JP3234893B2 - Method for producing fine hollow glass spheres coated with titanium oxide - Google Patents
Method for producing fine hollow glass spheres coated with titanium oxideInfo
- Publication number
- JP3234893B2 JP3234893B2 JP37692598A JP37692598A JP3234893B2 JP 3234893 B2 JP3234893 B2 JP 3234893B2 JP 37692598 A JP37692598 A JP 37692598A JP 37692598 A JP37692598 A JP 37692598A JP 3234893 B2 JP3234893 B2 JP 3234893B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- titanium oxide
- hollow glass
- fine hollow
- aqueous solution
- 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 - Lifetime
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title description 18
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000002245 particle Substances 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000013049 sediment Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 claims description 8
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 description 21
- 239000011521 glass Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005187 foaming Methods 0.000 description 15
- 238000000634 powder X-ray diffraction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010332 dry classification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005332 obsidian Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000005335 volcanic glass Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010333 wet classification Methods 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/003—General methods for coating; Devices therefor for hollow ware, e.g. containers
- C03C17/005—Coating the outside
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/256—Coating containing TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
- Catalysts (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、火山ガラス質堆積
物を原料として、高強度で白色度に優れ、かつ光触媒機
能を有する酸化チタン被覆微細中空ガラス球状体を効率
よく製造する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing a titanium oxide-coated fine hollow glass sphere having high strength, excellent whiteness, and a photocatalytic function from a volcanic glassy deposit. is there.
【0002】[0002]
【従来の技術】微細中空ガラス球状体は、比重が小さ
く、かつ耐熱性が優れていることから、各種金属、セラ
ミックス、コンクリート、プラスチックスなどの軽量化
充てん材として、また、酸化チタンは塗料、プラスチッ
クなどに対する光触媒機能を有する充填材としてそれぞ
れ注目され、最近その需要が著しく増加している。2. Description of the Related Art Fine hollow glass spheres have a low specific gravity and are excellent in heat resistance, so they are used as lightweight fillers for various metals, ceramics, concrete, plastics, and the like. Attention has been paid to each as a filler having a photocatalytic function for plastics and the like, and the demand thereof has increased remarkably recently.
【0003】これまで、火山ガラス質堆積物を原料とし
て、微細中空ガラス球状体を製造する方法としては、シ
ラスの微粒体を800〜1200℃の温度で10秒ない
し10分間焼成したのち、水中における比重分離又は空
気分級して微細中空ガラス球状体を製造する方法が知ら
れている(特公昭48−17645号公報)。しかしな
がら、この方法では、粒径が20μm以下の火山ガラス
質堆積物を処理しても、所望の微細中空ガラス球状体を
得ることは困難である。Hitherto, as a method for producing a fine hollow glass sphere from a volcanic vitreous sediment as a raw material, shirasu fine particles are fired at a temperature of 800 to 1200 ° C. for 10 seconds to 10 minutes and then fired in water. A method for producing a fine hollow glass sphere by specific gravity separation or air classification is known (Japanese Patent Publication No. 48-17645). However, in this method, it is difficult to obtain a desired fine hollow glass sphere even if a volcanic glassy deposit having a particle size of 20 μm or less is treated.
【0004】一方、微細中空ガラス球状体については原
料の前処理として、酸溶液を用いて加温処理を行うこと
(特公平4−296750号公報)、硫酸アルミニウム
及び尿素を用いて加温処理を行うこと(特開平8−20
8272号公報)、硫酸アルミニウムを含有する水溶液
中に分散させ、室温下で沈殿剤を添加すること(特開平
9−263425号公報)などにより品質を向上させる
方法が開発されている。On the other hand, for the fine hollow glass spheres, as a pretreatment of the raw material, a heating treatment is performed using an acid solution (Japanese Patent Publication No. 4-296750), and a heating treatment is performed using aluminum sulfate and urea. What to do (Japanese Patent Laid-Open No. 8-20
No. 8272) and a method of improving the quality by dispersing in an aqueous solution containing aluminum sulfate and adding a precipitant at room temperature (JP-A-9-263425) has been developed.
【0005】しかしながら、光触媒機能を有する酸化チ
タン被覆微細中空ガラス球状体を得るためには、これら
の方法により得られた微細中空ガラス球状体に対し、被
覆処理を施したのち、再度加熱処理を行う必要がある
が、この方法では効率が極めて悪いという欠点がある。[0005] However, in order to obtain a titanium oxide-coated fine hollow glass sphere having a photocatalytic function, the fine hollow glass sphere obtained by these methods is subjected to a coating treatment and then to a heat treatment again. Although it is necessary, this method has a disadvantage that the efficiency is extremely low.
【0006】[0006]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、火山ガラス質堆積物を原料とし、高強度
で白色度に優れ、かつ光触媒機能を有する酸化チタン被
覆微細中空ガラス球状体を、効率よく製造する方法を提
供することを目的としてなされたものである。SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a titanium oxide-coated fine hollow glass having high strength, excellent whiteness, and a photocatalytic function, using a volcanic glassy deposit as a raw material. The object of the present invention is to provide a method for efficiently producing a spherical body.
