JP2002326815A - Production method of titanium oxide - Google Patents
Production method of titanium oxideInfo
- Publication number
- JP2002326815A JP2002326815A JP2001132001A JP2001132001A JP2002326815A JP 2002326815 A JP2002326815 A JP 2002326815A JP 2001132001 A JP2001132001 A JP 2001132001A JP 2001132001 A JP2001132001 A JP 2001132001A JP 2002326815 A JP2002326815 A JP 2002326815A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- titanium
- ammonium
- acid
- titanium compound
- 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 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 18
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000003929 acidic solution Substances 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 9
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001678 irradiating effect Effects 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 abstract description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract 2
- 239000001099 ammonium carbonate Substances 0.000 abstract 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical class COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- -1 adipic acid Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 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
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
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、可視光線の照射に
より高い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 exhibiting high catalytic activity by irradiation with visible light.
【０００２】[0002]
【従来の技術】酸化チタンが示す光触媒作用によって、
大気中の悪臭物質や水中の有機溶剤、界面活性剤を分解
除去することが検討されている。最近では、汎用性、利
便性から光源に可視光線を使った分解除去方法が注目さ
れ、可視光線を照射したときに高い触媒活性を示す酸化
チタンの開発が期待されている。2. Description of the Related Art Titanium oxide exhibits photocatalysis,
It has been studied to decompose and remove malodorous substances in the air, organic solvents and surfactants in water. In recent years, attention has been paid to a decomposition and removal method using visible light as a light source for versatility and convenience, and development of titanium oxide exhibiting high catalytic activity when irradiated with visible light is expected.
【０００３】このような酸化チタンの製造方法として、
例えば、酸化チタンにバナジウムやクロムをイオン注入
法で導入する方法が知られている。しかし、イオン注入
法では真空容器を備えた装置が必要となり、酸化チタン
の量産化が困難であった。[0003] As a method for producing such titanium oxide,
For example, a method of introducing vanadium or chromium into titanium oxide by an ion implantation method is known. However, the ion implantation method requires a device equipped with a vacuum vessel, and it has been difficult to mass-produce titanium oxide.
【０００４】[0004]
【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り高い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 having high catalytic activity by irradiating visible light without using a specific apparatus equipped with a vacuum vessel. Is to do.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、光触媒用
途に好適な酸化チタンの製造方法について検討した結
果、本発明を完成するに至った。Means for Solving the Problems The present inventors have studied a method for producing titanium oxide suitable for photocatalyst use, and as a result, have completed the present invention.
【０００６】すなわち本発明は、チタン化合物の酸性溶
液とカルボン酸のアンモニウム塩を混合して前記チタン
化合物を加水分解し、この生成物を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。That is, the present invention provides a method for producing titanium oxide, comprising mixing an acidic solution of a titanium compound and an ammonium salt of a carboxylic acid to hydrolyze the titanium compound and calcining the product. Things.
【０００７】[0007]
【発明の実施の形態】以下、本発明の酸化チタンの製造
方法を詳細に説明する。本発明では、原料としてチタン
化合物の酸性溶液が使用される。ここで使用されるチタ
ン化合物の酸性溶液は、例えばオキシ硫酸チタン、硫酸
チタンのようなチタン塩の水溶液等である。チタン化合
物の酸性溶液は、通常、水に水溶性チタン塩を溶解する
方法、鉱酸例えば硫酸に酸化チタンもしくは水酸化チタ
ンを溶解する方法で調製することができる。酸性溶液中
のチタン化合物の濃度はＴｉとして通常１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。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the method for producing titanium oxide of the present invention will be described in detail. In the present invention, an acidic solution of a titanium compound is used as a raw material. The acidic solution of the titanium compound used here is, for example, an aqueous solution of a titanium salt such as titanium oxysulfate or titanium sulfate. The acidic solution of the titanium compound can be usually prepared by a method of dissolving a water-soluble titanium salt in water or a method of dissolving titanium oxide or titanium hydroxide in a mineral acid such as sulfuric acid. The concentration of the titanium compound in the acidic solution is usually 1% by weight or more, preferably 10% by weight or less, and more preferably 5% by weight or less as Ti.
