JP2016019957A - Titanium oxide water purifier, method of manufacturing titanium oxide water purifier, and water purification method with titanium oxide water purifier - Google Patents
Titanium oxide water purifier, method of manufacturing titanium oxide water purifier, and water purification method with titanium oxide water purifier Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000746 purification Methods 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 205
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 191
- 239000010936 titanium Substances 0.000 claims abstract description 191
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 23
- 238000010248 power generation Methods 0.000 claims description 11
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- 238000005520 cutting process Methods 0.000 claims description 6
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- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 7
- 238000004042 decolorization Methods 0.000 description 31
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 description 31
- 229960003988 indigo carmine Drugs 0.000 description 31
- 235000012738 indigotine Nutrition 0.000 description 31
- 239000004179 indigotine Substances 0.000 description 31
- 238000002474 experimental method Methods 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 238000007654 immersion Methods 0.000 description 15
- 239000003973 paint Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 239000008188 pellet Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
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- 238000005292 vacuum distillation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 239000012901 Milli-Q water Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 230000001954 sterilising effect Effects 0.000 description 1
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Landscapes
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、酸化チタン水質浄化体、同酸化チタン水質浄化体の製造方法および同酸化チタン水質浄化体による水質浄化方法に関する。 The present invention relates to a titanium oxide water purification body, a method for producing the titanium oxide water purification body, and a water purification method using the titanium oxide water purification body.
二酸化チタン（説明の便宜上、酸化チタンと呼ぶ）は、光触媒として利用されている。紫外光が照射されると、酸化チタンは強い酸化還元作用を生じるためである。
酸化チタンは、鉱石（ルチル鉱）を塩素化して四塩化チタンとして精製した後、酸化して脱塩素化して製造される。このため、酸化チタンは粉末となっている。酸化チタン粉末を塗料に加え、壁に同塗料を塗ることで壁面の殺菌が容易になるといった利用方法もある。
Titanium dioxide (referred to as titanium oxide for convenience of description) is used as a photocatalyst. This is because titanium oxide produces a strong redox effect when irradiated with ultraviolet light.
Titanium oxide is produced by chlorinating ore (rutile ore) and refining it as titanium tetrachloride, followed by oxidation and dechlorination. For this reason, titanium oxide is powdered. There is also a utilization method in which sterilization of the wall surface is facilitated by adding titanium oxide powder to the paint and applying the paint on the wall.
一方、水質浄化のためには、粉末であると流れてしまう。このため、ガラスビーズ表面に焼き付けて使用する方法やバインダーを用いて接着する方法が提案されている。 On the other hand, for water purification, it will flow if it is powder. For this reason, a method of baking on the surface of glass beads and a method of bonding using a binder have been proposed.
特許文献１に示される浄化処理方法では、表面に酸化チタンを形成した粒状のスポンジチタンと吸着作用を有する多孔質体の麦飯石との組み合わせにより水質を浄化する方法が提案されている。 In the purification treatment method disclosed in Patent Document 1, a method for purifying water quality by combining granular sponge titanium having titanium oxide formed on the surface and a porous barley stone having an adsorption action has been proposed.
汚染水を浄化するために酸化チタン粉末は流水に流されてしまうため不適である。また、ガラスビーズの表面に焼き付ける方法では、ガラスビーズ自体が流れ去ってしまうのは粉末と変わらない。流れ去らないようにビーズを大きくすることも考えられるが、表面積が低下して浄化能力の低下を招く。なお、ガラスビーズ表面に焼き付ける方法においてもバインダーを用いて接着する方法においても、表面に露出している部分にしか効果を生じないし、他物との接触により表面が剥離することにより効果が消失してしまう。
酸化チタン粉末でなく多孔質のスポンジチタンを使用することで浄化効率を高めることができるとともに表面の剥離への耐性も高めることができるが、特許文献１に示される浄化処理方法は、粒状のスポンジチタンを水槽の底に敷き詰めることのみを考慮しており、スポンジチタンを流路に配置することやスポンジチタン自体で流路を形成することについては考慮されていない。
In order to purify the contaminated water, the titanium oxide powder is unsuitable because it flows into the running water. Moreover, in the method of baking on the surface of a glass bead, it is not different from a powder that the glass bead itself flows away. Although it is conceivable to enlarge the beads so that they do not flow away, the surface area is reduced and the purification ability is reduced. In both the method of baking on the surface of the glass beads and the method of bonding using a binder, the effect only occurs on the exposed part of the surface, and the effect disappears due to the surface peeling by contact with other objects. End up.
