanic acid)
It may be. ) And the like. Also, hydroxylated titanium
Preferably, the resin contains an amorphous phase. Amorphous
The higher the proportion of phases, the more the resulting titanium oxide
Irradiation tends to exhibit high photocatalysis. Amorphous
The proportion of the phase can be determined by the X-ray diffraction method.
【0009】また、水酸化チタンは窒素又は窒素化合物を含
むものであることが好ましい。窒素又は窒素化合物（以
下、窒素化合物等という。）の含有量が高い水酸化チタ
ンを用いることによって、より高い光触媒作用を示す酸
化チタンを得ることが可能となる。窒素化合物等の含有
量は窒素原子換算で０．２重量％以上、好ましくは１．
０重量％以上、より好ましくは２．５重量％以上であ
る。窒素化合物等の含有量は、例えば、窒素分析装置を
用い、溶融法により求めることができる。[0009] The titanium hydroxide preferably contains nitrogen or a nitrogen compound. By using titanium hydroxide having a high content of nitrogen or a nitrogen compound (hereinafter, referred to as a nitrogen compound or the like), titanium oxide having a higher photocatalytic action can be obtained. The content of nitrogen compounds and the like is 0.2% by weight or more, preferably 1.
0% by weight or more, more preferably 2.5% by weight or more. The content of the nitrogen compound and the like can be determined, for example, by a melting method using a nitrogen analyzer.
【0010】この水酸化チタンは、例えば、オキシ硫酸チタ
ン溶液にアンモニア水又は水酸化アルカリ等のアルカリ
を添加して析出させる方法、塩化チタンに水又はアンモ
ニア水を添加して加水分解する方法で得ることができ
る。[0010] The titanium hydroxide is obtained by, for example, a method of adding ammonia water or an alkali such as an alkali hydroxide to a titanium oxysulfate solution to cause precipitation, or a method of adding water or ammonia water to titanium chloride and hydrolyzing it. be able to.
【0011】本発明で用いられる分解してアンモニアを発生
する化合物（以下、アンモニア発生化合物という。）と
しては、例えば、硫酸アンモニウム、塩化アンモニウ
ム、炭酸アンモニウム、硝酸アンモニウム、りん酸アン
モニウム、酢酸アンモニウム等のアンモニウム塩、尿
素、塩基性硫酸チタニウムアンモニウム（(ＮＨ4)2ＳＯ
4・ＴｉＯＳＯ4）のようなチタン含有アンモニウム塩が
挙げられる。これらの中でも硫酸アンモニウムを用いる
ことが好ましい。The compound used in the present invention that decomposes to generate ammonia (hereinafter, referred to as an ammonia-generating compound) includes, for example, ammonium salts such as ammonium sulfate, ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium phosphate, and ammonium acetate. , Urea, basic titanium ammonium sulfate ((NH 4 ) 2 SO
Titanium-containing ammonium salts such as 4 • TiOSO 4 ). Among them, it is preferable to use ammonium sulfate.
【0012】水酸化チタンに対するアンモニア発生化合物の
添加量は、当該水酸化チタンを４００℃の空気中で焼成
した後の重量に対する当該分解してアンモニアを発生す
る化合物中窒素原子の重量の比として、０．１重量％以
上、好ましくは０．３重量％以上、より好ましくは１．
０重量％以上であり、また、１０重量％以下、さらには
５重量％以下が適当である。The amount of the ammonia-generating compound added to the titanium hydroxide is defined as the ratio of the weight of nitrogen atoms in the compound that decomposes to generate ammonia to the weight after the titanium hydroxide is calcined in air at 400 ° C. 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 1.
It is at least 0% by weight, preferably at most 10% by weight, more preferably at most 5% by weight.
【0013】焼成は、水酸化チタンを酸化チタンに転移さ
せ、かつアンモニア発生化合物を分解させることができ
る温度で行うことが好ましく、通常、３００℃以上、好
ましくは３５０℃以上である。また、焼成温度は６００
℃以下、さらには５００℃以下が適当である。焼成温度
が高くなり過ぎると、得られる酸化チタンの触媒活性が
低下することがある。[0013] The calcination is preferably performed at a temperature at which titanium hydroxide can be transferred to titanium oxide and the ammonia-generating compound can be decomposed, and is usually 300 ° C or higher, preferably 350 ° C or higher. The firing temperature is 600
C. or lower, more preferably 500.degree. C. or lower. If the firing temperature is too high, the catalytic activity of the resulting titanium oxide may decrease.
