JP4563689B2 - Photocatalyst and method for producing the same - Google Patents
Photocatalyst and method for producing the same Download PDFInfo
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- JP4563689B2 JP4563689B2 JP2004011064A JP2004011064A JP4563689B2 JP 4563689 B2 JP4563689 B2 JP 4563689B2 JP 2004011064 A JP2004011064 A JP 2004011064A JP 2004011064 A JP2004011064 A JP 2004011064A JP 4563689 B2 JP4563689 B2 JP 4563689B2
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- 239000011941 photocatalyst Substances 0.000 title claims description 166
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 151
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 104
- 239000002245 particle Substances 0.000 claims description 71
- 239000000377 silicon dioxide Substances 0.000 claims description 60
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 29
- 239000000017 hydrogel Substances 0.000 claims description 27
- 239000010419 fine particle Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 22
- 239000002689 soil Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000001699 photocatalysis Effects 0.000 claims description 15
- 239000008119 colloidal silica Substances 0.000 claims description 14
- 239000005416 organic matter Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 239000004115 Sodium Silicate Substances 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910002028 silica xerogel Inorganic materials 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 10
- 239000003570 air Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- -1 titanium alkoxide Chemical class 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004887 air purification Methods 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
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Description
本発明は、光エネルギーを利用して、有機物を分解する光触媒体及びその製造方法並びにその使用方法に関するものであり、更に詳しくは、平均粒子径１〜５０ｎｍの光触媒粒子を０．０１〜１ｗｔ％と、平均細孔径が２〜１５ｎｍで平均粒子径が1〜３０μｍのシリカゲル複合体等からなる新しい光触媒体であって、光触媒体の内部にまで光が透過でき、光触媒粒子の持つ大きな表面積、及び高い光活性を維持したまま、光効率良く、耐久性に優れ、且つ、取り扱いが容易である新規光触媒体及びその製造方法並びにその使用方法に関するものである。
本発明は、水、大気又は土壌等の浄化技術、環境技術の次世代のキー・テクノロジーとして注目されている光触媒関連の技術分野において、従来製品では、光触媒体の内部まで光が透過できないため、大部分の光触媒は十分に働いていない、という大きな問題点があったことを踏まえ、この問題点を確実に解決することが可能で、光触媒体の内部（中心）にまで光が透過できるようにした光触媒体であって、少ない光触媒粒子を用いて、高い光触媒活性が効率良く得られるようにした、光効率、耐久性、及び取り扱い等に優れた新しい光触媒体を開発し、提供することを可能とするものであり、光触媒を応用する技術分野における新技術の開発・新産業の創出の大きな推進力となり得るものとして有用である。
The present invention relates to a photocatalyst that decomposes an organic substance using light energy, a method for producing the photocatalyst, and a method for using the photocatalyst, and more specifically, 0.01 to 1 wt t %, A new photocatalyst composed of a silica gel composite having an average pore diameter of 2 to 15 nm and an average particle diameter of 1 to 30 μm, which can transmit light to the inside of the photocatalyst, In addition, the present invention relates to a novel photocatalyst that is light efficient, excellent in durability, and easy to handle while maintaining high photoactivity, a method for producing the same, and a method for using the same.
In the technical field related to photocatalyst, which is attracting attention as the next-generation key technology of purification technology for water, air, soil, etc., conventional products cannot transmit light to the inside of the photocatalyst, Based on the big problem that most photocatalysts are not working well, it is possible to solve this problem reliably and to allow light to penetrate into the center of the photocatalyst. It is possible to develop and provide a new photocatalyst that is excellent in photoefficiency, durability, and handling, etc., in which high photocatalytic activity can be efficiently obtained by using few photocatalyst particles. It is useful as a potential driver for the development of new technologies and the creation of new industries in the technical field where photocatalysts are applied.
近年、光触媒技術は、ＵＶあるいは可視光を照射するのみで、環境問題に対処できる新技術として、大気、水質、及び土壌の各技術分野で注目を集めている。光触媒反応は、光エネルギーの存在下で光触媒を用いて、有機物等を分解する反応であり、この反応は、太陽光や蛍光灯、白熱灯等の室内照明から給せられる光に含まれる紫外線を利用して、有害な有機物、無機物等を分解する技術として、例えば、ＳＯｘ、ＮＯｘ等の無機酸性ガス、シックハウス症候群の原因物質とされているホルムアルデヒドのような有機ガス、あるいは焼却処理により発生するダイオキシン等の環境ホルモン物質等を、二次汚染なしに安全に分解、無害化する環境材料として、水や空気の浄化や、建材、及びタイル等の建築材料への応用等、広く注目を集め、研究されている。また、このような光触媒の特性を生かし、ガラス食器や観葉植物等の生活製品から高速道路や建築物の外壁等の工業用品まで幅広い分野で光触媒の実用化及び製品化が盛んに進められつつある。光触媒としては、二酸化チタン、酸化亜鉛、セレン化カドミウム、ガリウムヒ素、及びチタン酸ストロンチウム等が知られているが、一般には、二酸化チタンがよく用いられている。二酸化チタン等の光触媒の存在下に、有害有機物等に紫外線等を照射することによって、有機物等は分解され、無害化される。 In recent years, photocatalytic technology has attracted attention in the air, water quality, and soil technical fields as a new technology that can deal with environmental problems by simply irradiating UV or visible light. The photocatalytic reaction is a reaction that decomposes organic substances using a photocatalyst in the presence of light energy. This reaction uses ultraviolet light contained in light supplied from indoor lighting such as sunlight, fluorescent light, and incandescent light. For example, inorganic acid gases such as SOx and NOx, organic gases such as formaldehyde, which is a causative substance of sick house syndrome, or dioxins generated by incineration, are used as technologies for decomposing harmful organic and inorganic substances. As an environmental material that safely decomposes and detoxifies environmental hormone substances, etc. without secondary pollution, etc., it attracts widespread attention, such as purification of water and air, and application to building materials such as building materials and tiles. Has been. In addition, taking advantage of the characteristics of such photocatalysts, practical application and commercialization of photocatalysts are being actively promoted in a wide range of fields, from daily products such as glass tableware and foliage plants to industrial products such as highways and exterior walls of buildings. . As the photocatalyst, titanium dioxide, zinc oxide, cadmium selenide, gallium arsenide, strontium titanate, and the like are known, but in general, titanium dioxide is often used. In the presence of a photocatalyst such as titanium dioxide, the organic matter etc. is decomposed and rendered harmless by irradiating the harmful organic matter etc. with ultraviolet rays.
以下に、光触媒として、代表的な、二酸化チタン光触媒を例にして本発明の背景技術を説明する。
従来、二酸化チタン光触媒の原料としては、二酸化チタンの微粒子や、金属チタンのアルコキシド溶液等が利用されてきた。二酸化チタン微粒子を使用する場合には、例えば、二酸化チタン微粒子をそのまま用いる方法、バインダー等で固形物上に固定して用いる方法、塗料や水和物等に混合した後、固形物上に塗布、乾燥し、固定化して用いる方法等がある。金属チタンのアルコキシド溶液を使用する場合には、例えば、これを固形物上に塗布した後、乾操、焼成して二酸化チタン薄膜を生成させる、所謂、ゾルゲル法等がある。その他、例えば、CVD法、スパッタ法等で固形物上に二酸化チタン薄膜を生成させて使用する方法もある。
The background art of the present invention will be described below by taking a typical titanium dioxide photocatalyst as a photocatalyst.