【0007】[0007]
【課題を解決するための手段】本発明者らは、酸化チタ
ン被覆微細中空ガラス球状体の製造について鋭意研究を
重ねた結果、火山ガラス質堆積物粉体を加熱発泡処理す
るに際し、予め特定のチタン塩含有溶液を用いて該粉体
粒子表面を酸化チタン水和物で被覆しておけば、粒子内
部の水が確保されて発泡が効果的に起こり、しかもその
際、粒子表面に酸化チタン膜が形成されるので、粒子間
の融着が防止され、しかもこの酸化チタン膜は主として
光触媒機能が良好なアナターゼ型となることを見出し、
この知見に基づいて本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies on the production of fine hollow glass spheres coated with titanium oxide, and as a result, when heating and foaming the volcanic glassy sediment powder, a specific If the surface of the powder particles is coated with a titanium oxide hydrate using a titanium salt-containing solution, water inside the particles is secured and foaming occurs effectively, and at that time, a titanium oxide film is formed on the particle surface. Is formed, fusion between particles is prevented, and moreover, the titanium oxide film is found to be mainly an anatase type having a good photocatalytic function,
Based on this finding, the present invention has been completed.
【0008】すなわち、本発明は、塩化チタン含有塩酸
水溶液又は硫酸チタン含有硫酸水溶液中に、火山ガラス
質堆積物粉体を分散させ、アルカリ水溶液を滴下して該
粉体粒子表面に酸化チタン水和物を析出させたのち、9
00〜1100℃において1〜60秒間熱処理すること
を特徴とする酸化チタン被覆微細中空ガラス球状体の製
造方法を提供するものである。That is, according to the present invention, a volcanic glassy sediment powder is dispersed in a titanium chloride-containing hydrochloric acid aqueous solution or a titanium sulfate-containing sulfuric acid aqueous solution, and an alkaline aqueous solution is dropped to hydrate titanium oxide on the surface of the powder particles. After depositing the material, 9
An object of the present invention is to provide a method for producing a titanium oxide-coated fine hollow glass sphere, which is heat-treated at 00 to 1100 ° C for 1 to 60 seconds.
【0009】[0009]
【発明の実施の形態】本発明方法において、原料として
用いる火山ガラス質堆積物は、これまで微細中空ガラス
球状体の製造に通常用いられているものであって、例え
ばシラス、黒曜石、真珠岩、松脂岩などがある。これら
は通常SiO2、Al2O3、Fe2O3、CaO、M
gO、Na2O及びK2Oから構成され、水分3〜10
重量%を含んでいる。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, a volcanic glassy deposit used as a raw material is one which has been conventionally used for the production of fine hollow glass spheres, and includes, for example, shirasu, obsidian, perlite, There is pine rock. These are usually SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, M
gO, Na 2 O, and K 2 O, with a water content of 3 to 10
% By weight.
【0010】本発明方法においては、これらの火山ガラ
ス質堆積物を粉砕あるいは解砕し、粉砕物や解砕物を乾
式分級や湿式分級などにより、通常粒径50μm以下の
区分を分級して用いる。In the method of the present invention, these volcanic glassy deposits are pulverized or pulverized, and the pulverized or pulverized substances are usually classified by a dry classification or a wet classification into classes having a particle size of 50 μm or less.
【0011】本発明方法においては、まず、このように
して得られた火山ガラス質堆積物粉体表面に酸化チタン
水和物を析出させる。この酸化チタン水和物を析出させ
る方法としては、例えば塩化チタンを含有する塩酸水溶
液中に火山ガラス質堆積物粉体を分散させ、アルカリ水
溶液を滴下して、該粉体表面に酸化チタン水和物を析出
させる方法と、硫酸チタンを含有する硫酸水溶液中に火
山ガラス質堆積物粉体を分散させ、アルカリ水溶液を滴
下して、該粉体表面に酸化チタン水和物を析出させる方
法がある。In the method of the present invention, first, titanium oxide hydrate is precipitated on the surface of the thus obtained volcanic glassy sediment powder. As a method for precipitating this titanium oxide hydrate, for example, a volcanic glassy sediment powder is dispersed in a hydrochloric acid aqueous solution containing titanium chloride, and an alkaline aqueous solution is dropped, and the titanium oxide hydrate is deposited on the surface of the powder. And a method of dispersing a volcanic glassy sediment powder in a sulfuric acid aqueous solution containing titanium sulfate and dropping an alkaline aqueous solution to precipitate titanium oxide hydrate on the surface of the powder. .
