JP2005246180A - Method for manufacturing functional ultrafine particle material - Google Patents
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- JP2005246180A JP2005246180A JP2004058254A JP2004058254A JP2005246180A JP 2005246180 A JP2005246180 A JP 2005246180A JP 2004058254 A JP2004058254 A JP 2004058254A JP 2004058254 A JP2004058254 A JP 2004058254A JP 2005246180 A JP2005246180 A JP 2005246180A
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- 239000011882 ultra-fine particle Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000001699 photocatalysis Effects 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011941 photocatalyst Substances 0.000 claims description 23
- 238000010304 firing Methods 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 14
- 239000002440 industrial waste Substances 0.000 claims description 13
- 150000004703 alkoxides Chemical class 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000005350 fused silica glass Substances 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 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 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Description
本発明は、高い耐熱性を有する光触媒の原料となる機能性超微粒子材料の製造方法とその製品等に関するものであり、更に詳しくは、例えば、産業廃棄物の廃シリカガラス粉末等を利用して、金属アルコキシドを加水分解させて、基材表面にＴｉを被覆し、大気中で高温で焼成することで、高温で焼成ても光触媒機能を発現する機能性超微粒子材料を製造する方法及びその製品に関するものである。本発明は、酸化チタン光触媒、その製造方法及びその応用製品の技術分野において、従来の酸化チタン光触媒は、例えば、９００℃以上の高温で加熱すると、活性の高いアナターゼ相は、活性の低いルチル相へ変化してしまい、例えば、陶磁器用の光触媒としては使用することができないという問題があったことを踏まえ、高温で焼成しても、高い光触媒活性を発揮する耐熱性光触媒を製造することを可能とする新しい光触媒材料の製造技術を提供するものであり、本発明は、例えば、産業廃棄物の廃シリカガラス等を有効利用して新しい耐熱性光触媒及びその製品を製造し、提供することを実現化することにより、当技術分野における新技術・新産業の創出に資するものとして有用である。 The present invention relates to a method for producing a functional ultrafine particle material that is a raw material for a photocatalyst having high heat resistance and its product. More specifically, for example, waste silica glass powder of industrial waste is used. A method for producing a functional ultrafine particle material that exhibits a photocatalytic function even when baked at a high temperature by hydrolyzing a metal alkoxide, coating the surface of the substrate with Ti, and baking at high temperature in the air, and its product It is about. The present invention relates to a titanium oxide photocatalyst, a method for producing the same, and an applied product thereof. When a conventional titanium oxide photocatalyst is heated at a high temperature of, for example, 900 ° C. or higher, a highly active anatase phase is converted into a less active rutile phase It is possible to produce a heat-resistant photocatalyst that exhibits high photocatalytic activity even when baked at high temperature, considering that there is a problem that it cannot be used as a photocatalyst for ceramics, for example. The present invention provides a new heat-resistant photocatalyst and its product by effectively utilizing, for example, waste silica glass of industrial waste. It is useful for contributing to the creation of new technologies and new industries in this technical field.
従来、酸化チタンの光触媒効果を利用した方法及び製品は、例えば、防汚、脱臭、抗菌、大気浄化、及び浄水等の広範な用途に使用されている（例えば、特許文献１〜３参照）。しかし、この酸化チタン光触媒は、高温で焼成すると、活性の高いアナターゼ相から、活性の低いルチル相へ相変態を起こし、光触媒活性が低下すること、そのために、製造過程で高温焼成が必要とされる製品等への適用が制限されること、が知られている。 Conventionally, methods and products using the photocatalytic effect of titanium oxide have been used in a wide range of applications such as antifouling, deodorizing, antibacterial, air purification, and water purification (see, for example, Patent Documents 1 to 3). However, this titanium oxide photocatalyst undergoes a phase transformation from a highly active anatase phase to a less active rutile phase when calcined at a high temperature, resulting in a decrease in photocatalytic activity. For this reason, high temperature calcination is required in the production process. It is known that application to products and the like is limited.
