JP3374305B2 - Method for producing titania-based catalyst - Google Patents
Method for producing titania-based catalystInfo
- Publication number
- JP3374305B2 JP3374305B2 JP17832096A JP17832096A JP3374305B2 JP 3374305 B2 JP3374305 B2 JP 3374305B2 JP 17832096 A JP17832096 A JP 17832096A JP 17832096 A JP17832096 A JP 17832096A JP 3374305 B2 JP3374305 B2 JP 3374305B2
- Authority
- JP
- Japan
- Prior art keywords
- titania
- based catalyst
- catalytic activity
- producing
- catalyst
- 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.)
- Expired - Fee Related
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 90
- 239000003054 catalyst Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 4
- 229910003077 Ti−O Inorganic materials 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- 229910003089 Ti–OH Inorganic materials 0.000 claims description 2
- 229910003088 Ti−O−Ti Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 titanium alkoxide Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019833 protease Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 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
- 238000005507 spraying Methods 0.000 description 1
- 229910052861 titanite Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012808 vapor phase Substances 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、チタニア系触媒の製造
方法に関する。更に詳しくは、市販のチタニア（ＴｉＯ
2 ）から光触媒活性に優れた触媒を、容易に製造する方
法に関する。TECHNICAL FIELD The present invention relates to a method for producing a titania-based catalyst. More specifically, commercially available titania (TiO
2 ) A method for easily producing a catalyst excellent in photocatalytic activity from 2 ).
【０００２】[0002]
【従来の技術】チタニアは、触媒活性に優れた材料とし
て広く知られ、さまざまな光触媒反応が検討されてい
る。2. Description of the Related Art Titania is widely known as a material having excellent catalytic activity, and various photocatalytic reactions have been studied.
【０００３】光触媒反応は、(1) 触媒表面に反応分子が
近接する、(2) 触媒の内部で光照射によって励起された
電子・ホールが触媒表面にある反応分子を還元あるいは
酸化させることによって、化学反応を促進させると考え
られる。The photocatalytic reaction is carried out by (1) the reaction molecules are brought close to the catalyst surface, and (2) electrons and holes excited by light irradiation inside the catalyst reduce or oxidize the reaction molecules on the catalyst surface. It is thought to accelerate the chemical reaction.
【０００４】触媒活性を向上させるための手段として
は、触媒の比表面積の増大（触媒活性点の増大）につな
がる、触媒粉末の微細化、ないしは、多結晶であっても
結晶粒径（単一結晶の）の小径化が、即ち、結晶微細化
が有効な一手段として期待できる。そして、結晶微細化
の方法として、ゾルゲル法、気相法等が公知である。As means for improving the catalytic activity, the catalyst powder is made finer, which leads to an increase in the specific surface area of the catalyst (increase in the catalytic activity points), or even if it is polycrystalline, the crystal grain size (single It can be expected that reducing the diameter of the crystal), that is, refining the crystal, is an effective means. Then, as a method of refining crystals, a sol-gel method, a vapor phase method, etc. are known.
【０００５】さらに、１９９２年１月発行の「科学と工
業 第６６巻」に投稿された研究論文「白金およびルテ
ニウムを担持したＴｉＯ2 −ＳｉＯ2 触媒の調製と光触
媒活性」に、ゾルゲル法でチタニア系触媒粉末を調製す
る際に、シリカ（ＳｉＯ2 ）をドープ（添加）すると結
晶粒径が小さくなることが報告されている。Further, in the research paper “Preparation and Photocatalytic Activity of TiO 2 —SiO 2 Catalyst Supporting Platinum and Ruthenium” published in “Science and Industry Vol. 66” published in January 1992, titania by sol-gel method It has been reported that the crystal grain size becomes smaller when silica (SiO 2 ) is doped (added) when preparing the system catalyst powder.
【０００６】しかし、当該チタニア系触媒においては、
触媒助剤として白金とルテニウムを担持させて光触媒活
性を増大させることを前提とし、ＴｉＯ2 −ＳｉＯ2
は、触媒活性をほとんど期待しない担体としての役割を
担っていると推定される。However, in the titania-based catalyst,
Assuming that platinum and ruthenium are supported as a catalyst aid to increase the photocatalytic activity, TiO 2 —SiO 2
Is presumed to have a role as a carrier that hardly expects catalytic activity.
【０００７】そして、これらの担持操作は、貴金属を塩
化物水溶液の形にして行うため、面倒であり、かつ、コ
スト高となり易い。Since these supporting operations are carried out in the form of an aqueous chloride solution of the noble metal, it is troublesome and the cost tends to be high.