【0012】塩化チタンを含有する塩酸水溶液を用いる
方法は、まず、火山ガラス質堆積物粉体を、塩化チタン
を含有する塩酸水溶液中に5〜40重量%程度の濃度に
なるように均質に分散させて懸濁液を調製する。粉体濃
度が上記範囲を逸脱すると本発明の効果が十分に発揮さ
れないおそれがある。効果の点から、この粉体濃度の好
ましい範囲は、10〜30重量%である。In the method using an aqueous hydrochloric acid solution containing titanium chloride, first, a volcanic glassy sediment powder is homogeneously dispersed in an aqueous hydrochloric acid solution containing titanium chloride to a concentration of about 5 to 40% by weight. To prepare a suspension. If the powder concentration is outside the above range, the effects of the present invention may not be sufficiently exhibited. From the viewpoint of the effect, a preferable range of the powder concentration is 10 to 30% by weight.
【0013】また、塩酸水溶液中の塩化チタン濃度は
0.01モル/リットル以上が好ましく、特に0.05
〜0.2モル/リットルの範囲が好ましい。さらに塩酸
の濃度は0.01モル/リットル以上が好ましく、特に
0.1〜1モル/リットルの範囲が好ましい。The concentration of titanium chloride in the aqueous hydrochloric acid solution is preferably at least 0.01 mol / liter, particularly preferably 0.05 mol / l.
The range is preferably from 0.2 to 0.2 mol / liter. Further, the concentration of hydrochloric acid is preferably at least 0.01 mol / l, and particularly preferably in the range of 0.1 to 1 mol / l.
【0014】次に、このように調製された懸濁液をかき
まぜながら、これにアルカリ水溶液を徐々に添加して塩
化チタンを加水分解させ、粉体粒子表面に酸化チタン水
和物を析出させる。アルカリ水溶液としては、例えば炭
酸水素ナトリウム、炭酸水素カリウム、炭酸水素リチウ
ム、炭酸水素アンモニウムなどを1種又は2種以上含む
水溶液が挙げられるが、取り扱いやすく、収率が高いと
いう点から、炭酸水素アンモニウムを含む水溶液が好ま
しい。このアルカリ水溶液の濃度は2モル/リットル以
下が好ましく、特に0.5〜1.5モル/リットルの範
囲が好適である。このアルカリ水溶液の添加量は、懸濁
液中の塩化チタンに対し、アルカリが0.8〜1.2当
量倍になるように選ぶのが有利である。また、このアル
カリ水溶液を添加する際の懸濁液の温度は、一般に室温
で十分であるが、必要ならば適当に加温してもよい。次
に、硫酸チタンを含有する硫酸水溶液を用いる方法は、
上記の方法において、塩化チタンを硫酸チタンに、塩酸
水溶液を硫酸水溶液に変える以外は、上記の方法と同様
に操作すればよい。Next, while stirring the suspension thus prepared, an aqueous alkali solution is gradually added to the suspension to hydrolyze titanium chloride, thereby precipitating titanium oxide hydrate on the surface of the powder particles. Examples of the aqueous alkaline solution include aqueous solutions containing one or more of sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, ammonium hydrogencarbonate, and the like. An aqueous solution containing The concentration of the aqueous alkali solution is preferably 2 mol / l or less, and particularly preferably in the range of 0.5 to 1.5 mol / l. It is advantageous to select the amount of the aqueous alkali solution so that the alkali is 0.8 to 1.2 equivalent times the amount of titanium chloride in the suspension. In addition, the temperature of the suspension when adding the aqueous alkaline solution is generally room temperature, but may be appropriately heated if necessary. Next, a method using a sulfuric acid aqueous solution containing titanium sulfate is as follows:
In the above method, the operation may be performed in the same manner as in the above method, except that titanium chloride is changed to titanium sulfate and a hydrochloric acid aqueous solution is changed to a sulfuric acid aqueous solution.
【0015】次に、懸濁液を固液分離するが、これは例
えばろ過、遠心分離、デカンテーションなどの公知の手
段により行うことができる。このようにして分離された
固形分は次いで水洗などにより十分に洗浄したのち、乾
燥処理し、次いでこの乾燥粉体を900〜1100℃の
範囲の温度において1〜60秒間熱処理して発泡させ
る。この熱処理により、発泡粒子表面が酸化チタンで被
覆されるので、粒子間の融着が効果的に防止される。熱
処理温度が900℃未満では十分に発泡しないおそれが
あるし、1100℃を超えると粒子間の融着が生じるこ
とがある。また、熱処理時間が1秒未満では十分に発泡
しないおそれがあり、一方60秒を超えるとそれ以上の
発泡は起こらず、むしろ粒子間の融着など、好ましくな
い結果を招来する。Next, the suspension is subjected to solid-liquid separation, which can be performed by a known means such as filtration, centrifugation, decantation and the like. The solid content thus separated is then sufficiently washed by washing with water or the like, and then dried, and then the dried powder is heat-treated at a temperature in the range of 900 to 1100 ° C. for 1 to 60 seconds to foam. By this heat treatment, the surface of the expanded particles is covered with titanium oxide, so that fusion between the particles is effectively prevented. If the heat treatment temperature is lower than 900 ° C., the foam may not be sufficiently formed, and if it exceeds 1100 ° C., fusion between particles may occur. If the heat treatment time is less than 1 second, there is a possibility that the foaming may not be sufficiently performed. On the other hand, if the heat treatment time is more than 60 seconds, no further foaming occurs, which results in unfavorable results such as fusion between particles.