By using porous sponge titanium instead of titanium oxide powder, the purification efficiency can be increased and the resistance to surface peeling can be increased. However, the purification treatment method disclosed in Patent Document 1 is a granular sponge. It only considers laying titanium on the bottom of the water tank, and does not consider placing the titanium sponge in the flow path or forming the flow path with the sponge titanium itself.
本発明は、製造が容易で浄化能力の高い酸化チタン水質浄化体、同酸化チタン水質浄化体の製造方法および同酸化チタン水質浄化体による水質浄化方法を提供する。 The present invention provides a titanium oxide water purification body that is easy to produce and has a high purification capacity, a method for producing the titanium oxide water purification body, and a water purification method using the titanium oxide water purification body.
本発明は、真空溶解法でスポンジチタンを生成する際に形成される多孔質のチタンを、当該多孔質状態で薄板形状にし、酸化させて形成している。
使用する多孔質状のチタンとして、真空溶解法でチタンを生成する際に形成される多孔質のスポンジチタンを、当該スポンジチタンの状態で同チタンをスライス切削した後に、酸化させて形成することが可能である。
In the present invention, porous titanium formed when producing sponge titanium by a vacuum melting method is formed into a thin plate shape in the porous state and oxidized.
As porous titanium to be used, porous sponge titanium formed when titanium is produced by a vacuum melting method can be formed by slicing the titanium in the state of the sponge titanium and then oxidizing it. Is possible.
スポンジチタンは、一例として、クロール法と呼ばれる精製プロセスで生産される。
クロール法では、原料のUGIを塩素ガスと反応させて、四塩化チタンとし、次ぎに四塩化チタンを高温の溶融マグネシウムと反応させて還元し、金属チタンと副生成物である塩化マグネシウムを分離する。
この金属チタンには不純物として塩化マグネシウムや金属マグネシウムが含まれているため、真空溶解法（高真空蒸留）を行い不純物を除去する。
As an example, sponge titanium is produced by a purification process called a crawl method.
In the crawl method, raw material UGI is reacted with chlorine gas to form titanium tetrachloride, and then titanium tetrachloride is reacted with high-temperature molten magnesium to reduce and separate titanium metal and by-product magnesium chloride. .
Since this metal titanium contains magnesium chloride or metal magnesium as impurities, the impurities are removed by a vacuum melting method (high vacuum distillation).
真空分離を行なうと、溶融した状態の純チタンが滴下する。精製されて得た金属チタンの形状は海綿状であることからスポンジチタンとも称されている。
当該金属チタンは、多孔質状態で薄板形状にし、さらに酸化させる。一例として、電気炉に入れ、６００〜８００℃に加熱し、焼なましする。これにより、薄板形状とした多孔質状のチタン表面に酸化膜が形成される。
When vacuum separation is performed, pure titanium in a molten state is dropped. Since the refined metal titanium is spongy, it is also called sponge titanium.
The titanium metal is made into a thin plate shape in a porous state and further oxidized. As an example, it puts into an electric furnace, heats at 600-800 degreeC, and anneals. Thereby, an oxide film is formed on the porous titanium surface having a thin plate shape.
板状となることで、多孔質状の酸化チタンは水質浄化を必要とする被浄化液体の水路の流路に配置することが可能である。すなわち、薄板状とした状態で被浄化液体の流路を形成する。この場合、板材は流路を形成するのに適しており、被浄化液体が流路の板材に沿って流れることで、万遍なく水質浄化作用が発揮される。特に、蛇行流路を形成すれば、実質的に多くの被浄化液体が板材の表面に接することになり、効率的である。また、流路は被浄化液体の流路内に浸漬するものでもよいが、被浄化液体が板材の表面を流下する構成とすることも可能であり、この場合も多くの被浄化液体が板材の表面に接することになり、水質浄化作用を受けることになる。 By being plate-shaped, the porous titanium oxide can be disposed in the flow path of the liquid to be purified that requires water purification. That is, the flow path of the liquid to be purified is formed in a thin plate shape. In this case, the plate material is suitable for forming the flow path, and the water purification effect is exhibited evenly by allowing the liquid to be purified to flow along the plate material of the flow path. In particular, if a meandering flow path is formed, a substantial amount of liquid to be purified comes into contact with the surface of the plate material, which is efficient. Further, the flow path may be immersed in the flow path of the liquid to be purified, but it is also possible to adopt a configuration in which the liquid to be purified flows down the surface of the plate material. It comes in contact with the surface and receives a water purification effect.