【０００８】また、ＴｉＯ2 −ＳｉＯ2 だけでは、高い
触媒活性が得難いことが、本発明者らが試験検討した結
果、分かった。Further, as a result of examination and examination by the present inventors, it was found that it is difficult to obtain a high catalytic activity only with TiO 2 —SiO 2 .
【０００９】そこで、本発明者らは、特別に貴金属助触
媒等を担持させなくても、ＴｉＯ2又は、ＴｉＯ2 −Ｓ
ｉＯ2 だけで、触媒活性を増大させることができるチタ
ニア系触媒の製造方法を、特願平７−６７８９３号、特
願平７−２２８９６６号（共に本願出願時未公開）にお
いて、先に提案した。Therefore, the inventors of the present invention did not specially support a noble metal co-catalyst or the like on TiO 2 or TiO 2 —S.
iO 2 only, a method of manufacturing a titania-based catalyst capable of increasing the catalytic activity, Japanese Patent Application No. Hei 7-67893, Japanese Patent Application No. Hei 7-228966 in (unpublished at both the Applicant), previously proposed .
【００１０】「（１−ｘ）ＴｉＯ2 ・ｘＳｉＯ2 （ｘ＝
０〜０．５）のモル比となるように、チタンアルコキシ
ド及びシリコンアルコキシドを混合した加水分解ゾルを
ゲル化後、該ゲル化物を３５０〜１２００℃で焼成して
チタニア系触媒を製造する方法であって、焼成後のチタ
ニア系触媒を、酸またはアルカリで表面処理（化学処
理）する、更には、２００〜１２００℃の加熱処理する
ことを特徴とする。」"(1-x) TiO 2 .xSiO 2 (x =
In the method of producing a titania-based catalyst by gelling a hydrolyzed sol in which titanium alkoxide and silicon alkoxide are mixed so as to have a molar ratio of 0 to 0.5), and then firing the gelled product at 350 to 1200 ° C. It is characterized by subjecting the titania-based catalyst after calcination to a surface treatment (chemical treatment) with an acid or an alkali, and further to a heat treatment at 200 to 1200 ° C. "
【００１１】[0011]
【発明が解決しようとする課題】しかし、上記各方法の
場合、溶液濃度、攪拌時間、ゲル化条件、焼成条件等の
製造条件の制御を厳格にする必要があった。However, in the case of each of the above methods, it was necessary to strictly control the production conditions such as the solution concentration, the stirring time, the gelling condition and the firing condition.
【００１２】本発明は、上記にかんがみて、市販の安価
な汎用チタニアから光触媒活性に優れたチタニア系触媒
を容易に製造することができる方法を提供することを目
的とする。In view of the above, an object of the present invention is to provide a method capable of easily producing a titania-based catalyst excellent in photocatalytic activity from a commercially available inexpensive general-purpose titania.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく、鋭意開発に努力をする過程で、市販の安
価な汎用チタニアをアルカリ等で化学処理、更には、加
熱処理をすれば、触媒活性が増大することを見出し下記
構成の本発明に想到し得た。In order to solve the above-mentioned problems, the present inventors, in the process of earnestly developing, carry out chemical treatment of commercially available inexpensive general-purpose titania with an alkali or the like, and further heat treatment. Then, it was found that the catalytic activity is increased, and the present invention having the following constitution was conceived.
【００１４】 本発明は、アルカリで前記ＴｉＯ 2 の表
面層にアナターゼ型結晶を成長させるとともに、Ｔｉ−
ＯＨ又はＴｉ−Ｏという結合を形成する化学処理（表面
処理）をしたのち、さらに、３００〜８００℃の温度で
加熱処理してＴｉ−Ｏ−Ｔｉ結合させることを特徴とす
るチタニア系触媒の製造方法にある。The present invention is based on the above table of TiO 2 with alkali.
While growing anatase type crystal in the surface layer, Ti-
Chemical treatment to form OH or Ti-O bond (surface
Processing), and then at a temperature of 300 to 800 ° C.
A method for producing a titania-based catalyst is characterized in that a Ti—O—Ti bond is formed by heat treatment .
【００１５】 上記製造方法において、化学処理を、水
酸化ナトリウム濃度３％以上、温度２０〜１５０℃の条
件下で行うことが望ましい。 In the above manufacturing method, the chemical treatment is water.