【0016】このようにして加熱発泡させたものは軽量
の中空体であるが、さらに、比重差分別、例えば水中に
おける浮沈分離又は空気分級することにより、より軽量
の中空体を回収することもできる。The thus heat-foamed foam is a light-weight hollow body, but it is also possible to recover a lighter-weight hollow body by a specific gravity difference, for example, by floating separation in water or air classification. .
【0017】このような方法によれば、粒径が50μm
以下で、粒子密度1g/cm3以下の光触媒機能を有す
る酸化チタン被覆微細中空ガラス球状体を、原料の重量
に基づき50%以上という高い回収率で得ることができ
る。なお、微細中空ガラス球状体に被覆された酸化チタ
ンは、通常光触媒能の高いアナターゼ型となる。According to such a method, the particle size is 50 μm.
In the following, a titanium oxide-coated fine hollow glass sphere having a photocatalytic function having a particle density of 1 g / cm 3 or less can be obtained with a high recovery rate of 50% or more based on the weight of the raw material. It should be noted that the titanium oxide coated on the fine hollow glass sphere usually becomes an anatase type having high photocatalytic ability.
【0018】[0018]
【発明の効果】本発明によれば、火山ガラス質堆積物粉
体を原料として用い、高強度で白色度に優れ、かつ光触
媒機能を有する酸化チタン被覆微細中空ガラス球状体を
効率よく製造することができる。本発明方法で得られた
光触媒機能を有する酸化チタン被覆微細中空ガラス球状
体は、従来から利用されているセラミックス、コンクリ
ート、プラスチックスなどの軽量化充てん材として有用
である。また、主にアナターゼ型の酸化チタンが被覆さ
れているので、それ自体で太陽光によるNOxの分解や
水上に浮遊している油の分解などに有効に利用できる
し、あるいは塗料などに光触媒機能を付与する充てん材
として利用することができ、この塗料を塗布して光触媒
機能を有する環境浄化壁などを作製することができる。According to the present invention, it is possible to efficiently produce titanium oxide-coated fine hollow glass spheres having high strength, excellent whiteness, and a photocatalytic function by using volcanic glassy sediment powder as a raw material. Can be. The titanium oxide-coated fine hollow glass sphere having a photocatalytic function obtained by the method of the present invention is useful as a lightweight filler for conventionally used ceramics, concrete, plastics and the like. Also, mainly because of anatase type titanium oxide is coated, to be effectively used in such itself degradation of oil floating in the degradation and water of the NO x by sunlight, or the like to photocatalytic function paint This coating material can be used as a filler for imparting a water content, and an environmental purification wall having a photocatalytic function can be produced.
【0019】[0019]
【実施例】次に、本発明を実施例によりさらに詳細に説
明するが、本発明は、これらの例によってなんら限定さ
れるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【0020】なお、微細中空ガラス球状体の強度は次の
方法により測定した。すなわち、試料とるつぼ型ろ過器
の質量をそれぞれ測定し、試料を網ふるい製試料容器に
入れ、この試料容器を加圧容器中に入れて密閉し、8M
Paまで加圧したのち、試料容器を取り出す。次に、試
料をるつぼ型ろ過器で吸引ろ過し、乾燥して秤量する。
次式に従って算出した非破壊率Sc(重量%)をもって
強度とする。 Sc=[100−(Dpa−1−Dp−1)/(D−1−Dp−1)]×10 0 ただし、Dpaは加圧後の試料の粒子密度(g/c
m3)、Dpは加圧前の試料の粒子密度(g/c
m3)、Dは加圧後の破壊された粒子の粒子密度(2.
35g/cm3)を示す。The strength of the fine hollow glass sphere was measured by the following method. That is, the mass of each of the sample and the crucible-type filter was measured, and the sample was placed in a sample container made of a mesh sieve.
After pressurizing to Pa, the sample container is taken out. Next, the sample is suction-filtered with a crucible-type filter, dried, and weighed.
The strength is defined as the nondestructive rate Sc (% by weight) calculated according to the following equation. Sc = [100− (Dpa −1 −Dp −1 )) / (D −1 −Dp −1 )] × 100 where Dpa is the particle density (g / c) of the sample after pressurization.
m 3 ), and Dp is the particle density (g / c) of the sample before pressing.
m 3 ), D is the particle density of the broken particles after pressurization (2.
35 g / cm 3 ).
【0021】実施例1 表1に示す組成をもつ火山ガラス質堆積物(福島県福島
市飯坂町産出、通称福島白土)を解砕し、粉末原料を調
製した。Example 1 A volcanic glassy deposit having a composition shown in Table 1 (produced in Iizaka-machi, Fukushima City, Fukushima Prefecture, commonly known as Fukushima Shirato) was pulverized to prepare a powder raw material.