【０００８】チタン化合物の酸性溶液は、弱酸のアンモ
ニウム塩と混合され、加水分解される。混合される弱酸
のアンモニウム塩は、電離定数が約１×１０-3以下であ
る酸のアンモニウム塩であればよく、典型的にはカルボ
ン酸のアンモニウム塩であり、他には炭酸アンモニウ
ム、炭酸水素アンモニウム、ホウ酸アンモニウム等であ
る。カルボン酸のアンモニウム塩としては、ギ酸、酢
酸、プロピオン酸のようなモノカルボン酸のアンモニウ
ム塩、シュウ酸、グルタル酸、コハク酸、マロン酸、マ
レイン酸、アジピン酸のようなジカルボン酸のアンモニ
ウム塩、クエン酸のようなトリカルボン酸のアンモニウ
ム塩等が挙げられる。このような弱酸のアンモニウム塩
を混合してチタン化合物を加水分解することにより、最
終的に得られる酸化チタンは可視光線の照射によって高
い触媒活性を示すものとなる。弱酸のアンモニウム塩の
混合量は、チタン化合物の酸性溶液中のＴｉに対しＮＨ
4換算で１モル倍以上、さらには２モル倍以上であるこ
とが好ましく、また１０モル倍以下、さらには５モル倍
以下であることが適当である。チタン化合物の加水分解
は、弱酸のアンモニウム塩を混合することにより行わ
れ、具体的にはチタン化合物の酸性溶液に、攪拌下、弱
酸のアンモニウム塩を添加する方法、または弱酸のアン
モニウム塩の水溶液に、攪拌下、チタン化合物の酸性溶
液を添加する方法等で行うことができ、加水分解後に
は、通常、チタン化合物の加水分解生成物を含むスラリ
ーが得られる。加水分解は低い温度で行われることが好
ましく、例えば６０℃以下、さらには４０℃以下で行わ
れることが好ましい。An acidic solution of a titanium compound is mixed with a weak acid ammonium salt and hydrolyzed. The ammonium salt of the weak acid to be mixed may be an ammonium salt of an acid having an ionization constant of about 1 × 10 −3 or less, and is typically an ammonium salt of a carboxylic acid. Ammonium and ammonium borate. As ammonium salts of carboxylic acids, formic acid, acetic acid, ammonium salts of monocarboxylic acids such as propionic acid, oxalic acid, glutaric acid, succinic acid, malonic acid, maleic acid, ammonium salts of dicarboxylic acids such as adipic acid, And ammonium salts of tricarboxylic acids such as citric acid. By mixing such a weak acid ammonium salt to hydrolyze the titanium compound, the finally obtained titanium oxide has high catalytic activity by irradiation with visible light. The mixing amount of the ammonium salt of the weak acid is such that NH in the acidic solution of the titanium compound is
It is preferably at least 1 mol times, more preferably at least 2 mol times in terms of 4 , and suitably at most 10 mol times, more preferably at most 5 mol times. Hydrolysis of the titanium compound is performed by mixing an ammonium salt of a weak acid, specifically, a method of adding an ammonium salt of a weak acid to an acidic solution of the titanium compound with stirring, or an aqueous solution of an ammonium salt of a weak acid. The reaction can be carried out, for example, by adding an acidic solution of a titanium compound under stirring. After the hydrolysis, a slurry containing a hydrolysis product of the titanium compound is usually obtained. The hydrolysis is preferably performed at a low temperature, for example, at 60 ° C or lower, more preferably at 40 ° C or lower.
【０００９】加水分解生成物を含むスラリーは必要に応
じて固液分離され、生成物と、硫酸アンモニウムのよう
な、酸性溶液の成分である酸のアンモニウム塩等を含む
水溶液とに分けられる。固液分離された生成物には、さ
らに洗浄が施されることが好ましい。The slurry containing the hydrolysis product is subjected to solid-liquid separation, if necessary, and separated into the product and an aqueous solution containing an ammonium salt of an acid which is a component of an acidic solution such as ammonium sulfate. The solid-liquid separated product is preferably further washed.