Article having a sodium oxide concentration of 3% or more and a temperature of 20 to 150 ° C
It is desirable to do it under the circumstances.
【００１６】[0016]
【手段の詳細な説明】以下、本発明のチタニア系触媒の
製造方法を説明をする。[Detailed Description of Means] The method for producing the titania-based catalyst of the present invention will be described below.
【００１７】(1) 第一グループ発明のチタニア系触媒を
製造する方法は、結晶又は無定形のチタニアを、アルカ
リまたは酸で化学処理することを特徴とする。(1) The method for producing a titania-based catalyst of the first group invention is characterized in that crystalline or amorphous titania is chemically treated with an alkali or an acid.
【００１８】ここで、使用するチタニアは、通常、アナ
ターゼ型、ルチル型等の結晶粉末を使用するが、無定形
であってもよい。The titania used here is usually anatase-type, rutile-type, or the like, but may be amorphous.
【００１９】具体的には、鋭錐石（アナターゼ）、金紅
石（ルチル）、板チタン石（ブルッカイト）等のチタン
鉱石から下記液相法により調製したものや、下記気相法
で合成したものを挙げることができる。更に具体的に
は、「ＪＲＣ−ＴＩ０−１」、「ＪＲＣ−ＴＩ０−
２」、「ＪＲＣ−ＴＩ０−４」（以上「石原産業（株）
製」）、「JIS 特級試薬：アナターゼ型」等のアナター
ゼ型粉末や、「ＪＲＣ−ＴＩ０−３」、「ＪＲＣ−ＴＩ
０−５」（以上「石原産業（株）製」）、「JIS 特級試
薬：ルチル型」等のルチル型粉末を挙げることができ
る。以上は、いずれも粉末状であるが、塊状であっても
よい。Concretely, those prepared from the titanium ores such as anatase (anatase), gold pearlite (rutile), and titanite (brookite) by the following liquid phase method, or those synthesized by the following gas phase method. Can be mentioned. More specifically, "JRC-TI0-1", "JRC-TI0-"
2 "," JRC-TI0-4 "(above" Ishihara Sangyo Co., Ltd. "
Manufactured)), "JIS special grade reagent: anatase type" and other anatase type powders, "JRC-TI0-3", "JRC-TI"
0-5 "(above" Ishihara Sangyo Co., Ltd. ")," JIS special grade reagent: rutile type "and the like rutile type powders. All of the above are in powder form, but may be in lump form.
【００２０】ここで、「液相法」とは、チタン鉱石を、
硫酸等の強酸で、加熱加水分解して得られる含水酸化チ
タンを８００〜８５０℃で焼成してチタニアを製造する
方法のことである。Here, the "liquid phase method" means titanium ore
It is a method of producing titania by firing hydrous titanium oxide obtained by hydrolysis with a strong acid such as sulfuric acid at 800 to 850 ° C.
【００２１】また、「気相法」とは、ＴｉＣｌ4 にＯ2
及びＨ2 を接触させて、チタニアを製造する方法のこと
である。The "gas phase method" means that TiCl 4 and O 2 are added.
And H 2 are brought into contact with each other to produce titania.
【００２２】(2) 本発明は、上記方法でチタニア粉末を
アルカリまたは酸で化学処理する。その際の条件は、常
温・常圧（大気圧）下の条件でも良いが、水熱合成的反
応が発生する高温・加圧下の条件で行うことが、反応が
促進される等の見地から望ましい。(2) In the present invention, the titania powder is chemically treated with an alkali or an acid by the above method. The conditions at that time may be room temperature and atmospheric pressure (atmospheric pressure), but it is preferable to carry out under conditions of high temperature and pressure at which a hydrothermal synthetic reaction occurs in order to accelerate the reaction. .
【００２３】ここでアルカリとしては水酸化ナトリウム
・カリウムの水溶液等を、酸としてはフッ酸等を好適に
使用可能である。Here, an aqueous solution of sodium / potassium hydroxide or the like can be preferably used as the alkali, and hydrofluoric acid or the like can be suitably used as the acid.
【００２４】ここで、水熱合成的反応が発生する高温・
加圧下とは、例えば、水酸化ナトリウムで化学処理（表
面処理）をする場合、耐圧密閉容器内で、温度２０〜１
５０℃×１〜１００ｈ、望ましくは、１００〜１２０℃
×２〜１２０ｈの条件下で行う。Here, the high temperature / temperature at which the hydrothermal synthetic reaction occurs
When under pressure, for example, when chemical treatment (surface treatment) is performed with sodium hydroxide, the temperature is 20 to 1 in a pressure-resistant closed container.