Conventionally, fine particles of titanium dioxide, alkoxide solutions of titanium metal, and the like have been used as raw materials for titanium dioxide photocatalysts. When using titanium dioxide fine particles, for example, a method of using titanium dioxide fine particles as they are, a method of using the titanium dioxide fine particles fixed on a solid with a binder, etc., after mixing with a paint or hydrate, There are methods such as drying and immobilization. In the case of using a metal titanium alkoxide solution, for example, there is a so-called sol-gel method in which a titanium dioxide thin film is formed by applying the alkoxide solution onto a solid material, followed by drying and baking. In addition, there is a method in which a titanium dioxide thin film is formed on a solid material by, for example, a CVD method or a sputtering method.
二酸化チタン微粒子をそのまま光触媒として用いる場合には、その表面積が大きく、光活性が高く、有機物の吸着性が高いという長所がある。しかしながら、微粒子であるために取り扱いにくく、気相中や液相中で使用する場合には、微粒子の位置を制御することが困難である。また、飛散あるいは分散した場合には、紫外線を散乱してしまい、光効率が悪い上、回収することも困難である。バインダー等で固形物上に固定して使用する場合には、微粒子がバインダーに覆われたり、埋没したりしてしまうため、微粒子が、有機物等や酸素、紫外線と接触する表面積が低下し、その結果、有機物等の分解効率が低下してしまうという問題がある。また、有機バインダーを使用した場合には、バインダー自身が二酸化チタン微粒子で分解されるという問題が新たに生じる。そのため、例えば、バインダー、担持体である繊維類の分解又は劣化を防止する技術がいくつか提案されている（特許文献１、２参照）。 When titanium dioxide fine particles are used as they are as a photocatalyst, they have the advantages of a large surface area, high photoactivity, and high organic matter adsorption. However, since it is a fine particle, it is difficult to handle, and when used in a gas phase or a liquid phase, it is difficult to control the position of the fine particle. In addition, when scattered or dispersed, ultraviolet rays are scattered, which is inferior in light efficiency and difficult to recover. When fixed on a solid material with a binder or the like, since the fine particles are covered or buried in the binder, the surface area of the fine particles that come into contact with organic matter, oxygen, or ultraviolet rays is reduced. As a result, there is a problem that the decomposition efficiency of organic substances and the like is lowered. In addition, when an organic binder is used, there arises a new problem that the binder itself is decomposed by titanium dioxide fine particles. For this reason, for example, several techniques for preventing the decomposition or deterioration of the binder and the fibers as the support have been proposed (see Patent Documents 1 and 2).
金属チタンのアルコキシド溶液から、ゾルゲル法によって固形物上に薄膜を生成させて使用する場合（特許文献３参照）には、固形物の形態にほとんど影響を与えず、また、わずかな隙間にも膜を形成できるという長所がある。また、６００℃以下の温度で焼成することによって、光触媒活性の高いアナタース型結晶を形成できる（特許文献４参照）。しかしながら、アナタース型結晶の薄膜の調製には長時間を要する上、調製条件の制御も困難である。更に、薄膜であるために、二酸化チタンの微粒子に比べて有機物等との接触面積が小さくなるため、分解効率が低い、耐久性が低い、有機物等の吸着性が悪いという問題点がある。シリカゲル担体に担持してこれらの問題解決をはかっている例もあるが、アルコキシド溶液の分子径が大きいため、細孔内に担持するには１０ｎｍ以上の細孔径が必要であった。このため、シリカゲル自身の吸着性能を十分に発揮することはできない等の問題点があった。 When a thin film is formed on a solid by a sol-gel method from a metal titanium alkoxide solution (see Patent Document 3), the form of the solid is hardly affected, and the film is formed even in a slight gap. There is an advantage that can be formed. Moreover, an anatase type crystal with high photocatalytic activity can be formed by baking at the temperature of 600 degrees C or less (refer patent document 4). However, it takes a long time to prepare a thin film of anatase-type crystal, and it is difficult to control the preparation conditions. Furthermore, since it is a thin film, the contact area with the organic matter or the like is smaller than that of the fine particles of titanium dioxide, so that there are problems that the decomposition efficiency is low, the durability is low, and the adsorptivity of the organic matter is poor. Although there are examples in which these problems are solved by being supported on a silica gel carrier, the pore size of 10 nm or more is required for supporting in the pores because the molecular diameter of the alkoxide solution is large. For this reason, there existed problems, such as being unable to fully exhibit the adsorption performance of silica gel itself.
また、従来、光触媒体は、光を吸収して活性を示すものであるから、光透過性についてはあまり問題とされなかった。光透過性に関しては、例えば、金属化合物含有球状多孔質シリカよりなる粉末消臭剤において、光散乱や乱反射による透明性が失われる現象を抑制し、また、金属化合物の奏する効果を向上させるために、粒径及び屈折率を特定した中実多孔シリカビーズが提案されている（特許文献５参照）。しかしながら、これには、光触媒を示唆する技術的な記載はない。また、光触媒体は二酸化チタン微粒子に代表されるが、有機チタン等を用いる場合は言うまでもなく、微粒子二酸化チタンでさえも高価であり、この光触媒を多く含有する光触媒体も自ずと高価なものであった。 Conventionally, photocatalysts absorb light and exhibit activity, so that light transmittance has not been a major problem. Regarding light transmission, for example, in a powder deodorant made of metal compound-containing spherical porous silica, to suppress the phenomenon of loss of transparency due to light scattering and irregular reflection, and to improve the effect of the metal compound Solid porous silica beads having a specified particle size and refractive index have been proposed (see Patent Document 5). However, there is no technical description that suggests a photocatalyst. The photocatalyst is represented by fine titanium dioxide particles. Needless to say, when organic titanium or the like is used, even fine particle titanium dioxide is expensive, and the photocatalyst containing a large amount of the photocatalyst is naturally expensive. .
このような状況の中で、本発明者らは、上記従来技術に鑑みて、光触媒の内部まで光が透過できる新しいタイプの光触媒体を開発するとともに、環境問題の解決に有用であり、光触媒微粒子の長所を十分に発揮でき、光透過性の点でも優れた新しい光触媒体を開発することを目標として鋭意研究を積み重ねた結果、平均粒子径１〜５０ｎｍの光触媒粒子を０．０１〜１ｗｔ％と、平均細孔径が２〜１５ｎｍで平均粒子径1〜３０μｍのシリカゲルとその複合体からなる光触媒体を構築することによって、従来の問題点を解決できることを見出し、本発明を完成させるに至った。
即ち、本発明の目的は、光触媒体の内部にまで光を透過させることが可能であり、光触媒体の内部にまで十分に光活性が得られる新しいタイプの光触媒体を提供することである。
また、本発明の目的は、光触媒微粒子の特徴である、大きな表面積、高い有機物吸着性、及び光活性を維持した光触媒体を提供することである。
また、本発明の目的は、照射された光のエネルギーを効率良く利用することができる、光触媒体を提供することである。
また、本発明の目的は、耐久性に優れ、取り扱いが容易で、且つ、廉価な光触媒体を提供することである。
更に、本発明の目的は、水、大気及び土壌中に含有されている、有害な有機物等を効率良く除去するのに有用な光触媒体を提供することである。
Under such circumstances, the present inventors have developed a new type photocatalyst capable of transmitting light to the inside of the photocatalyst in view of the above-described conventional technology, and are useful for solving environmental problems. As a result of intensive research with the goal of developing a new photocatalyst that can fully demonstrate the advantages of light transmission and excellent in light transmittance, 0.01 to 1 wt% of photocatalyst particles having an average particle diameter of 1 to 50 nm are obtained. And found that the conventional problems can be solved by constructing a photocatalyst composed of a silica gel having an average pore diameter of 2 to 15 nm and an average particle diameter of 1 to 30 μm and a composite thereof, and has completed the present invention. .