【0022】[0022]
【表1】 [Table 1]
【0023】液体媒質として、水ガラス(JIS 3
号)0.2重量%水溶液を用い、前記の粉末原料を投入
し、粒子の水中沈降速度の差を利用する水簸により、分
離粒度5μm及び10μmで分級した。分級粒子中に含
まれる粒径10μmを超える粒子の割合は、いずれの場
合も10重量%以下であり、また粒径5μm未満の粒子
の割合は、いずれの場合も10重量%以下であった。As a liquid medium, water glass (JIS 3)
No.) Using a 0.2% by weight aqueous solution, the above-mentioned powdery raw material was charged, and classified by elutriation using a difference in the sedimentation speed of particles in water at separation particle sizes of 5 μm and 10 μm. The ratio of particles having a particle size exceeding 10 μm contained in the classified particles was 10% by weight or less in each case, and the ratio of particles having a particle size of less than 5 μm was 10% by weight or less in each case.
【0024】次に、この分級した粉末20重量部を、塩
化チタン0.029モル/リットル及び塩酸0.056
モル/リットルの濃度で含む水溶液100重量部に添加
して均質に分散させたのち、この懸濁液を室温下でかき
まぜながら、これに1モル/リットル濃度の炭酸水素ア
ンモニウム水溶液を塩化チタンが加水分解する当量とな
るように、5時間で滴下した。その後、被覆処理された
固形分をろ取したのち、水洗、乾燥した。Next, 20 parts by weight of the classified powder was mixed with 0.029 mol / liter of titanium chloride and 0.056 mol of hydrochloric acid.
The mixture was added to 100 parts by weight of an aqueous solution containing a concentration of 1 mol / liter and uniformly dispersed. After stirring the suspension at room temperature, a 1 mol / liter aqueous ammonium bicarbonate solution was added with titanium chloride. The solution was added dropwise over 5 hours so as to have an equivalent amount for decomposition. After that, the coated solid was collected by filtration, washed with water, and dried.
【0025】この乾燥粉末を、最高温度を1040℃と
した加熱発泡装置に供給し、装置内を数秒で通過させて
発泡させたのち、回収して回収物の粒子密度を測定する
とともに、粉末X線回折を行った。結果を表2に示す。
また粉末X線回折チャートを図1に示す。The dried powder is supplied to a heating and foaming apparatus having a maximum temperature of 1040 ° C., passed through the apparatus in a few seconds to foam, then collected and measured for the particle density of the recovered material. Line diffraction was performed. Table 2 shows the results.
FIG. 1 shows a powder X-ray diffraction chart.
【0026】比較例1 実施例1において、火山ガラス質堆積物の分級粉末に対
し、被覆処理を行わなかったこと以外は、実施例1と同
様にして操作した。しかし、加熱発泡装置内に火山ガラ
ス質堆積物の分級粉末が多量に溶融付着して連続処理が
できなかった。そこで、最高温度を1000℃としたと
ころ、連続処理が可能となった。結果を表2に示すとと
もに、粉末X線回折チャートを図1に示す。Comparative Example 1 The procedure of Example 1 was repeated, except that the classification powder of the volcanic glassy sediment was not coated. However, a large amount of the classification powder of the volcanic glassy sediment was melted and adhered to the heating and foaming apparatus, so that continuous treatment could not be performed. Then, when the maximum temperature was set to 1000 ° C., continuous processing became possible. The results are shown in Table 2, and the powder X-ray diffraction chart is shown in FIG.
【0027】[0027]
【表2】 [Table 2]
【0028】表2から分かるように、実施例1は、比較
例1に比べて加熱発泡物の粒子密度が小さい。なお、加
熱発泡前の粒子密度は、両者共2.35g/cm3であ
る。また、実施例1のものは、図1から、被覆した酸化
チタンがアナターゼ型であるのが分かる。As can be seen from Table 2, Example 1 has a smaller particle density of the heat-foamed product than Comparative Example 1. The particle density before heat foaming is 2.35 g / cm 3 for both. Further, in the case of Example 1, it can be seen from FIG. 1 that the coated titanium oxide is of an anatase type.
【0029】実施例2 実施例1で用いたものと同じ表1に示す組成の火山ガラ
ス質堆積物を解砕し、粉末原料を調製した。この粉末原
料を、目開き45μmの標準ふるいを用いて45μmで
分級した。通過した45μm以下の粒子をさらに空気分
級機を用いて分離粒径10μmで分級し、粗粒を回収し
た。分級粒子中に含まれる粒径10μm未満の粒子の割
合は、10重量%以下であった。Example 2 A volcanic glassy deposit having the same composition as shown in Table 1 and used in Example 1 was crushed to prepare a powder raw material. This powdery raw material was classified at 45 μm using a standard sieve having a mesh size of 45 μm. The passed particles of 45 μm or less were further classified with a separation particle size of 10 μm using an air classifier, and coarse particles were collected. The proportion of particles having a particle size of less than 10 μm contained in the classified particles was 10% by weight or less.