50 ° C x 1 to 100h, preferably 100 to 120 ° C
It is performed under the condition of × 2 to 120 hours.
【００２５】この化学処理による原料チタニアの触媒活
性向上の理由は、夫々下記の如くであると推定される。The reasons why the catalytic activity of the raw material titania is improved by this chemical treatment are presumed to be as follows.
【００２６】 参照例１の如く、結晶粒径が大きな（触
媒活性が低い。）場合は、触媒活性のチタニアの表面が
凹凸となり、比表面積が増大する。実施例の如く、相対
的に比表面積が大きい（結晶粒径が小さい）ルチル形結
晶の場合、ＴｉＯ2表面にアナターゼ結晶が成長するた
めに、結晶活性がさらに増大する。When the crystal grain size is large (the catalytic activity is low) as in Reference Example 1 , the surface of the catalytically active titania becomes uneven and the specific surface area increases. In the case of the rutile type crystal having a relatively large specific surface area (small crystal grain size) as in the example, the anatase crystal grows on the TiO 2 surface, so that the crystal activity further increases.
【００２７】また、各化学処理後は、水洗しておく。そ
して、アルカリで化学処理した場合、水洗後、希塩酸等
の無機酸で中和処理しておくことが望ましい。この、中
和処理方法は、通常、浸漬・噴霧等の方法で行う。After each chemical treatment, it is washed with water. When chemically treated with an alkali, it is desirable to neutralize with an inorganic acid such as dilute hydrochloric acid after washing with water. This neutralization treatment method is usually performed by a method such as dipping or spraying.
【００２８】(3) 上記のようにして調製した化学処理二
酸化チタンは、さらに、２００〜１２００℃×１０〜４
００分、望ましくは、３００〜８００℃×６０〜１６０
分の温度で加熱処理を行うことが望ましい。この加熱処
理により、ＴｉＯ2 の結晶性が向上して、触媒活性が向
上する。即ち、化学処理（表面処理）したとき、ＴｉＯ
2 の表面層に、Ｔｉ−ＯＨあるいはＴｉ−Ｏという結合
が形成されていると考えられ、これを熱処理すると、Ｔ
ｉ−Ｏ−Ｔｉの結合が形成され、相対的に触媒反応に寄
与するＴｉＯ2 量が増えるため、触媒活性が向上するも
のと推定される。(3) The chemically treated titanium dioxide prepared as above is further added at 200 to 1200 ° C. × 10 to 4
00 minutes, preferably 300-800 ° C x 60-160
It is desirable to perform the heat treatment at a temperature of minutes. This heat treatment improves the crystallinity of TiO 2 and improves the catalytic activity. That is, when chemically treated (surface treatment), TiO
It is considered that a bond of Ti-OH or Ti-O is formed in the surface layer of No. 2 , and when this is heat-treated, T
It is estimated that the i-O-Ti bond is formed and the amount of TiO 2 that contributes to the catalytic reaction relatively increases, so that the catalytic activity is improved.
【００２９】加熱処理温度が、２００℃未満では、Ｔｉ
−Ｏ−Ｔｉ結合が形成されず、１２００℃を越えると、
結晶が成長し、比表面積が減少するため触媒活性が低下
するおそれがある。When the heat treatment temperature is less than 200 ° C., Ti
If the -O-Ti bond is not formed and the temperature exceeds 1200 ° C,
The crystals grow and the specific surface area decreases, so the catalytic activity may decrease.
【００３０】(4) この加熱処理品は、そのまま、触媒
（光活性用）として使用してもよいが、通常、粉砕して
使用する。粉砕方法としては、通常、ボール・ロッドミ
ル、マイクロナイザー等の微粉砕機・超微粉砕機を使用
して行う。(4) This heat-treated product may be used as it is as a catalyst (for photoactivation), but it is usually crushed before use. As a pulverization method, a fine pulverizer or an ultrafine pulverizer such as a ball / rod mill or a micronizer is usually used.
【００３１】[0031]
【発明の作用・効果】本発明のチタニア系触媒の製造方
法は、上記のような構成により、下記のような作用・効
果を奏する。The operation and effect of the present invention has the following operation and effects due to the above-mentioned constitution.
【００３２】(1) チタニア粉末を、アルカリ又は酸で、
化学処理することにより、後述の実施例で支持される如
く、光触媒活性がに増大する。その理論的推定は、前述
の通りである。(1) Titania powder is treated with an alkali or an acid,
The chemical treatment increases the photocatalytic activity, as will be supported in the examples below. The theoretical estimation is as described above.