That is, an object of the present invention is to provide a new type of photocatalyst that can transmit light to the inside of the photocatalyst and can sufficiently obtain photoactivity to the inside of the photocatalyst.
Another object of the present invention is to provide a photocatalyst that maintains the large surface area, high organic matter adsorptivity, and photoactivity, which are the characteristics of the photocatalyst fine particles.
Moreover, the objective of this invention is providing the photocatalyst body which can utilize the energy of the irradiated light efficiently.
Another object of the present invention is to provide a photocatalyst that is excellent in durability, easy to handle, and inexpensive.
Furthermore, an object of the present invention is to provide a photocatalyst useful for efficiently removing harmful organic substances and the like contained in water, air and soil.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）チタニア混入シリカヒドロゲル複合体からなる、光透過性の光触媒体であって、上記複合体が、シリカ濃度２〜４５％のシリカゾルに、平均粒子径１〜５０ｎｍのチタニア粉体をシリカゾル中のシリカ固形分に対して０．０１〜１ｗｔ％を混入しチタニア混入シリカヒドロゾルとし、これをゲル化させたチタニア混入シリカヒドロゲル複合体であることを特徴とする光触媒体。
（２）複合体中に、コロイダルシリカ充填剤が含まれていることを特徴とする、前記（１）に記載の光触媒体。
（３）上記複合体が、チタニア微粒子、ケイ酸ソーダと硫酸の混合により得られるチタニア混入シリカゾルをゲル化させたものであることを特徴とする、前記（１）に記載の光触媒体。
（４）チタニア混入シリカヒドロゲル複合体からなる、光透過性の光触媒体の製造方法であって、シリカ濃度２〜４５％のシリカゾルに、粒子径１〜５０ｎｍのチタニア粉末をシリカゾル中のシリカ固形分に対して０．０１〜１ｗｔ％を混入しチタニア混入シリカヒドロゾルとし、これをゲル化させて、チタニア混入シリカヒドロゲル複合体にすることを特徴とする光触媒体の製造方法。
（５）得られたヒドロゲル複合体を熱水重合することを特徴とする、前記（４）に記載の光触媒体の製造方法。
（６）チタニア微粒子をケイ酸ソーダ及び硫酸に混入してチタニア混入シリカゾルを前駆体として得た後、ゲル化させてチタニア混入シリカヒドロゲル複合体にすることを特徴とする、前記（４）に記載の光触媒体の製造方法。
（７）チタニア混入シリカヒドロゲル複合体を乾燥して、チタニア混入シリカキセロゲルにすることを特徴とする、前記（４）に記載の光触媒体の製造方法。
（８）前記（１）から（３）のいずれかに記載の光触媒体を、水と接触させ、その光触媒作用により水浄化することを特徴とする、水浄化方法。
（９）前記（１）から（３）のいずれかに記載の光触媒を、空気と接触させ、その光触媒作用により気相吸着分解光触媒として使用することを特徴とする、空気浄化方法。
（１０）前記（６）に記載の前駆体である、チタニア混入シリカゾルを、土壌に注入することにより土壌構成鉱物間に光触媒体を固定化し、その土壌に含まれる有機物を光触媒作用により分解除去することを特徴とする、土壌浄化方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) consisting of titania mixed silica hydrogel complex, light transmitting an excessive of the photocatalyst, the complex, the silica concentration from 2 to 45% of silica sol, silica sol titania powder having an average particle diameter 1~50nm A photocatalyst characterized by being a titania-mixed silica hydrogel composite obtained by mixing 0.01 to 1 wt% of the solid content of silica into a titania-mixed silica hydrosol .
( 2 ) The photocatalyst according to ( 1) above, wherein the composite includes a colloidal silica filler.
( 3 ) The photocatalyst according to (1) above, wherein the composite is a gelled titania-mixed silica sol obtained by mixing titania fine particles, sodium silicate and sulfuric acid.
(4) consisting of titania mixed silica hydrogel complex, a method for producing a light transmission over of photocatalyst, silica concentration from 2 to 45% of silica sol, silica solid in the silica sol of titania powder having a particle size 1~50nm A method for producing a photocatalyst, characterized in that 0.01 to 1 wt% is mixed to form a titania-mixed silica hydrosol, which is gelled to form a titania-mixed silica hydrogel composite .
( 5 ) The method for producing a photocatalyst according to ( 4 ) above, wherein the obtained hydrogel composite is subjected to hydrothermal polymerization.
( 6 ) The titania fine particles are mixed with sodium silicate and sulfuric acid to obtain a titania-mixed silica sol as a precursor, and then gelled to form a titania-mixed silica hydrogel composite, as described in ( 4 ) above The manufacturing method of the photocatalyst body.
( 7 ) The method for producing a photocatalyst according to ( 4 ) above, wherein the titania-mixed silica hydrogel composite is dried to form a titania-mixed silica xerogel.
( 8 ) A water purification method, wherein the photocatalyst body according to any one of (1) to ( 3 ) is brought into contact with water and water is purified by the photocatalytic action.
( 9 ) An air purification method comprising using the photocatalyst according to any one of (1) to ( 3 ) in contact with air and using the photocatalyst as a gas-phase adsorption decomposition photocatalyst.
( 10 ) The titania-mixed silica sol, which is the precursor described in ( 6 ) above, is injected into the soil to fix the photocatalyst between the soil constituent minerals, and the organic matter contained in the soil is decomposed and removed by photocatalysis. The soil purification method characterized by the above-mentioned.
次に、本発明について更に詳細に説明する。
本発明の光触媒体は、光触媒体の内部（中心）にまで光が透過できるようにした光触媒体であって、平均粒子径１〜５０ｎｍの光触媒粒子を０．０１〜１ｗｔ％と、平均細孔径が２〜１５ｎｍで平均粒子径が１〜３０μｍのシリカゲル粉体との複合体からなること、及び平均粒子径１〜５０ｎｍの光触媒粒子を０．０１〜１ｗｔ％と、平均細孔径が２〜１５ｎｍで平均粒子径が１〜３０μｍのシリカゲルを含む光触媒粒子含有シリカヒドロゲル複合体からなることを特徴とするものである。光触媒体は、光を吸収して活性を示すことから、基本的には光透過性がないか、又は著しく低い。そのため、従来のシリカ成分をマトリックスとする光触媒体では、この光触媒粒子の量を単純に増やすこと、即ち、その含有量を１０％以上、例えば、５０％までにすること、で光活性を向上させる方策がとられていた。しかし、この方法で得られる光触媒体では、その内部にまで光が透過できないため、大部分の光触媒粒子は十分に働いていないという問題点があった。本発明は、こうした従来技術の問題点を解消するために、特定の光触媒粒子を所定の含有量で高分散させ、光触媒体の内部（中心）にまで光が透過できるようにして、光を十分に光触媒粒子に照射し得るように特別の工夫を凝らし、少ない光触媒粒子を用いて、高い光触媒活性が効率良く得られるようにした点に特徴を有するものである。即ち、本発明では、例えば、シリカキセロゲル粉体を用いる場合には、光触媒を十分にシリカキセロゲルにまとわり付かせるために、平均粒子径１〜５０ｎｍの光触媒粒子を使用し、シリカゲル粉体の平均細孔径を２〜１５ｎｍとし、平均粒子径を1〜３０μｍとし、その添加量を、０．０１〜１ｗｔ％として、キセロゲルに十分に分散した状態になるようにすると、成形により得られた粒子の内部にまで光が透過できる光触媒体を作製することが可能となるので、光触媒体の内部までにも十分に光活性が得られる状況になる。
Next, the present invention will be described in more detail.