さらに、流路には、水流を利用する発電機構と、同発電機構にて発電された電力で点灯する紫外線照明を設けてもよい。
流路に水流を利用する発電機構を設けることで、同発電機構にて発電された電力で紫外線照明を点灯させることで、安定的に水質浄化を実現できる。例えば、紫外線の照射を日光だけに頼らずに水質浄化を期待できる。
Further, the flow path may be provided with a power generation mechanism that uses a water flow and an ultraviolet illumination that is lit by the power generated by the power generation mechanism.
By providing a power generation mechanism using a water flow in the flow path, water quality purification can be realized stably by turning on the ultraviolet illumination with the power generated by the power generation mechanism. For example, water purification can be expected without relying only on sunlight for ultraviolet irradiation.
本発明によれば、多孔質の酸化チタンを板状等の様々な形状に成形することで様々な場所への設置を可能とし、所定の紫外線を照射することで凹凸のある細かな表面で強力な酸化作用を生じ、流路に設置すれば、流れる水などの水質を浄化できる。 According to the present invention, porous titanium oxide is molded into various shapes such as a plate shape, and can be installed in various places. By irradiating a predetermined ultraviolet ray, it is powerful on a fine surface with irregularities. If it is installed in the channel, it can purify water quality such as flowing water.
以下、図面も参照しつつ本発明の酸化チタン水質浄化体、酸化チタン水質浄化体の製造方法および酸化チタン水質浄化体を使用した水質浄化方法の実施形態を説明する。
本発明では、二酸化チタンを簡易的に酸化チタンと呼ぶが、一部においては、二酸化チタンと正確に称する。
チタンは、チタン鉱石及びUGI （濃縮したイルメナイト鉱）から製造される。また、中間原料であるスポンジチタンを経てインゴット、フェロチタン、チタン鋳造品、チタン粉末等に加工される。そのうち、多くは二酸化チタンとして利用されてきた。従来、二酸化チタンは主に隠蔽力が大きい白色顔料として利用され、主な製造方法として塩素法が知られている。
Hereinafter, embodiments of a titanium oxide water purification body, a method for producing a titanium oxide water purification body, and a water purification method using the titanium oxide water purification body according to the present invention will be described with reference to the drawings.
In the present invention, titanium dioxide is simply referred to as titanium oxide, but in some cases it is accurately referred to as titanium dioxide.
Titanium is produced from titanium ore and UGI (enriched ilmenite ore). In addition, it is processed into ingot, ferro-titanium, titanium casting, titanium powder, etc. via sponge titanium which is an intermediate raw material. Of these, many have been used as titanium dioxide. Conventionally, titanium dioxide is mainly used as a white pigment having a large hiding power, and the chlorine method is known as a main production method.
まず、従来の塩素法酸化チタンの製造法について説明する。
１．塩素化工程：ルチル鉱を1,000℃程度の高温で塩素ガスとカーボンに反応させ四塩化チタン（ＴｉＣｌ4）を合成する。
２．酸化工程：炉から出て来たガスから四塩化チタンを採りだし、高速で噴射しながら酸化することで二酸化チタン粒子が出来る。
しかし、粉末として製造される二酸化チタンは、液体の水質浄化剤として利用するには、液体と共に流れ落ちてしまうことや、効率よく多くの液体に接触させにくいといったデメリットがあった。そこで、本実施例では、以下のように真空溶解法でスポンジチタンを生成する際に形成される多孔質のチタンを利用する。
First, a conventional method for producing a chlorine method titanium oxide will be described.
1. Chlorination process: Titanium tetrachloride (TiCl4) is synthesized by reacting rutile ore with chlorine gas and carbon at a high temperature of about 1,000 ° C.
2. Oxidation process: Titanium tetrachloride is produced by extracting titanium tetrachloride from the gas coming out of the furnace and oxidizing it while jetting at high speed.
However, titanium dioxide produced as a powder has the disadvantages that it flows down with the liquid and is difficult to efficiently contact with many liquids in order to be used as a liquid water purification agent. Therefore, in this embodiment, porous titanium formed when producing sponge titanium by a vacuum melting method as described below is used.
ここで、スポンジチタンの製造法について説明する。
スポンジチタンは「クロール法」と呼ばれる精製プロセスで生産される。
１．塩素化工程：クロール法では、原料のUGI を塩素ガスと反応させて、四塩化チタン（ＴｉＣｌ4）とする。
２．マグネシウム還元工程：次ぎに四塩化チタン（ＴｉＣｌ4）を高温の溶融マグネシウムと反応させて還元し、金属チタンと副生成物である塩化マグネシウム（ＭｇＣｌ2 ）を分離する。
３．真空分離工程（真空溶解法）：金属チタンには不純物として塩化マグネシウム（ＭｇＣｌ2 ）や金属マグネシウム（Ｍｇ）が含まれているため、高真空蒸留を行い不純物を除去する。
真空溶解法では、不純物を除去された溶融状態の金属チタンが滴下し、積層されていく。このようにして真空分離を行なうことで高品質のスポンジチタンを製造できる。
Here, a method for producing sponge titanium will be described.