【0030】次に、この分級した粉末25重量部を、塩
化チタン0.1モル/リットル及び塩酸0.4モル/リ
ットルの濃度で含む水溶液250重量部に添加し、室温
下でかきまぜながら、1モル/リットル濃度の炭酸水素
アンモニウム水溶液を2時間で塩化チタンが加水分解す
る当量となるように滴下した。その後、被覆処理された
固形分をろ取したのち、水洗、乾燥した。Next, 25 parts by weight of the classified powder is added to 250 parts by weight of an aqueous solution containing 0.1 mol / l of titanium chloride and 0.4 mol / l of hydrochloric acid. An aqueous solution of ammonium bicarbonate having a concentration of mol / liter was added dropwise so that the titanium chloride was hydrolyzed in 2 hours. After that, the coated solid was collected by filtration, washed with water, and dried.
【0031】この乾燥粉末を、最高温度を1040℃と
した加熱発泡装置に供給し、装置内を数秒で通過させて
発泡させたのち、回収し、回収物の粒子密度を測定する
とともに、粉末X線回折を行った。結果を表3に示す。
また、粉末X線回折チャートを図2に示す。The dried powder is supplied to a heating and foaming apparatus having a maximum temperature of 1040 ° C., and is passed through the apparatus within a few seconds to foam. Then, the powder is recovered, and the particle density of the recovered material is measured. Line diffraction was performed. Table 3 shows the results.
FIG. 2 shows a powder X-ray diffraction chart.
【0032】比較例2 実施例2において、火山ガラス質堆積物の分級粉末につ
いて、被覆処理を行わなかったこと以外は、実施例2と
同様にして操作した。しかし、加熱発泡装置内に火山ガ
ラス質堆積物の分級粉末が多数溶融付着して連続処理が
できなかった。そこで、最高温度を1000℃としたと
ころ、連続処理が可能となった。結果を表3に示すとと
もに、粉末X線回折チャートを図2に示す。COMPARATIVE EXAMPLE 2 The procedure of Example 2 was repeated, except that the classification powder of the volcanic glassy sediment was not coated. However, a large number of classified powders of volcanic glassy deposits were melted and adhered in the heating and foaming apparatus, so that continuous treatment could not be performed. Then, when the maximum temperature was set to 1000 ° C., continuous processing became possible. The results are shown in Table 3, and the powder X-ray diffraction chart is shown in FIG.
【0033】[0033]
【表3】 [Table 3]
【0034】表3から分かるように、実施例2は、比較
例2に比べて加熱発泡物の粒子密度が小さい。なお、加
熱発泡物の粒子密度は、両者共2.35g/cm3であ
る。また、実施例2のものは、図2から、被覆した酸化
チタンがアナターゼ型であるのが分かる。比較例2のも
のは、当然ながら、被覆処理を行っていないので、ガラ
スのハローだけである。As can be seen from Table 3, Example 2 has a smaller particle density of the heat-foamed product than Comparative Example 2. The particle density of the heated foam is 2.35 g / cm 3 in both cases. In addition, in the case of Example 2, it can be seen from FIG. 2 that the coated titanium oxide is of an anatase type. In the case of Comparative Example 2, as a matter of course, only the glass halo was used because the coating treatment was not performed.
【0035】実施例3 実施例2に用いた分級粉末25重量部を、硫酸チタン
0.1モル/リットル及び硫酸0.2モル/リットルの
濃度で含む水溶液250重量部に添加し、室温下でかき
まぜながら、1モル/リットル濃度の炭酸水素アンモニ
ウム水溶液を2時間で硫酸チタンが加水分解する当量と
なるように滴下した。その後、被覆処理された固形分を
ろ取したのち、水洗、乾燥した。Example 3 25 parts by weight of the classified powder used in Example 2 were added to 250 parts by weight of an aqueous solution containing 0.1 mol / l of titanium sulfate and 0.2 mol / l of sulfuric acid at room temperature. While stirring, an aqueous solution of ammonium bicarbonate having a concentration of 1 mol / liter was added dropwise so that the titanium sulfate would be hydrolyzed in 2 hours. After that, the coated solid was collected by filtration, washed with water, and dried.
【0036】この乾燥粉末を、最高温度を1040℃と
した加熱発泡装置に供給し、装置内を数秒で通過させて
発泡させたのち、回収し、回収物の粒子密度を測定する
とともに、粉末X線回折を行った。結果を表4に示す。
また、粉末X線回折チャートを図3に示す。The dried powder is supplied to a heating and foaming apparatus having a maximum temperature of 1040 ° C., and is passed through the apparatus in a few seconds to foam. Then, the powder is recovered, and the particle density of the recovered material is measured. Line diffraction was performed. Table 4 shows the results.
FIG. 3 shows a powder X-ray diffraction chart.
【0037】実施例4 表4に示す組成をもつ火山ガラス質堆積物(島根県太田
市町産出)を解砕し、粉末原料を調製した。Example 4 A volcanic glassy deposit having a composition shown in Table 4 (produced in Ota City, Shimane Prefecture) was crushed to prepare a powder raw material.