光触媒の性能は、一般的には、例えば、メチレンブルー溶液の色素分解能力によって評価することができる。光触媒を高活性化するためには、光透過性と高い比表面積を有し、活性の高いアナターゼ相を持つようにすることが必要である。一例として、例えば、シリカに適当な金属アルコキシド溶液を添加して光触媒材料を製造する方法として、以下の方法が採用されている。すなわち、この方法は、シリカ粉末と金属アルコキシド溶液を所定量秤量し、水又は特定の溶媒中で加水分解を起こし、粉末表面に金属を被覆した後、この金属被覆粉末を大気中で焼成して光触媒材料とするものである。 In general, the performance of the photocatalyst can be evaluated by, for example, the ability of the methylene blue solution to decompose the dye. In order to make the photocatalyst highly active, it is necessary to have a light-transmitting property, a high specific surface area, and a highly active anatase phase. As an example, for example, the following method is employed as a method for producing a photocatalytic material by adding an appropriate metal alkoxide solution to silica. That is, in this method, a predetermined amount of silica powder and a metal alkoxide solution are weighed, hydrolyzed in water or a specific solvent, coated with metal on the powder surface, and then the metal-coated powder is fired in the air. It is a photocatalytic material.
しかし、このように、上記金属被覆粉末を大気中で焼成して光触媒粉末材料を製造する方法では、高い比表面積と活性の高いアナターゼ相を維持するために、低温焼成を行うことが必要とされる。すなわち、この種の光触媒粉末材料は、特に、９００℃以上で加熱してしまうと、活性の高いアナターゼ相は、活性の低いルチル相へ変化してしまうので、そのような加熱を施す製品へ適用することができず、例えば、その製造過程で高温焼成が必要とされる各種セラミックス、陶磁器素材、及び金属等の表面処理に使用することができないという問題があった。そこで、当技術分野では、例えば、９００℃以上の高温で焼成しても、高い光触媒活性を維持することが可能な耐熱性光触媒の開発が強く望まれていた。 However, as described above, in the method of producing the photocatalyst powder material by firing the metal-coated powder in the air, it is necessary to perform low-temperature firing in order to maintain a high specific surface area and a highly active anatase phase. The That is, this type of photocatalytic powder material is applied to products that are heated, especially when heated at 900 ° C. or higher, because the highly active anatase phase changes to the less active rutile phase. For example, there is a problem that it cannot be used for surface treatment of various ceramics, ceramic materials, metals, and the like that require high-temperature firing in the manufacturing process. Therefore, in this technical field, for example, development of a heat-resistant photocatalyst capable of maintaining high photocatalytic activity even when baked at a high temperature of 900 ° C. or higher has been strongly desired.
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、例えば、各種セラミックスや陶磁器の焼成過程で、高温焼成しても光触媒機能を維持する新しい高耐熱性光触媒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、シリカガラス粉末（産業廃棄物）と金属アルコキシド溶液を混合し、加水分解して得られる粉末を大気中で焼成することで、所期の目的が達成し得ることを知見し、更に研究を重ねて、本発明を完成するに至った。 Under such circumstances, the present inventors have developed a new high heat-resistant photocatalyst that maintains the photocatalytic function even when fired at a high temperature, for example, in the firing process of various ceramics and ceramics, in view of the above-described prior art. As a result of intensive research with the goal of achieving this goal, the desired purpose was achieved by mixing silica glass powder (industrial waste) and metal alkoxide solution and then firing the powder obtained by hydrolysis in the atmosphere. The inventors have found out that the present invention can be obtained, and have further researched to complete the present invention.
本発明は、原料としてシリカガラス粉末を利用して、粉末の状態で大気中で高温焼成しても、活性の高いアナターゼ相と高い比表面積を維持し、光透過性と耐熱性を有し、高い光触媒活性を発揮する新規な機能性超微粒子材料の製造方法を提供することを目的とするものである。
更に、本発明は、溶融シリカガラス粉末、廃シリカガラス粉末（産業廃棄物）を有効利用して、高温焼成しても高い比表面積と、活性の高いアナターゼ相を維持し、光透過性と耐熱性を有する光触媒粉末材料を、経済性に優れた方法で、低コストで作製することを可能とする新規な機能性超微粒子材料の製造方法、その機能性超微粒子材料及びその応用製品を提供することを目的とするものである。
The present invention uses silica glass powder as a raw material, maintains a highly active anatase phase and a high specific surface area even when calcined at high temperature in the air in the state of powder, has light transmittance and heat resistance, It is an object of the present invention to provide a method for producing a novel functional ultrafine particle material exhibiting high photocatalytic activity.