【００１０】加水分解による生成物を含むスラリーまた
は任意で行われる固液分離により得られる生成物は、焼
成される。焼成は、例えば、静置式焼成炉、流動焼成
炉、媒体流動焼成炉、回転炉、ベルト炉、トンネル炉、
遠赤外線焼成炉、マイクロ波焼成炉、通気焼成炉、シャ
フト炉等で行うことができる。焼成に供する生成物がス
ラリーであるときには、媒体流動焼成炉等を用いて焼成
することが好ましく、また生成物が固体であるときに
は、通気焼成炉等を用いることが推奨される。焼成温度
は通常３００℃以上であり、さらには３５０℃以上が好
ましく、また６００℃以下が適当である。焼成時間は、
焼成温度および使用する焼成炉の方式により異なり一義
的ではないが通常１０分以上、１０時間以内である。The slurry containing the product of the hydrolysis or the product obtained by optional solid-liquid separation is calcined. Firing, for example, a stationary firing furnace, a fluidized firing furnace, a medium fluidized firing furnace, a rotary furnace, a belt furnace, a tunnel furnace,
It can be performed in a far-infrared firing furnace, a microwave firing furnace, a ventilation firing furnace, a shaft furnace, or the like. When the product to be fired is a slurry, firing is preferably performed using a medium fluidized firing furnace or the like, and when the product is solid, it is recommended to use a vented firing furnace or the like. The firing temperature is usually 300 ° C. or higher, preferably 350 ° C. or higher, and more preferably 600 ° C. or lower. The firing time is
It is not unique depending on the firing temperature and the type of firing furnace to be used, but is usually 10 minutes or more and 10 hours or less.
【００１１】本発明の方法で得られる酸化チタンはその
まま光触媒体として用いることができる。酸化チタンに
は適当な結合剤を添加、混合した後、成形を施してもよ
い。このとき添加する結合剤としては、例えば、水ガラ
ス、コロイダルシリカ、リン酸アルミニウムのような無
機系結合剤、フッ素系ポリマー、シリコン系ポリマーの
ような有機系結合剤が挙げられる。この酸化チタンは溶
媒に分散させる方法によりコーティング液とされ、これ
は建築材料、自動車材料のような各種材料に塗布または
被覆することに使用できる。分散に用いる溶媒として
は、例えば、水、アルコール類およびケトン類が挙げら
れる。またコーティング液は酸化チタンを酸で解膠させ
る方法により調製することもできる。The titanium oxide obtained by the method of the present invention can be used as it is as a photocatalyst. After adding and mixing an appropriate binder to the titanium oxide, molding may be performed. Examples of the binder added at this time include inorganic binders such as water glass, colloidal silica, and aluminum phosphate, and organic binders such as a fluorine-based polymer and a silicon-based polymer. This titanium oxide is made into a coating liquid by a method of dispersing it in a solvent, which can be used for coating or coating various materials such as building materials and automobile materials. Examples of the solvent used for dispersion include water, alcohols and ketones. The coating liquid can also be prepared by a method of peptizing titanium oxide with an acid.
【００１２】本発明による酸化チタンを光触媒体として
使用するときの具体例としては、可視光線を透過するガ
ラス製容器に酸化チタンと被処理液または被処理気体と
を入れ、光源を用いて酸化チタンに波長が４３０ｎｍ以
上である可視光線を照射する方法等が挙げられる。照射
時間は、光源の光線の強度および、被処理液または被処
理気体の中の被処理物質の種類や量により適宜選択すれ
ばよい。用いる光源は、波長が４３０ｎｍ以上である可
視光線を照射できるものであれば制限されるものではな
く、太陽光線、蛍光灯、ハロゲンランプ、ブラックライ
ト、キセノンランプ、水銀灯またはナトリウムランプ等
が適用できる。As a specific example when the titanium oxide according to the present invention is used as a photocatalyst, the titanium oxide and the liquid to be treated or the gas to be treated are placed in a glass container that transmits visible light, and the titanium oxide is treated with a light source. And a method of irradiating visible light having a wavelength of 430 nm or more. The irradiation time may be appropriately selected depending on the intensity of the light beam from the light source and the type and amount of the substance to be treated in the liquid to be treated or the gas to be treated. The light source to be used is not limited as long as it can emit visible light having a wavelength of 430 nm or more, and sunlight, a fluorescent lamp, a halogen lamp, a black light, a xenon lamp, a mercury lamp, a sodium lamp, or the like can be used.