The photocatalyst of the present invention is a photocatalyst capable of transmitting light to the inside (center) of the photocatalyst, and has an average fine particle size of 0.01 to 1 wt% with an average particle diameter of 1 to 50 nm. It is composed of a composite with silica gel powder having a pore size of 2 to 15 nm and an average particle size of 1 to 30 μm, and 0.01 to 1 wt% of photocatalyst particles having an average particle size of 1 to 50 nm and an average pore size of 2 It consists of a photocatalyst particle-containing silica hydrogel composite containing silica gel having an average particle diameter of 1 to 30 μm at ˜15 nm. Since the photocatalyst absorbs light and exhibits activity, it basically has no light transmittance or is extremely low. Therefore, in the conventional photocatalyst using a silica component as a matrix, the photoactivity is improved by simply increasing the amount of the photocatalyst particles, that is, by increasing the content to 10% or more, for example, 50%. Measures were taken. However, the photocatalyst obtained by this method has a problem in that most of the photocatalyst particles do not work sufficiently because light cannot penetrate into the photocatalyst. In order to eliminate such problems of the prior art, the present invention sufficiently disperses specific photocatalyst particles with a predetermined content so that light can be transmitted to the inside (center) of the photocatalyst. In addition, the present invention is characterized in that a special device has been devised so that the photocatalyst particles can be irradiated, and that high photocatalytic activity can be obtained efficiently by using a small number of photocatalyst particles. That is, in the present invention, for example, when silica xerogel powder is used, photocatalyst particles having an average particle diameter of 1 to 50 nm are used in order to sufficiently bind the photocatalyst to silica xerogel. When the average pore diameter was 2 to 15 nm, the average particle diameter was 1 to 30 μm, and the addition amount was 0.01 to 1 wt%, the dispersion was sufficiently dispersed in the xerogel. Since it becomes possible to produce a photocatalyst capable of transmitting light to the inside of the particles, it is possible to obtain sufficient photoactivity even inside the photocatalyst.
また、シリカゾルを用いる場合でも、シリカ濃度２〜４５％のシリカゾルに、粒子径１〜５０ｎｍのチタニア粉体を、シリカゾル中のシリカ固形分に対して０．０１〜１％を混入して、シリカヒドロゾル光触媒体とし、また、このゾルをゲル化させ、チタニア混入シリカヒドロゲル複合体とすることで、光が、得られたヒドロゲル内を十分に透過し、光活性が十分発揮できる光触媒体を作製することが可能となる。本発明は、上記特定の構成を採用することで、シリカ成分をマトリックスとする光触媒体の内部（中心）にまで光が透過できるようにした光触媒体の製造を可能にしたものである。また、得られるシリカヒドロゾルとゲルは、通常は、乾燥して使用されるが、本発明では、この得られたゾル、ゲルについて、夫々適切な使用方法が提供され、ゾルの場合には、例えば、これを土壌中に注入することで、土壌粒子間に充填され、その間に存在する有機物を捕捉、固定し、光触媒作用で分解することができる。また、ヒドロゲルでは、例えば、水系で使用する場合には、十分な強度と耐水性を有し、キセロゲルにするための乾燥エネルギーも省略することができる。また、本発明では、好適な光活性を得るために、熱水処理によりヒドロゲルの物性を制御する方法が提供される。 Even when silica sol is used, a silica sol having a silica concentration of 2 to 45 % is mixed with a titania powder having a particle diameter of 1 to 50 nm and 0.01 to 1% of the silica solid content in the silica sol is mixed. By making this sol into a hydrosol photocatalyst and gelling it into a titania-mixed silica hydrogel composite, a photocatalyst capable of sufficiently transmitting light through the obtained hydrogel and exhibiting sufficient photoactivity is produced. It becomes possible to do. The present invention makes it possible to produce a photocatalyst that allows light to pass through the inside (center) of the photocatalyst using a silica component as a matrix by adopting the above specific configuration. Further, the obtained silica hydrosol and gel are usually used after being dried, but in the present invention, appropriate methods of use are provided for the obtained sol and gel, respectively. For example, by injecting this into the soil, it is possible to capture and fix organic substances that are filled between the soil particles and exist between them, and decompose by photocatalysis. In addition, when the hydrogel is used in an aqueous system, for example, it has sufficient strength and water resistance, and drying energy for making a xerogel can also be omitted. Moreover, in this invention, in order to obtain suitable photoactivity, the method of controlling the physical property of hydrogel by hydrothermal treatment is provided.
図１は、本発明の光触媒体の外観の一例を示す写真である。図２は、０．１％チタニア混入キセロゲル複合体の光学写真であり、断面に見られる小さな白い点がチタニア粒子で、シリカゲルの中に分散しているのが分かる。チタニア粒子による光分解作用はチタニアの近傍で生起すると考えられるので、チタニアの混入量を所定のレベルに下げた本発明では、この光分解サイトに接触していないシリカ部分に特定の機能を持つ有機化合物を導入することができ、例えば、光分解サイト以外のシリカに、特定の官能基、例えば、アミノ基等を導入すると、これが、ホルマリン等の吸着サイトとなり、シリカにはない特定の吸着性能を付加した光触媒として機能させることが可能となる。図３は、チタニア濃度と光透過率との関係を示す。 FIG. 1 is a photograph showing an example of the appearance of the photocatalyst of the present invention. FIG. 2 is an optical photograph of a 0.1% titania-mixed xerogel composite, and it can be seen that small white dots seen in the cross section are titania particles and are dispersed in silica gel. Since the photodegradation action by titania particles is considered to occur in the vicinity of titania, in the present invention in which the amount of titania mixed is lowered to a predetermined level, the organic part having a specific function in the silica portion not in contact with the photodecomposition site. A compound can be introduced. For example, when a specific functional group such as an amino group is introduced into silica other than the photolysis site, this becomes an adsorption site such as formalin, and has a specific adsorption performance not found in silica. It can function as an added photocatalyst. FIG. 3 shows the relationship between titania concentration and light transmittance.
本発明の光触媒体を使用して、成形体を製造するには、光触媒体とコロイダルシリカを含む混合物を成形し、次いで、乾燥する。上記成形は、造粒機、ベレタイザー、押出成形機、及び射出成形機から選ばれるいずれかの成形機で行うことが好ましい。また、上記成形及び乾燥は、６００℃以下の温度で行うことが好ましい。 In order to produce a molded body using the photocatalyst body of the present invention, a mixture containing the photocatalyst body and colloidal silica is molded and then dried. The molding is preferably performed by any molding machine selected from a granulator, a beretizer, an extrusion molding machine, and an injection molding machine. Moreover, it is preferable to perform the said shaping | molding and drying at the temperature of 600 degrees C or less.