Sponge titanium is produced by a refining process called “crawl process”.
1. Chlorination step: In the crawl method, raw material UGI is reacted with chlorine gas to form titanium tetrachloride (TiCl4).
2. Magnesium reduction step: Next, titanium tetrachloride (TiCl 4) is reacted with high-temperature molten magnesium to reduce the metal titanium and by-product magnesium chloride (MgCl 2).
3. Vacuum separation step (vacuum melting method): Since titanium metal contains magnesium chloride (MgCl2) and metal magnesium (Mg) as impurities, high vacuum distillation is performed to remove the impurities.
In the vacuum melting method, molten metal titanium from which impurities are removed is dropped and laminated. By performing vacuum separation in this way, high quality sponge titanium can be produced.
以上のようにして、多孔質のチタンを得た後、本発明の酸化チタン水質浄化体を製造するには、当該多孔質状態で薄板形状にし、その後、チタン表面を酸化させる。例えば、当該スポンジチタンの状態で同チタンをスライス切削した後に、チタン表面を酸化させる。スポンジチタンを溶解させて薄板形状や砂利状等の任意の形状に成形した後に、チタン表面を酸化させてもよい。
４．酸化工程：薄板形状になった板材のチタンを６００℃?８００℃に加熱し、焼きなましする。これにより、薄板形状とした多孔質状のチタン表面に酸化膜が形成される。
As described above, after obtaining porous titanium, in order to produce the titanium oxide water purification body of the present invention, a thin plate is formed in the porous state, and then the titanium surface is oxidized. For example, the titanium surface is oxidized after slicing and cutting the titanium in the state of the sponge titanium. The titanium surface may be oxidized after the sponge titanium is dissolved and formed into an arbitrary shape such as a thin plate shape or gravel shape.
4). Oxidation process: Titanium, which is a thin plate, is heated to 600 ° C. to 800 ° C. and annealed. Thereby, an oxide film is formed on the porous titanium surface having a thin plate shape.
薄板形状とすることで、全表面が酸素に触れ、かつ、６００℃〜８００℃にて焼きなましすることで、チタン表面に酸化膜が形成される。酸化工程を切削前に行ったとすれば、多孔質であっても全表面を酸化させることができない。薄板状であって多孔質であれば、表面積が大きな酸化チタン膜水質浄化体を製造できる。
なお、薄板状とするには、必ずしも一枚板である必要はない。例えば、一定形状でない多数の固体を用いて薄板状の状態にまとめ上げることも可能である。すなわち、真空溶解法でチタン塊を生成する際に、大きな一塊のスポンジチタンを破砕した際に生じる多孔質の砂利状のスポンジチタンを利用する。そして、当該砂利状の状態で、上述したのと同様な方法で酸化させた後、透光性素材の収容容器、もしくはフロロカーボン等の素材で編んだ収容袋（ネット）にて、砂利状の状態で分離しつつ収容して薄板状に形成すればよい。また、この砂利状のスポンジチタンは容器に収容できる最小の粒子が望ましい。
By making it a thin plate shape, the entire surface is exposed to oxygen and annealed at 600 ° C. to 800 ° C., whereby an oxide film is formed on the titanium surface. If the oxidation step is performed before cutting, the entire surface cannot be oxidized even if it is porous. If it is thin and porous, a titanium oxide film water purification body with a large surface area can be produced.
In addition, in order to make it thin plate shape, it does not necessarily need to be a single plate. For example, it is possible to use a large number of solids that are not fixed in shape to form a thin plate. That is, when a titanium lump is produced by a vacuum melting method, porous gravel-like sponge titanium generated when a large lump of sponge titanium is crushed is used. Then, in the state of gravel, after being oxidized by the same method as described above, in a gravel-like state in a container of translucent material or a storage bag (net) knitted with a material such as fluorocarbon And may be accommodated while being separated and formed into a thin plate shape. The gravel-like sponge titanium is preferably the smallest particle that can be accommodated in a container.
図１は、スポンジチタン１の状態で同チタンをスライス切削することで、多孔質状態で薄板形状のチタン２を形成する過程を示している。
薄板形状とすることで、液体の流路を形成することが可能である。
図２〜図４は、薄板形状とした酸化チタンで液体の流路を形成している。図２は斜視図により示しており、図３は製造過程を断面図により示しており、図４は使用状態を断面図により示している。
FIG. 1 shows a process of forming a thin plate-like titanium 2 in a porous state by slicing and cutting the same titanium in the state of the sponge titanium 1.