【００１３】[0013]
【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。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.
【００１４】実施例１ 〔酸化チタンの製造〕オキシ硫酸チタン（商品名“オキ
シ硫酸チタン”、添川理化学製）８９ｇを水３６１ｇに
溶解して、オキシ硫酸チタン水溶液を調製した。このオ
キシ硫酸チタン水溶液に酢酸アンモニウム（１級試薬、
和光純薬工業製）１１５ｇを、２００ｒｐｍで攪拌しな
がら、５ｍｌ／分で添加して２０℃で加水分解させ、ス
ラリーを得た。上で調製したオキシ硫酸チタン水溶液の
Ｔｉ濃度は３．９重量％であり、オキシ硫酸チタンの量
はＴｉとして０．３７モルである。また、酢酸アンモニ
ウムの量はＮＨ4として１．４９モルである。上で得ら
れたスラリーを濾過し、得られた固形物を乾燥し、６０
℃の温水で洗浄した後、１１０℃で乾燥して、粉末を得
た。この粉末を５００℃の空気気流中で１時間焼成し
て、粒子状酸化チタンを得た。Example 1 [Production of Titanium Oxide] 89 g of titanium oxysulfate (trade name "Titanium oxysulfate", manufactured by Soegawa Rikagaku) was dissolved in 361 g of water to prepare an aqueous solution of titanium oxysulfate. Ammonium acetate (a first-order reagent,
115 g (Wako Pure Chemical Industries, Ltd.) was added at 5 ml / min while stirring at 200 rpm and hydrolyzed at 20 ° C. to obtain a slurry. The Ti concentration of the titanium oxysulfate aqueous solution prepared above is 3.9% by weight, and the amount of titanium oxysulfate is 0.37 mol as Ti. The amount of ammonium acetate is 1.49 mol as NH 4 . The slurry obtained above was filtered and the solid obtained was dried,
After washing with warm water at 110 ° C., the powder was dried at 110 ° C. to obtain a powder. This powder was fired in an air stream at 500 ° C. for 1 hour to obtain particulate titanium oxide.
【００１５】〔酸化チタンの活性評価〕直径８ｃｍ、高
さ１０ｃｍ、容量約０．５Ｌの密閉式ガラス製反応容器
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０．３ｇを
置いた。容器内を酸素２０容量％と窒素８０容量％とか
らなる混合気体で満たし、アセトアルデヒドを１３．４
μｍｏｌ封入し、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（商品名
“ランプＵＸＬ−５００ＳＸ”、ウシオ電機製）を取り
付けた光源装置（商品名“オプティカルモジュレックス
ＳＸ−ＵＩ５００ＸＱ”、ウシオ電機製）に、波長約４
３０ｎｍ以下の紫外線をカットするフィルター（商品名
“Ｙ−４５”、旭テクノガラス製）と波長約８３０ｎｍ
以上の赤外線をカットするフィルター（商品名“スーパ
ーコールドフィルター”、ウシオ電機製）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（１３１２
型、ＩＮＮＯＶＡ製）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。この例
における二酸化炭素の生成速度は酸化チタン１ｇあたり
３．０８μｍｏｌ／ｈであった。[Evaluation of the activity of titanium oxide] A glass petri dish having a diameter of 5 cm was placed in a sealed glass reaction vessel having a diameter of 8 cm, a height of 10 cm, and a capacity of about 0.5 L. 0.3 g of the obtained particulate titanium oxide was placed. The container was filled with a mixed gas consisting of 20% by volume of oxygen and 80% by volume of nitrogen, and acetaldehyde was added at 13.4%.