Furthermore, the present invention makes effective use of fused silica glass powder and waste silica glass powder (industrial waste), maintains a high specific surface area and a highly active anatase phase even when fired at high temperature, and is light transmissive and heat resistant. Provided a novel functional ultrafine particle material production method capable of producing a photocatalytic powder material having a property by an economical method at a low cost, the functional ultrafine particle material, and an application product thereof It is for the purpose.
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）高温で焼成しても、高い光触媒活性を発現する、耐熱性光触媒材料用の機能性超微粒子を製造する方法であって、シリカガラス粉末と金属アルコシキド溶液を所定量秤量し、水又は特定の溶媒中で加水分解を起こし、シリカガラス粉末表面にＴｉを被覆し、大気中で６００〜１３００℃で焼成して、酸化チタン微粒子をシリカガラス粒子の表面に強固に担持させた機能性超微粒子を製造することを特徴とする、上記特性を有する機能性超微粒子の製造方法。
（２）シリカガラス粉末表面に、０〜４０℃の温度範囲で、Ｔｉを被覆することを特徴とする、前記（１）に記載の機能性超微粒子の製造方法。
（３）大気中で９００〜１３００℃の温度範囲で焼成することを特徴とする、前記（１）に記載の機能性超微粒子の製造方法。
（４）原料として、シリカガラス粉末、溶融シリカガラス粉末、又は産業廃棄物の廃シリカガラス粉末を使用することを特徴とする、前記（１）に記載の機能性超微粒子の製造方法。
（５）前記（１）から（４）のいずれかに記載の方法で作製した機能性超微粒子からなることを特徴とする耐熱性光触媒。
（６）前記（５）に記載の耐熱性光触媒を製品素材の表面に担持させ、９００℃以上で高温焼成して製品化したことを特徴とする光触媒製品。
（７）製品が、セラミックス製品、陶磁器製品又は金属製品であることを特徴とする前記（６）に記載の光触媒製品。
（８）前記（１）から（４）のいずれかに記載の方法により、産業廃棄物の廃シリカガラス粉末を光触媒材料用の機能性超微粒子として再利用することを特徴とする、廃シリカガラス粉末の再資源化方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) A method for producing functional ultrafine particles for a heat-resistant photocatalytic material that exhibits high photocatalytic activity even when baked at a high temperature, wherein a predetermined amount of silica glass powder and a metal alkoxide solution are weighed, and water or Hydrolysis in a specific solvent, coating the surface of the silica glass powder with Ti, firing at 600-1300 ° C. in the atmosphere, and supporting the titanium oxide fine particles firmly on the surface of the silica glass particles A method for producing functional ultrafine particles having the above characteristics, characterized by producing fine particles.
(2) The method for producing functional ultrafine particles according to (1), wherein the silica glass powder surface is coated with Ti in a temperature range of 0 to 40 ° C.
(3) The method for producing functional ultrafine particles according to the above (1), characterized by firing in the air at a temperature range of 900 to 1300 ° C.
(4) The method for producing functional ultrafine particles according to (1) above, wherein silica glass powder, fused silica glass powder, or waste silica glass powder of industrial waste is used as a raw material.
(5) A heat-resistant photocatalyst comprising functional ultrafine particles produced by the method according to any one of (1) to (4).
(6) A photocatalytic product obtained by supporting the heat-resistant photocatalyst described in (5) on the surface of a product material and firing the product at a high temperature of 900 ° C. or higher.
(7) The photocatalytic product according to (6), wherein the product is a ceramic product, a ceramic product, or a metal product.
(8) Waste silica glass, wherein waste silica glass powder of industrial waste is reused as functional ultrafine particles for photocatalyst material by the method according to any one of (1) to (4) How to recycle powder.
次に、本発明について更に詳細に説明する。
本発明は、例えば、シリカガラス粉末や溶融シリカガラス粉末にＴｉ金属アルコキシドを混合して、加水分解し、得られた粉末を大気中で焼成することにより酸化チタン微粒子をシリカガラス粒子の表面に強固に担持させた機能性超微粒子材料を製造することを特徴とするものである。本発明では、機能性超微粒子材料の構成元素として、酸化シリコン、シリカガラス及びガラス等が用いられ、例えば、これらの構成元素を含むシリカガラス粉末、溶融シリカガラス粉末、上記構成元素を含む産業廃棄物の廃シリカガラス粉末等が原料として用いられるが、これらの原料に限らず、これらの原料と同等あるいは類似の原料であれば同様に使用することができる。すなわち、本発明では、構成元素として、上記酸化シリコン、シリカガラス粉末及びガラス等を含む複合材料であれば同様に使用することができる。
Next, the present invention will be described in more detail.