【0014】本発明で得られる酸化チタンは、通常、結晶構
造がアナターゼ型である。この酸化チタンは波長が４３
０ｎｍ以上である可視光線の照射によって優れた光触媒
活性を示すので、これをそのまま又は成形加工して用い
ることにより、大気中のＮＯｘの分解、居住空間や作業
空間での悪臭物質やカビなどの分解除去、あるいは水中
の有機溶剤や農薬、界面活性剤などの分解除去に適用で
きる光触媒とすることができる。The titanium oxide obtained in the present invention usually has an anatase type crystal structure. This titanium oxide has a wavelength of 43
It shows excellent photocatalytic activity by irradiation with visible light of 0 nm or more. By using this as it is or by molding it, it can decompose NOx in the air and decompose odorous substances and mold in living and working spaces. The photocatalyst can be used for removal or decomposition and removal of organic solvents, pesticides, surfactants and the like in water.
【0015】[0015]
【実施例】以下、実施例により本発明をさらに詳細に説
明するが、本発明は本実施例に限定されるものではな
い。水酸化チタン及び酸化チタンの結晶構造は以下の方
法で求めた。 水酸化チタン及び酸化チタンの結晶構造：Ｘ線回折装置
（商品名：ＲＡＤ−ＩＩＡ、理学電機工業製）を用い
て、Ｘ線管球Ｃｕ、管電圧４０ｋＶ、管電流３５ｍＡ、
発散スリット１度、散乱スリット１度、受光スリット
０．３０ｍｍ、サンプリング幅０．０２０度、走査速度
２．００度／分、測定積算回数１回の条件でＸ線回折ス
ペクトルを測定し結晶構造を同定した。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The crystal structures of titanium hydroxide and titanium oxide were determined by the following method. Crystal structure of titanium hydroxide and titanium oxide: Using an X-ray diffractometer (trade name: RAD-IIA, manufactured by Rigaku Corporation), X-ray tube Cu, tube voltage 40 kV, tube current 35 mA,
The X-ray diffraction spectrum was measured under the conditions of a divergence slit of 1 degree, a scattering slit of 1 degree, a light receiving slit of 0.30 mm, a sampling width of 0.020 degrees, a scanning speed of 2.00 degrees / minute, and a measurement integration number of 1 to determine the crystal structure. Identified.
【0016】実施例１ ［水酸化チタンの調製］０．５Ｌフラスコに水８０ｇを
入れた後、攪拌下でオキシ硫酸チタン（添川理化学製、
商品名：オキシ硫酸チタン）２０ｇを混合し溶解した。
次いで、室温で２５％アンモニア水（和光純薬製、特
級）２２．６ｇを２０秒で滴下して固形物を沈澱させ、
固形物をろ過、洗浄、乾燥して水酸化チタンを調製し
た。得られた水酸化チタンは結晶構造が非晶質であっ
た。また、この水酸化チタンにつき、窒素分析装置（商
品名：ＥＭＧＡ−２８００、堀場製作所製）を用いて、
試料量１ｍｇ、検出器 熱伝導度型、抽出温度（電力）
５７５０Ｗ、溶融金属Ｎｉ0.8g＋Ｓｎ0.5g、ルツボ メ
カニカル製、標準試料 窒化けい素（粉末、日本セラミ
ックス協会）の条件で窒素含有量を測定した結果、窒素
原子換算で３．３重量％であった。この水酸化チタン
２．００ｇを４００℃の空気中で焼成した後の重量は
１．５６ｇであった。Example 1 [Preparation of Titanium Hydroxide] After placing 80 g of water in a 0.5 L flask, titanium oxysulfate (manufactured by Soegawa Rikagaku Co., Ltd.
(Trade name: titanium oxysulfate) 20 g was mixed and dissolved.
Next, 22.6 g of 25% aqueous ammonia (manufactured by Wako Pure Chemical Industries, special grade) was dropped at room temperature in 20 seconds to precipitate a solid,
The solid was filtered, washed, and dried to prepare titanium hydroxide. The crystal structure of the obtained titanium hydroxide was amorphous. The titanium hydroxide was analyzed using a nitrogen analyzer (trade name: EMGA-2800, manufactured by Horiba, Ltd.).