【0038】[0038]
【表4】 [Table 4]
【0039】目開き45μmのJISふるいを用いた水
ふるいと、実施例1と同様の粒子の水中沈降速度の差を
利用する水簸により、分離粒度10μm及び45μmで
分級した。なお、分級粒子の平均粒径は28.8μmで
あった。A water sieve using a JIS sieve having a mesh size of 45 μm and a elutriation using the difference in the sedimentation speed of the particles in water in the same manner as in Example 1 were used to classify particles having a separation particle size of 10 μm and 45 μm. The average particle size of the classified particles was 28.8 μm.
【0040】次に、この分級した粉末40重量部を、塩
化チタン0.029モル/リットル及び塩酸0.056
モル/リットルの濃度で含む水溶液100重量部に添加
して均質に分散させたのち、この懸濁液を室温下でかき
まぜながら、これに1モル/リットル濃度の炭酸水素ア
ンモニウム水溶液を塩化チタンが加水分解する当量とな
るように、4時間で滴下した。その後、被覆処理された
固形分をろ取したのち、水洗、乾燥した。Next, 40 parts by weight of the classified powder were mixed with 0.029 mol / liter of titanium chloride and 0.056 mol of hydrochloric acid.
The mixture was added to 100 parts by weight of an aqueous solution containing a concentration of 1 mol / liter and uniformly dispersed. After stirring the suspension at room temperature, a 1 mol / liter aqueous ammonium bicarbonate solution was added with titanium chloride. The solution was added dropwise over 4 hours so as to have an equivalent amount for decomposition. After that, the coated solid was collected by filtration, washed with water, and dried.
【0041】この乾燥粉末を、最高温度を960、10
00℃とした加熱発泡装置に供給し、装置内を数秒で通
過させて発泡させたのち、回収して回収物の粒子密度を
測定するとともに、粉末X線回折を行った。結果を表5
示す。また粉末X線回折チャートを図4に示す。The dried powder was heated at a maximum temperature of 960, 10
The mixture was supplied to a heating and foaming apparatus at 00 ° C., passed through the apparatus for foaming in a few seconds, foamed, collected, measured for particle density of the collected matter, and subjected to powder X-ray diffraction. Table 5 shows the results
Show. FIG. 4 shows a powder X-ray diffraction chart.
【0042】[0042]
【表5】 [Table 5]
【0043】表5から分かるように、温度上昇と共に加
熱発泡物の粒子密度が小さくなっている。なお、加熱発
泡前の粒子密度は、すべて2.35g/cm3である。
また、図4から、いずれも被覆した酸化チタンがアナタ
ーゼ型であることが分かるとともに、原料中に若干含ま
れる長石も認められる。As can be seen from Table 5, the particle density of the heated foam decreases with increasing temperature. In addition, the particle densities before heat foaming are all 2.35 g / cm 3 .
In addition, from FIG. 4, it can be seen that the coated titanium oxide is anatase type, and feldspar slightly contained in the raw material is also recognized.
【0044】実施例5 鹿児島県鹿屋市に産する火山ガラス質堆積物を、目開き
150μm及び300μmのJISふるいを用いた水ふ
るいにより、分離粒度150μm及び300μmで分級
したのち、密度2.4g/cm3の臭化亜鉛水溶液を用
いて浮沈分離を行い、密度2.4g/cm3以下の火山
ガラス粉末を回収した。回収した粒径150〜300μ
mの火山ガラス粉末の組成を表6に示す。Example 5 A volcanic glassy sediment produced in Kanaya City, Kagoshima Prefecture was classified with a water sieve using a JIS sieve having openings of 150 μm and 300 μm at a separation particle size of 150 μm and 300 μm, and the density was 2.4 g / g. Using a zinc bromide aqueous solution of cm 3 , floatation and sedimentation was performed, and a volcanic glass powder having a density of 2.4 g / cm 3 or less was recovered. Collected particle size 150-300μ
Table 6 shows the composition of m volcano glass powder.
【0045】[0045]
【表6】 [Table 6]
【0046】次に、この分級した粉末10重量部を、塩
化チタン0.047モル/リットル及び塩酸0.188
モル/リットルの濃度で含む水溶液100重量部に添加
して均質に分散させたのち、この懸濁液を室温下でかき
まぜながら、これに1モル/リットル濃度の炭酸水素ア
ンモニウム水溶液を塩化チタンが加水分解する当量とな
るように、8時間で滴下した。その後、被覆処理された
固形分をろ取したのち、水洗、乾燥した。Next, 10 parts by weight of the classified powder was mixed with 0.047 mol / l of titanium chloride and 0.188 mol of hydrochloric acid.
The mixture was added to 100 parts by weight of an aqueous solution containing a concentration of 1 mol / liter and uniformly dispersed. After stirring the suspension at room temperature, a 1 mol / liter aqueous ammonium bicarbonate solution was added with titanium chloride. The solution was added dropwise over 8 hours so as to have a decomposition equivalent. After that, the coated solid was collected by filtration, washed with water, and dried.