In the present invention, for example, a silica glass powder or a fused silica glass powder is mixed with a Ti metal alkoxide, hydrolyzed, and the obtained powder is fired in the air to firmly attach titanium oxide fine particles to the surface of the silica glass particles. It is characterized in that a functional ultrafine particle material supported on the substrate is produced. In the present invention, silicon oxide, silica glass, glass and the like are used as constituent elements of the functional ultrafine particle material. For example, silica glass powder containing these constituent elements, fused silica glass powder, and industrial waste containing the constituent elements. Waste silica glass powder or the like is used as a raw material, but is not limited to these raw materials, and any raw material equivalent to or similar to these raw materials can be used in the same manner. That is, in this invention, if it is a composite material containing the said silicon oxide, silica glass powder, glass etc. as a structural element, it can be used similarly.
また、本発明では、目的とする光触媒粉末材料を得るために、Ｔｉ金属アルコキシドが用いられる。このような金属アルコキシドとしては、好適には、例えば、Ｔｉ（ＯＣ2 Ｈ5 ）4 〔テトラエチルオルトチタン酸）、Ｔｉ（（ＣＨ3 ）2 ＣＨＯ）4 〔チタニウムテトライソプロポキシド〕又はＴｉ（ＯＣ4 Ｈ9 ）4 〔チタニウムテトラ−ｎ−ブトキシド〕を例示することができるが、これらに制限されるものではなく、これらと同効のものであれば同様に使用することができる。 In the present invention, Ti metal alkoxide is used in order to obtain the desired photocatalytic powder material. As such a metal alkoxide, for example, Ti (OC 2 H 5 ) 4 [tetraethylorthotitanic acid], Ti ((CH 3 ) 2 CHO) 4 [titanium tetraisopropoxide] or Ti (OC 4 H 9 ) 4 [titanium tetra-n-butoxide] can be exemplified, but the present invention is not limited to these, and any compound having the same effect as these can be used.
本発明では、原料として、これらの機能性超微粒子材料の構成元素及びＴｉ金属アルコキシドを所定量秤量したものを配合し、この配合物を水又は特定の溶媒中で加水分解させ、乾燥後、大気中で焼成することで目的の機能性超微粒子粉末を得ることができる。 In the present invention, as a raw material, a component obtained by weighing a predetermined amount of the constituent elements of these functional ultrafine particle materials and Ti metal alkoxide is blended, the blend is hydrolyzed in water or a specific solvent, dried, and then air The target functional ultrafine particle powder can be obtained by firing in the medium.
本発明において、Ｔｉの配合比率は、シリカガラス粉末に対して１〜２００％以上であり、この配合比率でシリカガラス粉末にＴｉ源を配合して加水分解を起こし、Ｔｉをシリカガラス粉末表面に被覆する。Ｔｉの被覆は、好適には、例えば、０〜４０℃で行われる。次いで、これを大気中、６００〜１３００℃で焼成する。焼成時間は０．０１〜５時間が望ましい。しかし、これらの条件は、これらに制限されるものではない。このように、大気中で焼成を行うことによって、耐熱性で、例えば、９００℃以上の高温で焼成しても、活性の高いアナターゼ相と高い比表面積を維持し、高い光触媒機能を発現することが可能な機能性超微粒子が得られる。 In the present invention, the blending ratio of Ti is 1 to 200% or more with respect to the silica glass powder, and the Ti source is blended with the silica glass powder at this blending ratio to cause hydrolysis, and Ti is added to the silica glass powder surface. Cover. The Ti coating is preferably performed at 0 to 40 ° C., for example. Subsequently, this is baked at 600-1300 degreeC in air | atmosphere. The firing time is preferably 0.01 to 5 hours. However, these conditions are not limited to these. Thus, by firing in the air, it is heat resistant, for example, maintains a highly active anatase phase and a high specific surface area even when fired at a high temperature of 900 ° C. or higher, and exhibits a high photocatalytic function. Can be obtained.