本発明で用いられる光触媒粒子としては、光触媒反応を行うことができるものであれば特に制限はないが、例えば、二酸化チタン、酸化亜鉛、セレン化カドミウム、ガリウムヒ素、チタン酸ストロンチウム等の公知の光触媒粒子、市販の光触媒粒子を使用することができ、好ましくは二酸化チタン粒子が用いられる。光触媒粒子は、平均粒子径が１〜５０ｎｍのものであり、好ましくは５〜５０ｎｍ、更に好ましい範囲は１０〜３０ｎｍの平均粒子径を有する。このような平均粒子径を有する光触媒粒子は、表面積が大きく、光活性が高いため、好ましいものであるが、平均粒子径が１ｎｍ未満となると、光活性が低下するので好ましくなく、５０ｎｍを超えると、表面積が低下し、活性が低下するので好ましくない。本発明では、光触媒粒子は、シリカ固形分に対して、０．０１〜１ｗｔ％含まれる。０．０１未満では、光触媒作用が低い（光吸収粒子による光吸収が低下する）ので好ましくなく、上記範囲を超えると、表面粒子のみしか光が当たらないようになり、また、ゾル−ゲル反応後の強度が弱くなるので好ましくない。 The photocatalyst particles used in the present invention are not particularly limited as long as they can perform a photocatalytic reaction. For example, known photocatalysts such as titanium dioxide, zinc oxide, cadmium selenide, gallium arsenide, strontium titanate, etc. Particles and commercially available photocatalyst particles can be used, and titanium dioxide particles are preferably used. The photocatalyst particles have an average particle diameter of 1 to 50 nm, preferably 5 to 50 nm, and more preferably 10 to 30 nm. Photocatalyst particles having such an average particle size are preferable because of their large surface area and high photoactivity, but when the average particle size is less than 1 nm, the photoactivity decreases, and when it exceeds 50 nm. , It is not preferable because the surface area is decreased and the activity is decreased. In the present invention, the photocatalyst particles, the silica solids, Ru contains 0.01 to 1 w t%. If it is less than 0.01, the photocatalytic action is low (light absorption by the light-absorbing particles decreases), which is not preferable. If it exceeds the above range , only the surface particles are exposed to light, and after the sol-gel reaction Since the intensity | strength of becomes weak, it is not preferable.
本発明では、シリカゲル粉体は、平均細孔径が２〜１５ｎｍ、更に好ましくは、３〜１０ｎｍであり、平均粒子径が１〜３０μｍ、更に好ましい範囲は、２〜１５μｍである。この細孔径の範囲では、各種有機物の吸着特性が制御され、また、光の透過率も良好であるため、成形した粒子内にも十分に光が透過して光触媒粒子に届き、光活性を十分に発揮できるものである。しかし、平均細孔径が、２ｎｍ未満のシリカゲルは簡単には得られないし、また、１５ｎｍを超えると、表面積が低下し、吸着力も低下するので好ましくない。また、平均粒子径が、１μｍ未満では、凝集体となり、実質的に１μｍ以上となるので好ましくなく、３０μｍを超える平均粒子径では、成形性が悪いので好ましくない。 In the present invention, the silica gel powder has an average pore diameter of 2 to 15 nm, more preferably 3 to 10 nm, an average particle diameter of 1 to 30 μm, and a more preferable range of 2 to 15 μm. Within this pore size range, the adsorption characteristics of various organic substances are controlled, and the light transmittance is also good, so that light is sufficiently transmitted through the shaped particles to reach the photocatalyst particles, and the photoactivity is sufficient. It can be demonstrated to. However, silica gel having an average pore diameter of less than 2 nm cannot be easily obtained, and if it exceeds 15 nm, the surface area decreases and the adsorptive power also decreases. Further, if the average particle size is less than 1 μm, it becomes an aggregate and becomes substantially 1 μm or more, which is not preferable. The average particle size exceeding 30 μm is not preferable because the moldability is poor.
本発明で、上述の光触媒粒子とシリカゲルを混合して、光触媒体を製造するには、これらを十分に混合し、高分散ないし均一分散させて、両者が高度に分散された状態が得られるまで混合することが重要である。この場合、通常の混合手段が使用できる。これにより、光触媒体の内部（中心）にまで光が透過できるようになり、表面粒子のみではなく内部の粒子にも光るが当たるようにすることが可能となる。本発明の、特定の平均細孔径、及び平均粒子径を有するシリカゲル粉体は、市販のシリカ微粉末から入手可能であり、好適なものとして、例えば、市販の製品（富士シリシア化学製、商品名サイリシア、グレード＃５３０、＃３５０、＃７７０、＃４５０）が挙げられる。 In the present invention, in order to produce a photocatalyst by mixing the above-mentioned photocatalyst particles and silica gel, they are sufficiently mixed and highly dispersed or uniformly dispersed until a state in which both are highly dispersed is obtained. It is important to mix. In this case, a normal mixing means can be used. As a result, light can be transmitted to the inside (center) of the photocatalyst body, and not only the surface particles but also the internal particles can be irradiated with light. The silica gel powder having a specific average pore diameter and an average particle diameter of the present invention can be obtained from commercially available silica fine powder. As a suitable product, for example, a commercially available product (manufactured by Fuji Silysia Chemical Co., Ltd., trade name) Cylicia, grades # 530, # 350, # 770, # 450).
また、本発明の他の態様は、シリカ濃度２〜４５％のシリカゾルと、粒子径１〜５０ｎｍの光触媒粒子を、シリカゾル中のシリカ固形分に対して０．０１〜１％を混入したシリカヒドロゾル光触媒体、又は、このゾルをゲル化したチタニア混入シリカヒドロゲル複合体からなる光触媒体、である。本発明で使用するシリカゾルの、シリカ濃度は２〜４５％の範囲、更に好ましくは、５〜２５％、であるが、シリカ濃度が２％未満であると、ゲル化しにくく、含水が多いため乾燥費が高くつくので好ましくなく、４５％を超えると、実質的にゾルが得られない。シリカゾルの製造には、アルカリ金属ケイ酸塩と、アルカリ金属ケイ酸塩との反応で不溶性シリカを生成する化合物とを混合して行われる。アルカリ金属ケイ酸塩としては、例えば、ケイ酸ナトリウム、ケイ酸カリウム等が挙げられるが、ＳｉＯ２／Ｎａ２Ｏのモル比が２〜４のケイ酸ナトリウムの使用が好ましい。 In another aspect of the present invention, silica hydrolyzate containing silica sol having a silica concentration of 2 to 45% and photocatalyst particles having a particle diameter of 1 to 50 nm in an amount of 0.01 to 1% based on the silica solid content in the silica sol. A sol photocatalyst or a photocatalyst comprising a titania-mixed silica hydrogel composite obtained by gelling this sol. The silica sol used in the present invention has a silica concentration in the range of 2 to 45%, more preferably 5 to 25%. However, when the silica concentration is less than 2%, the silica sol is difficult to gel and has a high water content. Since the cost is high, it is not preferable. If it exceeds 45%, a sol cannot be obtained substantially. The production of the silica sol is performed by mixing an alkali metal silicate and a compound that generates insoluble silica by reaction with the alkali metal silicate. Examples of the alkali metal silicate include sodium silicate and potassium silicate, and it is preferable to use sodium silicate having a SiO 2 / Na 2 O molar ratio of 2 to 4.