Sample amount 1mg, detector thermal conductivity type, extraction temperature (power)
As a result of measuring the nitrogen content under the conditions of 5750 W, 0.8 g of molten metal Ni + 0.5 g of Sn, made of crucible mechanical, standard sample silicon nitride (powder, Japan Ceramic Society), it was 3.3% by weight in terms of nitrogen atoms. The weight after firing 2.00 g of this titanium hydroxide in air at 400 ° C. was 1.56 g.
【0017】上で調製した水酸化チタン２．００ｇに３０重
量％硫酸アンモニウム水溶液０．３４ｇを添加し、乳鉢
を用いて混合した後、乾燥して混合物を得た。ここで用
いた３０％硫酸アンモニウム水溶液０．３４ｇ中の窒素
原子の重量は０．０２２ｇであった。上で得られた混合
物１ｇをアルミナ製ルツボに入れ、箱型電気炉を用いて
４００℃の空気中で１時間焼成し、その後冷却して酸化
チタンを得た。室温から４００℃までの昇温は２００℃
／ｈで行った。得られた酸化チタンは粒子状であり、結
晶構造がアナターゼ型であった。[0017] To 2.00 g of the titanium hydroxide prepared above, 0.34 g of a 30 wt% ammonium sulfate aqueous solution was added, mixed using a mortar, and dried to obtain a mixture. The weight of nitrogen atoms in 0.34 g of the 30% ammonium sulfate aqueous solution used here was 0.022 g. 1 g of the mixture obtained above was placed in an alumina crucible, fired in a box-type electric furnace at 400 ° C. for 1 hour, and then cooled to obtain titanium oxide. 200 ° C from room temperature to 400 ° C
/ H. The obtained titanium oxide was in the form of particles and had a crystal structure of an anatase type.
【0018】直径８ｃｍ、高さ１０ｃｍ、容量約０．５リッ
トルである密閉式のパイレックス（登録商標）製反応容
器内に、直径５ｃｍのガラス製シャーレを設置し、その
シャーレ上に、上で得られた粒子状酸化チタンを置い
た。反応容器内を混合ガス（酸素と窒素との体積比が
１：４である。）で満たし、アセトアルデヒドを１３．
４μｍｏｌ封入し、反応容器の外から可視光線を照射し
た。可視光線の照射には、５００Ｗキセノンランプ（ウ
シオ電機製、商品名：オプティカルモジュレックスＳＸ
−ＵＩ５００ＸＱ、ランプＵＸＬ−５００ＳＸ）に、波
長約４３０ｎｍ以下の紫外線をカットするフィルター
（東芝硝子製、商品名：Ｙ−４５）と波長約８３０ｎｍ
以上の赤外線をカットするフィルター（ウシオ電機製、
商品名：スーパーコールドフィルター）とを装着したも
のを光源として用いた。可視光線の照射によりアセトア
ルデヒドが分解すると、二酸化炭素が発生するので二酸
化炭素の濃度を光音響マルチガスモニタ（ＩＮＮＯＶＡ
製、１３１２型）で経時的に測定し、濃度変化より算出
した二酸化炭素の生成速度により、酸化チタンのアセト
アルデヒドに対する光分解作用を評価した。二酸化炭素
の生成速度は酸化チタン１ｇあたり７９．９μｍｏｌ／
ｈであった。A glass Petri dish having a diameter of 5 cm is placed in a sealed Pyrex (registered trademark) reaction vessel having a diameter of 8 cm, a height of 10 cm, and a capacity of about 0.5 liter. The resulting particulate titanium oxide was placed. 12. Fill the reaction vessel with a mixed gas (volume ratio of oxygen to nitrogen is 1: 4) and acetaldehyde.
4 μmol was sealed, and visible light was irradiated from outside the reaction vessel. For irradiation of visible light, use a 500 W xenon lamp (made by Ushio Inc., trade name: Optical Modlex SX)
-UI500XQ, lamp UXL-500SX) and a filter (Y-45, manufactured by Toshiba Glass Co., Ltd., product name: Y-45) that cuts ultraviolet light having a wavelength of about 430 nm or less, and a wavelength of about 830 nm
A filter that cuts the above infrared rays (made by Ushio,
(Trade name: super cold filter) was used as a light source. When acetaldehyde is decomposed by irradiation of visible light, carbon dioxide is generated. Therefore, the concentration of carbon dioxide is measured by a photoacoustic multi-gas monitor (INNOVA).