【0047】この乾燥粉末を、最高温度940℃とした
加熱発泡装置に供給し、供給から排出までの滞留時間を
60秒間として発泡させたのち、回収した。回収物の粒
子密度は0.85g/cm3、水中浮揚物含有割合は4
7.7重量%、強度は83.3重量%であった。なお、
加熱発泡前の粒子密度は2.35g/cm3である。図
5に、粉末X線回折チャートを示す。この図5から分か
るように、被覆した酸化チタンはルチル型である。The dried powder was supplied to a heating and foaming apparatus having a maximum temperature of 940 ° C., foamed with a residence time from supply to discharge of 60 seconds, and then collected. The particle density of the recovered material is 0.85 g / cm 3 , and the floating content in water is 4
7.7% by weight and strength was 83.3% by weight. In addition,
The particle density before heat foaming is 2.35 g / cm 3 . FIG. 5 shows a powder X-ray diffraction chart. As can be seen from FIG. 5, the coated titanium oxide is of a rutile type.
【0048】比較例3 実施例5において、火山ガラス質堆積物の分級粉末につ
いて、被覆処理を行わなかったこと以外は、実施例5と
同様に実施した。回収物の粒子密度、水中浮揚物含有割
合及び強度は被覆処理試料とほぼ同じである。図5に、
粉末X線回折チャートを示す。Comparative Example 3 The procedure of Example 5 was repeated, except that the classification powder of the volcanic glassy sediment was not coated. The particle density, levitated matter content and strength of the recovered material are almost the same as those of the coated sample. In FIG.
3 shows a powder X-ray diffraction chart.
【図1】 実施例1及び比較例1で得られた微細中空ガ
ラス球状体の粉末X線回折チャート。FIG. 1 is a powder X-ray diffraction chart of the fine hollow glass spheres obtained in Example 1 and Comparative Example 1.
【図2】 実施例2及び比較例2で得られた微細中空ガ
ラス球状体の粉末X線回折チャート。FIG. 2 is a powder X-ray diffraction chart of the fine hollow glass spheres obtained in Example 2 and Comparative Example 2.
【図3】 実施例3で得られた微細中空ガラス球状体の
粉末X線回折チャート。FIG. 3 is a powder X-ray diffraction chart of the fine hollow glass sphere obtained in Example 3.
【図4】 実施例4で得られた微細中空ガラス球状体の
粉末X線回折チャート。FIG. 4 is a powder X-ray diffraction chart of the fine hollow glass sphere obtained in Example 4.
【図5】 実施例5及び比較例3で得られた微細中空ガ
ラス球状体の粉末X線回折チャート。FIG. 5 is a powder X-ray diffraction chart of the fine hollow glass sphere obtained in Example 5 and Comparative Example 3.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI C04B 14/16 C04B 14/16 (58)調査した分野(Int.Cl.7,DB名) C03C 15/00 - 23/00 C03C 11/00 C04B 14/16 - 14/30 B01J 32/00 - 37/00 C03B 19/08 ──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 7 identification code FI C04B 14/16 C04B 14/16 (58) Investigated field (Int.Cl. 7 , DB name) C03C 15/00-23/00 C03C 11/00 C04B 14/16-14/30 B01J 32/00-37/00 C03B 19/08
Claims (1)
ン含有硫酸水溶液中に、火山ガラス質堆積物粉体を分散
させ、アルカリ水溶液を滴下して該粉体粒子表面に酸化
チタン水和物を析出させたのち、900〜1100℃に
おいて1〜60秒間熱処理することを特徴とする酸化チ
タン被覆微細中空ガラス球状体の製造方法。1. A volcanic glassy sediment powder is dispersed in a titanium chloride-containing hydrochloric acid aqueous solution or a titanium sulfate-containing sulfuric acid aqueous solution, and an alkaline aqueous solution is dropped to precipitate titanium oxide hydrate on the surface of the powder particles. Thereafter, a heat treatment is performed at 900 to 1100 ° C. for 1 to 60 seconds.
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JP2002326815A (en) * | 2001-04-27 | 2002-11-12 | Sumitomo Chem Co Ltd | Production method of titanium oxide |
JP2005199261A (en) * | 2003-12-17 | 2005-07-28 | Fujikura Kasei Co Ltd | Photocatalyst composite material, coating composition comprising photocatalyst and self-cleaning type coating film |
JP2006307198A (en) * | 2005-03-30 | 2006-11-09 | Seiko Epson Corp | White pigment for aqueous ink and ink composition using the same |
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CN102993781B (en) * | 2012-11-22 | 2014-05-21 | 嘉兴学院 | Preparation method of magnetic nano ferroferric oxide modified hollow glass microsphere |
JP6096536B2 (en) * | 2013-03-07 | 2017-03-15 | 宇部エクシモ株式会社 | Photocatalyst composite particles and method for producing the same |
JP6765101B2 (en) * | 2016-09-02 | 2020-10-07 | 国立大学法人九州工業大学 | Method for producing biodiesel fuel, decarboxylation catalyst, and method for regenerating decarboxylation catalyst used for producing biodiesel fuel |
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