大気中で焼成して得られた上記機能性超微粒子は、特に、高温焼成、高温環境下で高い光触媒活性を発揮する光触媒材料として、例えば、自動車の排ガスなどから排出される窒素酸化物（ＮＯｘ）や硫黄酸化物（ＳＯｘ）などの環境汚染物質を除去したり、汚染水に含まれるテトラクロロエチレンやトリハロメタンなどの有機塩素化合物を分解除去するための光触媒として好適に用いられる。 The functional ultrafine particles obtained by firing in the atmosphere are used as photocatalyst materials that exhibit high photocatalytic activity under high-temperature firing and high-temperature environments, for example, nitrogen oxide (NOx) emitted from automobile exhaust gas, etc. ) And sulfur oxides (SOx), and is suitably used as a photocatalyst for decomposing and removing organic chlorine compounds such as tetrachloroethylene and trihalomethane contained in contaminated water.
本発明の機能性超微粒子は、粉体自体又は他の製品に複合化されて光触媒材料として使用される。この機能性超微粒子は、耐熱性を有し、高温で焼成しても、アナターゼ相に基づく高い光触媒活性を維持している。そのため、本発明の機能性超微粒子は、例えば、各種セラミックス、金属製品及び陶磁器素材等の表面処理に使用可能であり、例えば、板状、ブロック状、パイプ状のセラミックス製品等に応用できる。本発明は、基本的に、その製造過程で高温焼成が必要とされる製品であれば、その種類に制限されることなく好適に適用し得るものであり、これらの製品に光触媒機能を付加する方法及び材料として有用である。更に、光触媒作用を有する酸化チタン微粒子は、シリカ粒子の表面に強固に担持されており、例えば、水系における処理にも好適に利用することができる。 The functional ultrafine particles of the present invention are used as a photocatalyst material by being combined with powder itself or other products. The functional ultrafine particles have heat resistance and maintain high photocatalytic activity based on the anatase phase even when baked at a high temperature. Therefore, the functional ultrafine particles of the present invention can be used for surface treatment of various ceramics, metal products, ceramic materials, and the like, and can be applied to, for example, plate-shaped, block-shaped, and pipe-shaped ceramic products. Basically, the present invention can be suitably applied to any product that requires high-temperature firing in the production process without being limited to the type thereof, and a photocatalytic function is added to these products. Useful as methods and materials. Furthermore, the titanium oxide fine particles having a photocatalytic action are firmly supported on the surface of the silica particles, and can be suitably used for, for example, treatment in an aqueous system.
本発明により、１）高温で焼成しても、活性の高いアナターゼ相と高い比表面積を維持し、高い光触媒活性を発揮する機能性超微粒子材料が得られる、２）光透過性と高い比表面積を有し、活性の高いアナターゼ相を持つ耐熱性光触媒材料を製造し、提供できる、３）本発明の機能性超微粒子材料を利用することにより、製品の製造過程で高温焼成することが必要とされる各種セラミックス、金属製品及び陶磁器製品等に光触媒機能を付加することができる、４）産業廃棄物の廃シリカガラス粉末を有効利用して再資源化することを可能とする新技術を提供できる、という格別の効果が奏される。 According to the present invention, 1) a functional ultrafine particle material that maintains a highly active anatase phase and a high specific surface area and exhibits high photocatalytic activity even when baked at a high temperature can be obtained. 2) Light transmittance and high specific surface area 3) It is necessary to produce and provide a heat-resistant photocatalytic material having a highly active anatase phase, and 3) by using the functional ultrafine particle material of the present invention, it is necessary to perform high-temperature firing in the production process of the product. Photocatalytic function can be added to various ceramics, metal products, ceramic products, etc. 4) It is possible to provide new technology that makes it possible to effectively utilize and recycle waste silica glass powder of industrial waste , There is a special effect.
次に、実施例に基づいて本発明を具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.