, 1312), and the photodecomposition effect of titanium oxide on acetaldehyde was evaluated based on the carbon dioxide generation rate calculated from the concentration change. The production rate of carbon dioxide was 79.9 μmol / g of titanium oxide.
h.
【0019】実施例２ 実施例１において、水酸化チタンとして窒素含有量が
０．２重量％であり、結晶構造が非晶質とアナターゼ型
とである市販の水酸化チタン（商品名：β−水酸化チタ
ン、キシダ化学製）２．００ｇを用いた以外は同様にし
て酸化チタンを製造した。酸化チタンは結晶構造がアナ
ターゼ型であった。Example 2 In Example 1, commercially available titanium hydroxide having a nitrogen content of 0.2% by weight and having an amorphous and anatase crystal structure as titanium hydroxide (trade name: β- Titanium oxide was produced in the same manner except that 2.00 g of titanium hydroxide (manufactured by Kishida Chemical) was used. The titanium oxide had an anatase crystal structure.
【0020】次いで、実施例１と同様にしてアセトアルデヒ
ドに対する光分解作用を評価した。二酸化炭素の生成速
度は酸化チタン１ｇあたり１１．９μｍｏｌ／ｈであっ
た。Next, the photodegradation effect on acetaldehyde was evaluated in the same manner as in Example 1. The generation rate of carbon dioxide was 11.9 μmol / h per g of titanium oxide.
【0021】実施例３ 窒素含有量が０．２重量％であり、結晶構造が非晶質と
アナターゼ型とである市販の水酸化チタン（商品名：β
−水酸化チタン、キシダ化学製）６．００ｇに１３重量
％塩化アンモニウム水溶液４６ｇを添加し混合した後、
乾燥して混合物を得た。ここで用いたと同じ水酸化チタ
ン６．００ｇを４００℃の空気中で焼成した後の重量は
４．７６ｇであり、ここで用いた１３重量％塩化アンモ
ニウム水溶液４６ｇ中の窒素原子の重量は１．５７ｇで
あった。上で得られた混合物を実施例１と同様に焼成し
て酸化チタンを製造した。得られた酸化チタンは粒子状
であり、結晶構造がアナターゼ型であった。Example 3 Commercially available titanium hydroxide having a nitrogen content of 0.2% by weight and having an amorphous and anatase crystal structure (trade name: β
-Titanium hydroxide, manufactured by Kishida Chemical Co., Ltd.) and 6.0 g of 13 wt% aqueous ammonium chloride solution were added and mixed,
Dry to obtain a mixture. The weight after calcination of 6.00 g of the same titanium hydroxide used in the air at 400 ° C. was 4.76 g, and the weight of nitrogen atoms in 46 g of the 13% by weight aqueous ammonium chloride solution used was 1.76 g. 57 g. The mixture obtained above was fired in the same manner as in Example 1 to produce titanium oxide. The obtained titanium oxide was in the form of particles and had a crystal structure of an anatase type.
【0022】次いで、実施例１と同様にしてアセトアルデヒ
ドに対する光分解作用を評価した。二酸化炭素の生成速
度は酸化チタン１ｇあたり４．６μｍｏｌ／ｈであっ
た。Next, the photolytic action on acetaldehyde was evaluated in the same manner as in Example 1. The generation rate of carbon dioxide was 4.6 μmol / h per 1 g of titanium oxide.
【0023】比較例１ 市販の酸化チタン（商品名：Ｐ−２５、デグッサ製）の
アセトアルデヒドに対する光分解作用を実施例１と同様
にして評価した。二酸化炭素の生成速度は酸化チタン１
ｇあたり０．０μｍｏｌ／ｈであった。Comparative Example 1 The photodegradation effect of a commercially available titanium oxide (trade name: P-25, manufactured by Degussa) on acetaldehyde was evaluated in the same manner as in Example 1. The generation rate of carbon dioxide is 1
It was 0.0 μmol / h per g.