アルカリ金属ケイ酸塩との反応でシリカを生成する化合物としては、例えば、硫酸、硝酸、塩酸等が挙げられるが、最も好ましいのは、硫酸である。これらの化合物は、アルカリ金属ケイ酸塩１モルに対して、アルカリモル数と化学量論量の９５〜１５０％程度、好ましくは、９８〜１２０モルの割合で使用される。シリカゾルは、水系媒体中での反応により得られ、反応液の濃度、混合割合、反応時間、及び攪拌条件等については、特に限定されないが、所望の最終製品の性状に応じて適宜決定することができる。 Examples of the compound that generates silica by reaction with an alkali metal silicate include sulfuric acid, nitric acid, hydrochloric acid, and the like, and most preferred is sulfuric acid. These compounds are used in an amount of about 95 to 150%, preferably 98 to 120 moles of the number of moles of alkali and stoichiometric amount with respect to 1 mole of alkali metal silicate. The silica sol is obtained by a reaction in an aqueous medium, and the concentration of the reaction solution, the mixing ratio, the reaction time, the stirring conditions, etc. are not particularly limited, but may be appropriately determined according to the properties of the desired final product. it can.
シリカゾルと光触媒粒子とのゲル化物を得るには、上述の方法で合成したシリカゾルに光触媒粒子を混入した後、ゲル化する方法、又は、アルカリ金属ケイ酸塩とアルカリ金属ケイ酸塩との反応で不溶性シリカを生成する化合物と光触媒粒子の、三者の混合物をゾル化した後、ゲル化する方法でも製造することができる。シリカゾルと光触媒粒子との混合物をゲル化するには、公知の方法、例えば、過剰酸量の調整、ｐＨ調整、加熱、濃縮制御等が使用される。 In order to obtain a gelled product of silica sol and photocatalyst particles, the photocatalyst particles are mixed into the silica sol synthesized by the above method and then gelled, or the reaction between alkali metal silicate and alkali metal silicate is performed. It can also be produced by a method in which a mixture of three compounds of a compound that forms insoluble silica and photocatalyst particles is made into a sol and then gelled. In order to gel the mixture of silica sol and photocatalyst particles, a known method, for example, adjustment of excess acid amount, pH adjustment, heating, concentration control or the like is used.
そして、これらの方法により、本発明のシリカゲル複合体を含む光触媒体を製造することができるが、この場合、濃度２０〜２７％、ＳｉＯ２／Ｎａ２Ｏのモル比が、３．０〜３．５のケイ酸ナトリウムと濃度２０〜２５％の硫酸とを、３〜１対１で混合した系が最も好ましい。 また、上述のゲル製造方法の途中で生成する、光触媒粒子を含むゾルは、ゲル化しないで、光触媒体として使用することができる。このゾルは、主として、土壌中に注入することにより、土壌鉱物間に固定化され、土壌中に含まれる有機物等を光触媒作用により分解除去するために特に有用である。 And by these methods, the photocatalyst containing the silica gel composite of the present invention can be produced. In this case, the concentration is 20 to 27% and the molar ratio of SiO 2 / Na 2 O is 3.0 to 3. Most preferred is a system in which 5 to 5 sodium silicate and sulfuric acid having a concentration of 20 to 25% are mixed in a 3 to 1 to 1 ratio. Moreover, the sol containing photocatalyst particles produced in the middle of the above-described gel production method can be used as a photocatalyst without gelation. This sol is fixed between soil minerals mainly by being injected into the soil, and is particularly useful for decomposing and removing organic substances and the like contained in the soil by photocatalysis.
本発明により製造された光触媒体を、熱水処理することにより物性と光触媒活性を向上させることができる。熱水処理は、具体的には、例えば、光触媒体を、水に浸漬し、ｐＨを調整し、加熱する処理であり、例えば、水の存在下に、大気圧力下、ｐＨ７．０、温度８０℃で処理するものである。しかし、これらに限定されるものではない。この処理によって、細孔径が向上し、吸着活性に適した細孔径が得られる。したがって、光触媒体の製造にあたっては、水熱処理は有用である。 Physical properties and photocatalytic activity can be improved by subjecting the photocatalyst produced according to the present invention to hot water treatment. Specifically, the hydrothermal treatment is, for example, a treatment in which a photocatalyst is immersed in water, pH is adjusted, and heated. For example, in the presence of water, atmospheric pressure, pH 7.0, temperature 80 It is to be processed at ℃. However, it is not limited to these. By this treatment, the pore diameter is improved, and a pore diameter suitable for adsorption activity is obtained. Therefore, hydrothermal treatment is useful in the production of the photocatalyst.
また、本発明の光触媒体は、必要に応じて、バインダー及び／又は充填剤と混合され、成形体とした後に使用されるが、この場合、例えば、粒状、ペレット状、及びハニカム状等の様々な形で使用される。バインダーとしては、特に限定されないが、例えば、コロイダルシリカ、コロイダルアルミナ、モンモリロナイト、及びカオリナイト等が例示され、コロイダルシリカが最も好ましい。充填剤としては、特に限定されないが、例えば、メチルセルロースが例示される。本発明で、バインダーとして用いられるコロイダルシリカは、アモルファスシリカのコロイド粒子が水溶液中に安定に分散しているものであり、乾燥することによって、このコロイド粒子の凝集結合力が作用して、シリカの３次元長鎖状網目構造となる。このようなコロイダルシリカをバインダーとして使用すると、シリカの３次元長鎖状網目構造の隙間に光触媒微粒子が挟み込まれた状態で保持され、光触媒粒子と、分解対象物質である有機物、紫外線、及び酸素との接触を阻害しないように成形できる。また、光触媒粒子の表面積や光活性も高く維持できる。更に、得られた光触媒体は、機械的強度や耐久性にも優れたものとなる。 Further, the photocatalyst body of the present invention is used after being mixed with a binder and / or a filler as necessary to form a molded body. In this case, for example, various forms such as a granular form, a pellet form, and a honeycomb form are used. Is used in various forms. Although it does not specifically limit as a binder, For example, colloidal silica, colloidal alumina, montmorillonite, kaolinite, etc. are illustrated and colloidal silica is the most preferable. Although it does not specifically limit as a filler, For example, methylcellulose is illustrated. In the present invention, colloidal silica used as a binder is one in which colloidal particles of amorphous silica are stably dispersed in an aqueous solution. It becomes a three-dimensional long chain network structure. When such colloidal silica is used as a binder, the photocatalyst fine particles are held in the gap between the three-dimensional long-chain network structure of silica, and the photocatalyst particles and organic substances, ultraviolet rays, and oxygen, which are decomposition target substances, are retained. Can be molded so as not to impede contact. Further, the surface area and photoactivity of the photocatalyst particles can be maintained high. Furthermore, the obtained photocatalyst is excellent in mechanical strength and durability.