【００３３】(2) 上記化学処理後のチタニア粉末を、加
熱処理することにより、後述の実施例で支持される如
く、光触媒特性が格段に増大する。(2) By subjecting the titania powder after the above chemical treatment to a heat treatment, the photocatalytic properties are remarkably increased, as will be supported in Examples described later.
【００３４】この加熱処理により、ＴｉＯ2 表面の各結
晶の触媒活性が増大するように改質されるものと推定さ
れる。It is estimated that this heat treatment modifies each crystal on the TiO 2 surface so that the catalytic activity of each crystal increases.
【００３５】以上の如く、本発明のチタニア系触媒の製
造方法は、安価な市販の汎用チタニアを、アルカリまた
は酸で化学処理するだけ、または、更には加熱処理する
だけで、チタニアの触媒活性を増大（特に、加熱処理し
た場合には格段に）させることができる。即ち、市販の
安価な汎用チタニアから光触媒活性に優れたチタニア系
触媒の容易に製造することができる。As described above, according to the method for producing a titania-based catalyst of the present invention, the catalytic activity of titania is obtained by chemically treating inexpensive commercially available general-purpose titania with an alkali or an acid, or by further heat treatment. It can be increased (particularly significantly when heat-treated). That is, a titania-based catalyst having excellent photocatalytic activity can be easily produced from commercially available inexpensive general-purpose titania.
【００３６】[0036]
【実施例】以下、本発明の効果を確認するために行った
実施例について説明をする。[Examples] Examples performed to confirm the effects of the present invention will be described below.
【００３７】 （１）実施例・参照例１〜３
表1に示す仕様の各チタニア粉末を使用して、表示の条
件で化学処理（耐圧密閉容器内）したもの、及び、加熱
処理したものについて、光触媒活性を、下記方法で測定
をした（図１参照）。化学処理は、アルカリ処理後、水
洗し、ＨＣｌａｑ（０．１Ｎ）で酸洗浄して完了した。(1) Examples / Reference Examples 1 to 3 Each of the titania powders having the specifications shown in Table 1 was chemically treated (in a pressure-resistant airtight container) under the indicated conditions, and heat-treated. The photocatalytic activity was measured by the following method (see FIG. 1). The chemical treatment was completed by rinsing with water after alkali treatment and acid washing with HClaq (0.1N).
【００３８】 ＜触媒活性試験＞
酢酸水溶液（濃度５ｍモル／Ｌ）を１０ｍＬビーカ１２
に充満させた後、各実施例・参照例のチタニアを添加
し、磁石式スターラ１４で攪拌するとともに、酸素をバ
ブリングしながら、キセノンランプ（５００Ｗ）で光照
射しながら、酢酸水溶液を光分解させた。そのとき、残
存酢酸の濃度をガスクロマトグラフィーで測定して、１
５分ごとに分解率を求めた。<Catalyst activity test> Aqueous acetic acid solution (concentration 5 mmol / L) was added to 10 mL beaker 12
After filling, the titania in the Examples and Reference Example was added pressure, with stirring with a magnet type stirrer 14, while bubbling oxygen, while irradiation with a xenon lamp (500 W), photolysis aqueous solution of acetic acid Let At that time, the concentration of residual acetic acid was measured by gas chromatography to be 1
The decomposition rate was obtained every 5 minutes.
【００３９】 (2)試験結果
各試験結果を図２〜５に示す。当該試験結果から、参照
例・実施例のいずれにおいても、化学処理・加熱処理品
は、格段に触媒活性が増大していることが分かる。化学
処理品においても、参照例２（図４）を除いて、触媒活
性が増大していることが分かる。参照例２は、当初か
ら、比表面積が大きく、かつ、化学処理時間が４０ｈと
長いため、触媒活性を担うアナタ−ゼがアモルファス化
（無定形化）して、触媒活性が低下すると推定される。(2) Test Results Each test result is shown in FIGS. Reference from the test results
In each of the examples and examples, it can be seen that the chemical treatment / heat treatment product has a markedly increased catalytic activity. It can be seen that also in the chemically treated product, the catalytic activity is increased except for Reference Example 2 (FIG. 4) . Reference Example 2, from the beginning, a large specific surface area, and since chemical treatment time is long and 40h, ANATA responsible for catalytic activity - peptidase is amorphous (amorphization) that the catalytic activity is estimated to decrease .