シリカガラス粉末とガラス粉末をペレット状に成形し、吸光度測定を行った。この結果、シリカガラス粉末はガラス粉末に比べて、短波長（紫外線）領域で低い吸光度を示すことがわかった。本発明では、原料として、例えば、シリカ粉末やガラス粉末とは別異のシリカガラス粉末、溶融シリカガラス粉末等が用いられ、更に、シリカガラス粉末を含有する産業廃棄物の廃シリカガラス粉末が用いられるが、本実施例では、シリカガラス粉末含有未処理産業廃棄物を用いた例を示す。尚、他のシリカガラス粉末を用いた場合にも、同様の結果が得られた。 Silica glass powder and glass powder were formed into pellets, and the absorbance was measured. As a result, it was found that the silica glass powder showed lower absorbance in the short wavelength (ultraviolet) region than the glass powder. In the present invention, as a raw material, for example, silica glass powder different from silica powder or glass powder, fused silica glass powder or the like is used, and further, waste silica glass powder of industrial waste containing silica glass powder is used. However, in this embodiment, an example using untreated industrial waste containing silica glass powder is shown. Similar results were obtained when other silica glass powders were used.
３００ｍｌフラスコ中に１００ｍｌ無水エタノールとシリカガラス粉末含有未処理産業廃棄物（以下、単にシリカガラス粉末と記載する。）とＴｉ源（テトラエチルオルトチタン酸、チタニウムテトライソプロポキシド、チタニウムテトラ−ｎ−ブトキシのいずれか）を所定量秤量し、混合した。このフラスコを４０℃に保持した恒温槽に固定してフラスコ内に水を所定量入れてから３０分間攪拌した。その後、遠心分離機を用いて固液分離し、超音波で洗浄した。その後、１１０℃で２４時間乾燥させた。その後、大気中、６００〜１３００℃で１０分間焼成した。 Untreated industrial waste containing 100 ml absolute ethanol and silica glass powder in a 300 ml flask (hereinafter simply referred to as silica glass powder) and Ti source (tetraethylorthotitanic acid, titanium tetraisopropoxide, titanium tetra-n-butoxy) 1) was weighed out and mixed. This flask was fixed to a thermostat kept at 40 ° C., and a predetermined amount of water was put into the flask, followed by stirring for 30 minutes. Thereafter, solid-liquid separation was performed using a centrifuge, and washing was performed with ultrasonic waves. Then, it was dried at 110 ° C. for 24 hours. Then, it baked for 10 minutes at 600-1300 degreeC in air | atmosphere.
恒温槽を４０℃で保持した時に、種々のＴｉ源でシリカガラス粉末に被覆した試料を図１に示す。テトラエチルオルトチタン酸をＴｉ源として使用した場合、シリカガラス粉末表面にＴｉが被覆された様子が観察されなかった。しかし、Ｔｉ源にチタニウムテトライソプロポキシドやチタニウムテトラ−ｎ−ブトキシを使用すると、シリカガラス粉末表面にＴｉが被覆され、Ｔｉ被覆粉末が得られることが分かった。 Samples coated with silica glass powder with various Ti sources when the thermostat is held at 40 ° C. are shown in FIG. When tetraethylorthotitanic acid was used as the Ti source, it was not observed that the silica glass powder surface was coated with Ti. However, it has been found that when titanium tetraisopropoxide or titanium tetra-n-butoxy is used as the Ti source, the silica glass powder surface is coated with Ti and a Ti-coated powder is obtained.
実施例１で説明した操作内容で、Ｔｉ源をチタニウムテトライソプロポキシドに固定して反応温度を０〜４０℃に変化させた場合のシリカガラス粉末の表面を図２に示す。この結果から、Ｔｉ源にチタニウムテトライソプロポキシドを用いれば、０〜４０℃の温度範囲でシリカガラス粉末表面にＴｉをコーティング可能であり、Ｔｉ被覆粉末が得られることが分かった。 FIG. 2 shows the surface of the silica glass powder when the Ti source is fixed to titanium tetraisopropoxide and the reaction temperature is changed to 0 to 40 ° C. with the operation described in Example 1. From this result, it was found that if titanium tetraisopropoxide is used as the Ti source, Ti can be coated on the surface of the silica glass powder in a temperature range of 0 to 40 ° C., and a Ti-coated powder can be obtained.