コロイダルシリカとしては、特に制限はないが、アモルファスシリカの含有率が、２〜５０重量％であるものが好ましい。アモルファスシリカの含有率が５０重量％以上のコロイダルシリカは、アモルファスシリカの含有率が大きすぎて、安定な分散状態が維持できず、使用に適さない場合がある。 また、アモルファスシリカの粒径は３０〜５０ｎｍ程度が好ましい。粒径が１０ｎｍ未満では、顆粒体の強度不足となる場合があり、５０ｎｍを超えると、光触媒粒子の保持性能低下となる場合がある。更に、コロイダルシリカは、コロイド粒子の分散状態を安定化させるために、通常、アルカリ性になっていて、Ｎａ２Ｏ等のアルカリ成分がコロイダルシリカ中、０．２重量％以下の割合で含まれている。このようなコロイダルシリカのうち、特に乾燥時に連鎖状結合体を形成し、通気性の大きな形状となるものが好ましく、具体例として、例えば、スノーテックスPSシリーズ（日産化学工業（株）製）が例示される。 Although there is no restriction | limiting in particular as colloidal silica, The thing whose content rate of an amorphous silica is 2 to 50 weight% is preferable. Colloidal silica having an amorphous silica content of 50% by weight or more may not be suitable for use because the amorphous silica content is too high to maintain a stable dispersion state. The particle size of the amorphous silica is preferably about 30 to 50 nm. If the particle size is less than 10 nm, the strength of the granule may be insufficient, and if it exceeds 50 nm, the retention performance of the photocatalyst particles may be reduced. Further, colloidal silica is usually alkaline in order to stabilize the dispersion state of the colloidal particles, and an alkali component such as Na 2 O is contained in the colloidal silica in a proportion of 0.2% by weight or less. Yes. Among these colloidal silicas, those that form a chain-like combined body when dried and have a large air permeability are preferable. Specific examples include, for example, Snowtex PS series (manufactured by Nissan Chemical Industries, Ltd.). Illustrated.
本発明では、光触媒体とコロイダルシリカを含む混合物を成形し、乾燥して光触媒顆粒体とすることが可能であって、この場合、前記光触媒顆粒体中の光触媒体の含有率は、１０重量％以上であることが好ましい。光触媒顆粒体中の光触媒体の含有率が１０重量％未満では、光触媒活性が不十分となる。また、光触媒体とコロイダルシリカを含む混合物中には、充填剤が添加されてもいてもよい。充填剤が添加されることによって、光触媒顆粒体への成形性、機械強度、及び耐久性等が向上するとともに、有機物の吸着性も向上する。また、充填剤の添加により、光触媒の成形体の体積、及び密度等を適宜調節することもできる。 In the present invention, a mixture containing a photocatalyst and a colloidal silica can be molded and dried to form a photocatalyst granule. In this case, the content of the photocatalyst in the photocatalyst granule is 10% by weight. The above is preferable. When the content of the photocatalyst in the photocatalyst granule is less than 10% by weight, the photocatalytic activity becomes insufficient. Further, a filler may be added to the mixture containing the photocatalyst and the colloidal silica. By adding the filler, the moldability to the photocatalyst granule, the mechanical strength, the durability, and the like are improved, and the adsorbability of the organic matter is also improved. The volume and density of the photocatalyst molded body can be appropriately adjusted by adding a filler.
このような光触媒顆粒体は、次のようにして製造することができる。まず、光触媒体とコロイダルシリカをよく混練して混合物を得る。この場合、必要に応じて充填剤を添加してもよい。次いで、得られた混合物を、造粒機、ベレタイザー、押出成形機、及び射出成形機等の成形機に充填して成形し、得られた成形体を乾燥して硬化する。成形体の形状には制限はなく、例えば、円柱状、角柱状、球状等、及び用途に応じて適宜選択できる。また、成形体の乾燥条件は、光触媒粒子が二酸化チタンの場合には、その結晶型がアナタース型の場合に特に光触媒活性が高いため、乾操温度を６００℃以下にしてアナタース型の酸化チタンにする。以上説明したように、本発明は、従来にはない、光触媒体の内部にまで光を透過させ、光触媒体の内部の触媒微粒子までも十分に光活性を発揮できる新規光触媒体を製造し、提供するものであり、その作用効果を初めて実証したものである。 Such a photocatalyst granule can be produced as follows. First, a photocatalyst and a colloidal silica are kneaded well to obtain a mixture. In this case, you may add a filler as needed. Next, the obtained mixture is filled in a molding machine such as a granulator, a beretizer, an extrusion molding machine, and an injection molding machine and molded, and the obtained molded body is dried and cured. There is no restriction | limiting in the shape of a molded object, For example, it can select suitably according to a column shape, prismatic shape, spherical shape, etc., and a use. In addition, when the photocatalyst particles are titanium dioxide, the drying conditions of the molded body are particularly high in photocatalytic activity when the crystal type is anatase type. Therefore, the drying temperature is set to 600 ° C. or less to form anatase type titanium oxide. To do. As described above, the present invention manufactures and provides a novel photocatalyst that can transmit light to the inside of the photocatalyst, which is unconventional, and can fully exhibit the photoactivity up to the catalyst fine particles inside the photocatalyst. This is the first demonstration of its effects.
本発明は、光触媒微粒子を使用した、新しい光触媒体及びその製造方法並びにその光触媒体の使用方法に係るものであり、（１）光触媒体の内部（中心）にまで光を透過させ、光触媒体の内部の触媒微粒子までも十分に光活性を発揮できるようにした光触媒体を提供することができる、（２）照射された光のエネルギーが効率良く利用される光触媒体を提供することができる、（３）光触媒微粒子の特徴である、大きな表面積、高い有機物吸着性、及び光活性をそのまま維持した光触媒体を提供することができる、（４）耐久性に優れ、取り扱いが容易で、且つ、廉価な光触媒体を提供することができる、（５）水、大気及び土壌中に存在する有害な有機物を効率良く無害化することができる、という効果が奏される。 The present invention relates to a new photocatalyst using a photocatalyst fine particle, a method for producing the photocatalyst, and a method for using the photocatalyst. (1) Transmitting light to the inside (center) of the photocatalyst, It is possible to provide a photocatalyst capable of sufficiently exhibiting photoactivity up to the internal catalyst fine particles. (2) It is possible to provide a photocatalyst that efficiently uses the energy of irradiated light. 3) It is possible to provide a photocatalyst that maintains the large surface area, high organic matter adsorptivity, and photoactivity that are the characteristics of the photocatalyst fine particles. (4) Excellent durability, easy handling, and inexpensive. It is possible to provide a photocatalyst, and (5) it is possible to efficiently detoxify harmful organic substances present in water, air and soil.
次に、本発明の光触媒体及びその製造方法並びにその光触媒体の使用例について、実施例に基づいて具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。 Next, the photocatalyst of the present invention, the production method thereof, and usage examples of the photocatalyst will be specifically described based on examples, but the present invention is not limited to these examples.
微粉末シリカ（サイリシア、グレード＃５３０：富士シリシア化学製（表面積４５３ｍ2/ｇ、粒子径５．２μｍ））９９部に、チタニア（チタニア粉末、粒径３０ｎｍ、ＡＭＦ６００：テイカ社製）を1部混合した。これに、シリカゾル（スノーテックス、グレード４０、日産化学社製、濃度４０％）を１０部混合し、マルメライザー造粒機により造粒した後、１５０℃で乾燥し、粒子径３ｍｍの球状粒子を得た。 99 parts fine silica (Silicia, Grade # 530: manufactured by Fuji Silysia Chemical (surface area 453 m <2> / g, particle size 5.2 [mu] m)) and 1 part of titania (titania powder, particle size 30 nm, AMF 600: manufactured by Teica) were mixed. did. To this, 10 parts of silica sol (Snowtex, grade 40, manufactured by Nissan Chemical Co., Ltd., concentration 40%) was mixed, granulated by a Malmerizer granulator, dried at 150 ° C., and spherical particles having a particle diameter of 3 mm were obtained. Obtained.