【0024】比較例２ 窒素含有量が０．２重量％であり、結晶構造が非晶質と
アナターゼ型とである市販の水酸化チタン（商品名：β
−水酸化チタン、キシダ化学製）を４００℃の空気中で
１時間焼成して、酸化チタンを製造した。得られた酸化
チタンは結晶構造がアナターゼ型であった。Comparative Example 2 Commercially available titanium hydroxide having a nitrogen content of 0.2% by weight and having a crystalline structure of amorphous and anatase type (trade name: β
-Titanium hydroxide, manufactured by Kishida Chemical Co., Ltd.) was fired in air at 400 ° C. for 1 hour to produce titanium oxide. The obtained titanium oxide had an anatase crystal structure.
【0025】次いで実施例１と同様にしてアセトアルデヒド
に対する光分解作用を評価した。二酸化炭素の生成速度
は酸化チタン１ｇあたり０．９３μｍｏｌ／ｈであっ
た。Next, the photolytic action on acetaldehyde was evaluated in the same manner as in Example 1. The generation rate of carbon dioxide was 0.93 μmol / h per 1 g of titanium oxide.
【0026】[0026]
【発明の効果】以上説明した様に、本発明によれば、波
長が４３０ｎｍ以上である可視光線を照射することによ
って優れた光触媒活性を示す酸化チタンを水酸化チタン
から簡易に製造することができる。As described above, according to the present invention, by irradiating visible light having a wavelength of 430 nm or more, titanium oxide having excellent photocatalytic activity can be easily produced from titanium hydroxide. .
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小池 宏信 愛媛県新居浜市惣開町５番１号 住友化学 工業株式会社内 Ｆターム(参考） 4G047 CA02 CB05 CC03 CD03 CD07 4G069 AA02 AA08 AA09 BA04A BA04B BA48A BB01C BB05C BC50C BD01C BD02C BD06C BD08C CA10 CA17 EA01Y EC22Y FA01 FB30 FC02 FC04 FC07 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hironobu Koike 5-1 Sokai-cho, Niihama-shi, Ehime F-term (reference) in Sumitomo Chemical Co., Ltd. 4G047 CA02 CB05 CC03 CD03 CD07 4G069 AA02 AA08 AA09 BA04A BA04B BA48A BB01C BB05C BC50C BD01C BD02C BD06C BD08C CA10 CA17 EA01Y EC22Y FA01 FB30 FC02 FC04 FC07
Claims (7)
発生する化合物を添加した後、焼成することを特徴とす
る酸化チタンの製造方法。1. A method for producing titanium oxide, comprising adding a compound that decomposes to generate ammonia to titanium hydroxide, followed by firing.
載の方法。2. The method according to claim 1, wherein the titanium hydroxide is amorphous.
有し、その含有量が窒素原子換算で０．２重量％以上で
ある請求項１又は２記載の方法。3. The method according to claim 1, wherein the titanium hydroxide contains nitrogen or a nitrogen compound, and the content thereof is 0.2% by weight or more in terms of nitrogen atoms.
アを発生する化合物の添加量が、当該水酸化チタンを４
００℃の空気中で焼成した後の重量に対する当該分解し
てアンモニアを発生する化合物中窒素原子の重量の比と
して、０．１重量％以上である請求項１〜３のいずれか
１項に記載の方法。4. The amount of a compound that decomposes titanium hydroxide to generate ammonia is added to the titanium hydroxide.
The ratio of the weight of nitrogen atoms in the compound that decomposes to generate ammonia to the weight after calcination in air at 00 ° C. is 0.1% by weight or more, according to any one of claims 1 to 3. the method of.
アンモニウム塩である請求項１〜４のいずれか１項に記
載の方法。5. The method according to claim 1, wherein the compound that decomposes to generate ammonia is an ammonium salt.
硫酸アンモニウムである請求項５記載の方法。6. The method according to claim 5, wherein the compound that decomposes to generate ammonia is ammonium sulfate.