実施例２で説明した操作内容で、恒温槽を０℃で保持して反応させた試料を、大気中、６００℃と１３００℃で１０分間焼成した後の粉末のＸ線回折測定の結果を図３に示す。これによれば、６００℃で焼成した粉末は、単一のアナターゼ相のみであることが分かった、そして、１３００℃で焼成した粉末は、アナターゼ相とルチル相を持つことが分かった。このように、シリカガラス粉末の表面にＴｉを被覆して作製したＴｉ被覆粉末は、高温焼成（１３００℃）しても、活性の高いアナターゼ相を維持しており、耐熱性を有することが分かった。 The result of the X-ray diffraction measurement of the powder after baking the sample which carried out the reaction which hold | maintained the thermostat at 0 degreeC by the operation content demonstrated in Example 2 at 600 degreeC and 1300 degreeC for 10 minutes in air | atmosphere. 3 shows. According to this, it was found that the powder fired at 600 ° C. has only a single anatase phase, and the powder fired at 1300 ° C. has an anatase phase and a rutile phase. Thus, it was found that the Ti-coated powder produced by coating the surface of silica glass powder with Ti maintains a highly active anatase phase even at high temperature firing (1300 ° C.) and has heat resistance. It was.
実施例２で説明した操作内容で、恒温槽を０℃で保持して反応させた試料を、大気中、１０００℃で１０分間保持した後の粉末と５時間保持した後の粉末のＸ線回折測定の結果を図４に示す。これによれば、保持時間が異なっても同じ結晶相の強度を示すことが分かった。このように、Ｔｉで表面処理したシリカガラス粉末は、耐熱性を持つ光触媒材料として有用であることが分かった。 X-ray diffraction of a sample obtained by maintaining the thermostatic chamber at 0 ° C. and reacting in the same manner as described in Example 2 in the air, after holding at 1000 ° C. for 10 minutes, and after holding for 5 hours The measurement results are shown in FIG. According to this, it was found that the same crystal phase strength was exhibited even with different holding times. Thus, it turned out that the silica glass powder surface-treated with Ti is useful as a photocatalytic material having heat resistance.
実施例３で説明した内容の試料を、焼成温度を変えて作製し、各試料について、メチレンブルー溶液の色素分解能力を評価した。サンプルは、６００℃、９００℃、１０００℃、１１００℃、１２００℃及び１３００℃でそれぞれ１０分間焼成したものを使用した。各試料のメチレンブルー色素分解能力を評価した結果を図５に示す。その結果、大気中、１０００℃で１０分間焼成した試料が、最も高い分解能力を示すことが分かった。 Samples having the contents described in Example 3 were prepared by changing the firing temperature, and the dye decomposition ability of the methylene blue solution was evaluated for each sample. The samples used were calcined at 600 ° C., 900 ° C., 1000 ° C., 1100 ° C., 1200 ° C. and 1300 ° C. for 10 minutes, respectively. The results of evaluating the ability of each sample to decompose methylene blue are shown in FIG. As a result, it was found that a sample fired at 1000 ° C. for 10 minutes in the atmosphere exhibits the highest decomposition ability.
以上詳述したように、本発明は、機能性超微粒子材料の製造方法に係るものであり、本発明の方法によって得られた機能性超微粒子材料は、高温で焼成しても活性の高いアナターゼ相を維持し、高い耐熱性を示し、また、光透過性を有し、高い光触媒活性を発揮する。本発明の方法は、粉末の焼成が大気中でできるので、経済性に優れており、低コストで光触媒材料を作成することができる。本発明の機能性超微粒子材料は、高温で焼成ても、高い光触媒機能を発現するため、各種セラミックス、金属製品及び陶磁器素材等の表面処理に代表される、製品の製造過程で高温焼成が必要とされる種々の製品に適用することが可能である。 As described above in detail, the present invention relates to a method for producing a functional ultrafine particle material, and the functional ultrafine particle material obtained by the method of the present invention is highly active anatase even when fired at a high temperature. Maintains the phase, exhibits high heat resistance, has light permeability, and exhibits high photocatalytic activity. The method of the present invention is excellent in economic efficiency because the powder can be fired in the air, and a photocatalytic material can be produced at low cost. Since the functional ultrafine particle material of the present invention exhibits a high photocatalytic function even when fired at high temperatures, high-temperature firing is required in the production process of products represented by surface treatment of various ceramics, metal products and ceramic materials. It is possible to apply to various products.
Claims (8)
A method for recycling waste silica glass powder, wherein the waste silica glass powder of industrial waste is reused as functional ultrafine particles for photocatalyst material by the method according to any one of claims 1 to 4. .
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