【００４０】[0040]
【表１】 [Table 1]
【図１】 光触媒活性試験に使用する装置のモデル図FIG. 1 Model diagram of an apparatus used for photocatalytic activity test
【図２】 参照例１におけるチタニアの触媒活性試験の
結果を示すグラフ図FIG. 2 is a graph showing the results of a titania catalytic activity test in Reference Example 1 .
【図３】 実施例におけるチタニアの触媒活性試験の結
果を示すグラフ図FIG. 3 is a graph showing the results of a titania catalytic activity test in Examples .
【図４】 参照例２におけるチタニアの触媒活性試験の
結果を示すグラフ図FIG. 4 is a graph showing the results of a titania catalytic activity test in Reference Example 2 .
【図５】 参照例３におけるチタニアの触媒活性試験の
結果を示すグラフ図FIG. 5 is a graph showing the results of a titania catalytic activity test in Reference Example 3 .
１２ ビーカ １４ スターラ 12 beakers 14 Stirrer
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平８−117556（ＪＰ，Ａ) 特開 平７−303835（ＪＰ，Ａ) 特開 平７−819（ＪＰ，Ａ) 特開 昭51−64498（ＪＰ，Ａ) 特開 平４−90825（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 C01G 23/00 - 23/08 ─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-8-117556 (JP, A) JP-A-7-303835 (JP, A) JP-A-7-819 (JP, A) JP-A-51- 64498 (JP, A) JP-A-4-90825 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B01J 21/00-38/74 C01G 23/00-23/08
Claims (2)
（ＴｉＯ 2 ）のルチル型結晶粉末を、アルカリで前記Ｔ
ｉＯ 2 の表面層にアナターゼ型結晶を成長させるととも
に、Ｔｉ−ＯＨ又はＴｉ−Ｏという結合を形成する化学
処理（表面処理）をしたのち、さらに、３００〜８００
℃の温度で加熱処理してＴｉ−Ｏ−Ｔｉ結合させること
を特徴とするチタニア系触媒の製造方法。1. A titania synthesized by a liquid phase method or a gas phase method.
The rutile type crystal powder of (TiO 2 ) is treated with the above-mentioned T with an alkali.
The growth of anatase type crystals on the surface layer of iO 2
To form Ti-OH or Ti-O bond
After treatment (surface treatment), 300-800
A method for producing a titania-based catalyst, which comprises heat-treating at a temperature of ° C to bond Ti-O-Ti .
酸化ナトリウム濃度３％以上、温度２０〜１５０℃の条
件下で行うことを特徴とするチタニア系触媒の製造方
法。2. The chemical treatment according to claim 1, wherein the chemical treatment is water.
Article having a sodium oxide concentration of 3% or more and a temperature of 20 to 150 ° C
A method for producing a titania-based catalyst, which is performed under conditions .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17832096A JP3374305B2 (en) | 1996-07-08 | 1996-07-08 | Method for producing titania-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17832096A JP3374305B2 (en) | 1996-07-08 | 1996-07-08 | Method for producing titania-based catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1015387A JPH1015387A (en) | 1998-01-20 |
| JP3374305B2 true JP3374305B2 (en) | 2003-02-04 |
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ID=16046430
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| JP17832096A Expired - Fee Related JP3374305B2 (en) | 1996-07-08 | 1996-07-08 | Method for producing titania-based catalyst |
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| US6414213B2 (en) * | 1999-01-07 | 2002-07-02 | Showa Denko K.K. | Titanium oxide particle-coated interior member or indoor equipment |
| KR100430405B1 (en) * | 1999-04-23 | 2004-05-03 | 주식회사 나노 | manufacturing method of titanium dioxide powder for photocatalyst |
| JP4628011B2 (en) * | 2004-04-14 | 2011-02-09 | ダイセル化学工業株式会社 | Titanium oxide crystal, photocatalyst, and organic compound oxidation method |
| JP4628010B2 (en) * | 2004-04-14 | 2011-02-09 | ダイセル化学工業株式会社 | Purification method of titanium oxide |
| KR101993236B1 (en) * | 2017-06-29 | 2019-06-26 | 허경삼 | Method for manufacturing visible-light active titanium dioxide photocatalyst by using chemicasurface modification |
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| KR102212649B1 (en) | 2019-04-01 | 2021-02-08 | 한국과학기술연구원 | Platinum-titanium dioxide catalyst, its production method, and its production apparatus |
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