１〜６のいずれか１項に記載の方法。7. The method according to any one of claims 1 to 6, wherein the calcination is performed at 300 ° C to 600 ° C.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000122126A JP2001302241A (en) | 2000-04-24 | 2000-04-24 | Method for producing titanium oxide |
| CA002342566A CA2342566A1 (en) | 2000-03-31 | 2001-03-29 | Process for producing titanium oxide |
| KR1020010016457A KR20010095089A (en) | 2000-03-31 | 2001-03-29 | Process for producing titanium oxide |
| US09/819,790 US6827922B2 (en) | 2000-03-31 | 2001-03-29 | Process for producing titanium oxide |
| CNB011121653A CN1210100C (en) | 2000-03-31 | 2001-03-29 | Method for preparing titanium dioxide |
| DE60107991T DE60107991T2 (en) | 2000-03-31 | 2001-03-29 | Process for producing titanium oxide |
| AU31406/01A AU781370B2 (en) | 2000-03-31 | 2001-03-29 | Process for producing titanium oxide |
| EP01302987A EP1138634B1 (en) | 2000-03-31 | 2001-03-29 | Process for producing titanium oxide |
| US10/606,295 US20040037772A1 (en) | 2000-03-31 | 2003-06-26 | Process for producing titanium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000122126A JP2001302241A (en) | 2000-04-24 | 2000-04-24 | Method for producing titanium oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001302241A true JP2001302241A (en) | 2001-10-31 |
Family
ID=18632645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000122126A Pending JP2001302241A (en) | 2000-03-31 | 2000-04-24 | Method for producing titanium oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001302241A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1338564A2 (en) | 2002-02-25 | 2003-08-27 | Sumitomo Chemical Co.,Ltd. | Titanium oxide precursor and production method thereof, and production method of titanium oxide using the precursor |
| JP2005187294A (en) * | 2003-12-26 | 2005-07-14 | Dowa Mining Co Ltd | Titanium dioxide for visible light response type catalyst and its manufacturing method |
| WO2005087372A1 (en) * | 2004-03-12 | 2005-09-22 | Toho Titanium Co., Ltd. | Titanium oxide photocatalyst and method for preparation thereof |
| JP2006055746A (en) * | 2004-08-20 | 2006-03-02 | Tayca Corp | Titanium oxide photocatalyst having photocatalytic activity in wide range of wavelength and manufacturing method therefor |
| US7521391B2 (en) | 2004-03-17 | 2009-04-21 | Sumitomo Chemical Company, Limited | Coating composition of photocatalyst |
| EP2130587A2 (en) | 2008-06-05 | 2009-12-09 | Sumitomo Chemical Company, Limited | Photocatalyst dispersion liquid and process for producing the same |
| EP2281628A2 (en) | 2009-08-07 | 2011-02-09 | Sumitomo Chemical Company, Limited | Method for producing noble metal-supported photocatalyst particles |
| DE102010045549A1 (en) | 2009-09-16 | 2011-08-25 | Sumitomo Chemical Company, Limited | Photocatalyst composite and using this photocatalytically active product |
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2000
- 2000-04-24 JP JP2000122126A patent/JP2001302241A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1338564A2 (en) | 2002-02-25 | 2003-08-27 | Sumitomo Chemical Co.,Ltd. | Titanium oxide precursor and production method thereof, and production method of titanium oxide using the precursor |
| JP2005187294A (en) * | 2003-12-26 | 2005-07-14 | Dowa Mining Co Ltd | Titanium dioxide for visible light response type catalyst and its manufacturing method |
| WO2005087372A1 (en) * | 2004-03-12 | 2005-09-22 | Toho Titanium Co., Ltd. | Titanium oxide photocatalyst and method for preparation thereof |
| US7521391B2 (en) | 2004-03-17 | 2009-04-21 | Sumitomo Chemical Company, Limited | Coating composition of photocatalyst |
| JP2006055746A (en) * | 2004-08-20 | 2006-03-02 | Tayca Corp | Titanium oxide photocatalyst having photocatalytic activity in wide range of wavelength and manufacturing method therefor |
| JP4580197B2 (en) * | 2004-08-20 | 2010-11-10 | テイカ株式会社 | Titanium oxide photocatalyst having photocatalytic activity in a wide wavelength region and method for producing the same |
| EP2130587A2 (en) | 2008-06-05 | 2009-12-09 | Sumitomo Chemical Company, Limited | Photocatalyst dispersion liquid and process for producing the same |
| EP2281628A2 (en) | 2009-08-07 | 2011-02-09 | Sumitomo Chemical Company, Limited | Method for producing noble metal-supported photocatalyst particles |
| DE102010045549A1 (en) | 2009-09-16 | 2011-08-25 | Sumitomo Chemical Company, Limited | Photocatalyst composite and using this photocatalytically active product |
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