μmol was sealed, and visible light was irradiated from outside the container. For irradiation of visible light, a light source device (trade name “Optical Modlex SX-UI500XQ”, trade name “Lamp UXL-500SX”, manufactured by USHIO Inc., manufactured by USHIO Inc.) with a wavelength of about 4
A filter (trade name “Y-45”, made by Asahi Techno Glass) that cuts ultraviolet rays of 30 nm or less and a wavelength of about 830 nm
A light source equipped with the above-described filter for cutting off infrared rays (trade name “Super Cold Filter”, manufactured by Ushio Inc.) was used. When acetaldehyde is decomposed by irradiation with visible light, carbon dioxide is generated,
Photoacoustic multi-gas monitor (1312)
(Manufactured by INNOVA) over time, and the photodecomposition effect of titanium oxide on acetaldehyde was evaluated based on the carbon dioxide generation rate calculated from the concentration change. The generation rate of carbon dioxide in this example was 3.08 μmol / h per 1 g of titanium oxide.
【００１６】比較例１ 市販の酸化チタン（商品名“ＳＴ−０１”、石原産業
製）について、実施例１の〔酸化チタンの活性評価〕と
同条件で評価した。この例における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。Comparative Example 1 A commercially available titanium oxide (trade name "ST-01", manufactured by Ishihara Sangyo) was evaluated under the same conditions as in [Evaluation of titanium oxide activity] in Example 1. The generation rate of carbon dioxide in this example was 0.93 μmol / h per 1 g of titanium oxide.
【００１７】[0017]
【発明の効果】本発明によれば、可視光線を照射するこ
とにより高い触媒活性を示す酸化チタンを簡易に得るこ
とができる。According to the present invention, titanium oxide exhibiting high catalytic activity can be easily obtained by irradiating visible light.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D048 AA19 AB03 BA07X BA41X BB01 EA01 4G047 CA02 CB05 CC03 CD03 4G069 AA02 AA08 BA04A BA04B BA48A BB10C BB20C BC50C BE08C BE17C CA01 CA10 CA11 DA05 EA02Y FA01 FB08 FB30 FC02 FC03 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D048 AA19 AB03 BA07X BA41X BB01 EA01 4G047 CA02 CB05 CC03 CD03 4G069 AA02 AA08 BA04A BA04B BA48A BB10C BB20C BC50C BE08C BE17C CA01 CA10 CA11 DA05 FC02 FC03
Claims (3)
ニウム塩を混合して前記チタン化合物を加水分解し、こ
の生成物を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 mixing an acidic solution of a titanium compound and an ammonium salt of a weak acid to hydrolyze the titanium compound and calcining the product.
方法。2. The method according to claim 1, wherein the weak acid is a carboxylic acid.
硫酸チタンである請求項１または２記載の方法。3. The method according to claim 1, wherein the titanium compound is titanium sulfate or titanium oxysulfate.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001132001A JP2002326815A (en) | 2001-04-27 | 2001-04-27 | Production method of titanium oxide |
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|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11197503A (en) * | 1998-01-14 | 1999-07-27 | Toyota Central Res & Dev Lab Inc | Composite particles |
| JP2000086292A (en) * | 1998-07-02 | 2000-03-28 | Agency Of Ind Science & Technol | Production of titanium oxide-coated fine hollow glass sphere |
| JP2001038211A (en) * | 1999-07-30 | 2001-02-13 | Toyota Central Res & Dev Lab Inc | Catalyst and method for cleaning exhaust gas |
| WO2001010552A1 (en) * | 1999-08-05 | 2001-02-15 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalytic material, photocatalytic article and method for their preparation |
| JP2002255555A (en) * | 2000-01-31 | 2002-09-11 | Kankyo Device Kenkyusho:Kk | Visible light responsive material and method for producing the same |
-
2001
- 2001-04-27 JP JP2001132001A patent/JP2002326815A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11197503A (en) * | 1998-01-14 | 1999-07-27 | Toyota Central Res & Dev Lab Inc | Composite particles |
| JP2000086292A (en) * | 1998-07-02 | 2000-03-28 | Agency Of Ind Science & Technol | Production of titanium oxide-coated fine hollow glass sphere |
| JP2001038211A (en) * | 1999-07-30 | 2001-02-13 | Toyota Central Res & Dev Lab Inc | Catalyst and method for cleaning exhaust gas |
| WO2001010552A1 (en) * | 1999-08-05 | 2001-02-15 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalytic material, photocatalytic article and method for their preparation |
| JP2002255555A (en) * | 2000-01-31 | 2002-09-11 | Kankyo Device Kenkyusho:Kk | Visible light responsive material and method for producing the same |
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