珪酸ソーダ２３％（富士化学社製、濃度２３％ＳｉＯ２、ＳｉＯ２／Ｎａ２Ｏのモル比３．３）を１００部と、１１Ｎ硫酸を６４部とを、混合反応させて、シリカゾル（シリカｗｔ％：１４％）を得た。これに、チタニア（Ｄ３００、テイカ社製）を、ゾル中のシリカに対し１％添加し攪拌した後、ゲル化させた。得られたチタニア含有ヒドロゲルを、水洗し、８０℃、ｐＨ７．６で、１２時間加熱することにより熱水重合させ、乾燥時の表面積４６０ｍ2/ｇのチタニア含有シリカヒドロゲルを得た。 100 parts of sodium silicate 23% (manufactured by Fuji Chemical Co., Ltd., concentration 23% SiO 2 , SiO 2 / Na 2 O molar ratio 3.3) and 64 parts of 11N sulfuric acid were mixed and reacted to produce silica sol (silica wt%: 14%). To this, 1% of titania (D300, manufactured by Teica) was added to the silica in the sol and stirred, and then gelled. The obtained titania-containing hydrogel was washed with water and subjected to hydrothermal polymerization by heating at 80 ° C. and pH 7.6 for 12 hours to obtain a titania-containing silica hydrogel having a dry surface area of 460 m 2 / g.
珪酸ソーダ２３％（富士化学社製、濃度２３％、ＳｉＯ２／Ｎａ２Ｏのモル比３．３）に、チタニア（ＰＷ−２５、エコデバイス社製）をシリカに対して１％添加混合した。この溶液１００部と、１１Ｎ硫酸６４部を混合し、反応させて、シリカゾル（シリカｗｔ％：１４％）を得た。これをゲル化させた。この得られたチタニア含有ヒドロゲルを、水洗後、温度８０℃、ｐＨ７．６で、１２時間加熱することにより熱水重合させ、乾燥時の表面積４６０ｍ2/ｇのチタニア含有シリカヒドロゲルを得た。 1% of titania (PW-25, manufactured by Ecodevices) was added to and mixed with 23% sodium silicate (made by Fuji Chemical Co., Ltd., concentration 23%, SiO 2 / Na 2 O molar ratio 3.3) with respect to silica. . 100 parts of this solution and 64 parts of 11N sulfuric acid were mixed and reacted to obtain silica sol (silica wt%: 14%). This was gelled. The obtained titania-containing hydrogel was washed with water and then subjected to hydrothermal polymerization by heating at 80 ° C. and pH 7.6 for 12 hours to obtain a titania-containing silica hydrogel having a dry surface area of 460 m 2 / g.
珪酸ソーダ２３％（富士化学社製、濃度２３％、ＳｉＯ２／Ｎａ２Ｏのモル比３．３）を ９９部と、チタニア（ＡＭＴ６００、テイカ社製）をシリカに対して１％添加し、混合した。この溶液１００部と、１１Ｎ硫酸６４部と混合し、反応させて、シリカゾル（シリカｗｔ％：１４％）を得た。次いで、これをゲル化させた。得られたチタニア含有ヒドロゲルを、水洗後、８０℃、ｐＨ７．６で１２時間加熱することにより熱水重合させ、乾燥時の表面積４６０ｍ2/ｇのチタニア含有シリカヒドロゲルを得た。 99% of sodium silicate 23% (Fuji Chemical Co., Ltd., concentration 23%, SiO 2 / Na 2 O molar ratio 3.3) and 1% of titania (AMT600, manufactured by Teica) were added to silica, Mixed. 100 parts of this solution and 64 parts of 11N sulfuric acid were mixed and reacted to obtain silica sol (silica wt%: 14%). This was then gelled. The obtained titania-containing hydrogel was washed with water and heated for 12 hours at 80 ° C. and pH 7.6 to undergo hydrothermal polymerization to obtain a titania-containing silica hydrogel having a surface area of 460 m 2 / g when dried.
実施例３で得られたチタニア含有シリカヒドロゲル１０ｇに、１００ｐｐｍメチレンブルー溶液１００ｍｌを添加した後、紫外線を照射した。３時間後の液中メチレンブルー濃度は、１ｐｐｍ以下であった。 After adding 100 ml of a 100 ppm methylene blue solution to 10 g of the titania-containing silica hydrogel obtained in Example 3, ultraviolet rays were irradiated. The concentration of methylene blue in the liquid after 3 hours was 1 ppm or less.
実施例３で得られたシリカヒドロゾルを、メチレンブルーを３ｐｐｍ含有する土壌に混合した。これを太陽光に晒し、６時間後の土壌中のメチレンブルーの濃度を測定したところ、０．１ｐｐｍ以下であった。 The silica hydrosol obtained in Example 3 was mixed with soil containing 3 ppm of methylene blue. When this was exposed to sunlight and the concentration of methylene blue in the soil after 6 hours was measured, it was 0.1 ppm or less.
以上詳述したように、本発明は、光触媒体及びその製造方法並びにその使用法に係るものであり、本発明は、大きな表面積、高い光活性を維持したまま、光効率が良く、耐久性に優れ、且つ、取り扱いが容易である光触媒体及びその製造方法並びにその使用法を提供するものである。本発明は、従来の光触媒体の問題点を解決し、光触媒体による、水、大気又は土壌等の新しい浄化技術、環境技術として有用である。そして、本発明は、光触媒体の内部にまで光を透過させることにより、光触媒体の内部の触媒微粒子にまでも十分に光活性が得られる光触媒体を提供することができ、光触媒微粒子の特徴である、大きな表面積、高い有機物吸着性、及び光活性を十分に維持した光触媒体を提供することができる。また、本発明は、照射された光のエネルギーを効率良く利用することができ、耐久性に優れ、取り扱いが容易で、且つ、廉価な光触媒体を提供することができる。更に、本発明は、土壌中、廃水中及び大気中に含まれている有害有機物を、分解し、除去する技術を提供するものであり、高い産業上の利用価値を有する。 As described above in detail, the present invention relates to a photocatalyst, a method for producing the same, and a method for using the photocatalyst, and the present invention has high light efficiency and durability while maintaining a large surface area and high photoactivity. The present invention provides a photocatalyst that is excellent and easy to handle, a method for producing the photocatalyst, and a method for using the photocatalyst. The present invention solves the problems of conventional photocatalysts, and is useful as a new purification technology and environmental technology for water, air, soil, etc. using photocatalysts. The present invention, by causing transmission of light to the inside of the photocatalyst, to the inside of the catalyst particles of the photocatalyst can also provide sufficient photocatalyst optical activity is obtained, the feature of the photocatalyst fine particles It is possible to provide a photocatalyst that sufficiently maintains a certain large surface area, high organic matter adsorptivity, and photoactivity. In addition, the present invention can provide an inexpensive photocatalyst that can efficiently use the energy of irradiated light, has excellent durability, is easy to handle, and is inexpensive. Furthermore, the present invention provides a technique for decomposing and removing harmful organic substances contained in soil, wastewater and air, and has high industrial utility value.
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