By using a thin plate shape, a liquid flow path can be formed.
In FIGS. 2 to 4, a liquid channel is formed of titanium oxide having a thin plate shape. 2 is a perspective view, FIG. 3 is a sectional view showing the manufacturing process, and FIG. 4 is a sectional view showing the state of use.
図２および図３に示すように、流路３は断面が逆台形となっている。すなわち、底４が狭まるように両側の壁面５を傾斜させている。開口の方が底４よりも広いことで、外部からの照射光が内周面（底４と壁面５の表面）を照射しやすくなる。流路３をそのまま液体が流れてしまうと、大部分の液体は酸化チタンの表面に接することなく流れ去ってしまうので、互い違いの形状とした堰板（邪魔板）６ａ，６ｂを配置することで、迷路状にしている。堰板６ａ，６ｂは、共に底４と接続するものの、壁面５，５に対しては一方の壁面５にのみ接続し、他方の壁面５との間に隙間を形成する形状となっている。この結果、流路３を液体が流れる際、堰板６ａ，６ｂごとに、右から左、左から右へと進路を変えられる。流路長が長くなるのに伴い、底４、壁面５、堰板６ａ，６ｂの表面に触れる。
むろんこれらの表面は全て薄板形状とした酸化チタンであり、図４に示すように、上面に紫外線灯７を設置することで、かかる流路全体を酸化チタン水質浄化体となっている。
As shown in FIGS. 2 and 3, the flow path 3 has an inverted trapezoidal cross section. That is, the wall surfaces 5 on both sides are inclined so that the bottom 4 is narrowed. Since the opening is wider than the bottom 4, the irradiation light from the outside can easily irradiate the inner peripheral surface (the surfaces of the bottom 4 and the wall surface 5). If the liquid flows through the flow path 3 as it is, most of the liquid will flow without contacting the surface of the titanium oxide, so by arranging the dam plates (baffle plates) 6a and 6b having alternate shapes, It's a maze. Although the weir plates 6 a and 6 b are both connected to the bottom 4, the wall surfaces 5 and 5 are connected to only one wall surface 5 and form a gap between the other wall surface 5. As a result, when the liquid flows through the flow path 3, the path can be changed from right to left and from left to right for each of the barrier plates 6a and 6b. As the flow path length increases, the surface of the bottom 4, the wall surface 5, and the weir plates 6a and 6b are touched.
Of course, these surfaces are all made of titanium oxide having a thin plate shape, and as shown in FIG. 4, by installing an ultraviolet lamp 7 on the upper surface, the entire flow path becomes a titanium oxide water purification body.
次に、図５は、真空溶解法で不純物を除去した金属チタンを製造する際、一塊のスポンジチタンとするのではなく、砂利状の固体として製造された金属チタン８を示している。
また、図６は、砂利状の金属チタン８を使用しつつ薄板形状とした酸化チタン水質浄化体を斜視図により示している。
砂利状であっても、小粒のものであれば、全体の形状として薄板形状とすることは可能である。図６は、ネット状とした透光性素材の収容容器９にて、砂利状の状態で分離しつつ金属チタン８を収容して薄板状に形成している。透光性素材の収容容器９として、ネット状のみならず、透明アクリル板などで挟み込み、その間に砂利状の金属チタン８を挟み込んで位置を固定し、さらに被浄化液体を挟み込んだ間を流路として流下させればよい。いずれの場合でも、外部から紫外線灯で紫外線を照射すれば、内部に収納された金属チタン８の酸化膜表面で水質浄化作用が行われる。
Next, FIG. 5 shows the metal titanium 8 manufactured as a gravel-like solid, not as a lump of sponge titanium when manufacturing metal titanium from which impurities are removed by a vacuum melting method.
FIG. 6 is a perspective view showing a titanium oxide water purification body having a thin plate shape using gravel-like metal titanium 8.
Even if it is gravel, it can be a thin plate as a whole if it is small. FIG. 6 shows a container 9 made of a translucent material in the form of a net, in which the titanium metal 8 is accommodated while being separated in a gravel state, and is formed into a thin plate shape. The translucent material container 9 is sandwiched not only by the net shape but also by a transparent acrylic plate or the like, sandwiched between gravel-like metal titanium 8 and fixed in position, and further, the flow path between the liquid to be purified. As it flows down. In any case, when ultraviolet rays are irradiated from the outside with an ultraviolet lamp, a water purification action is performed on the surface of the oxide film of the titanium metal 8 housed inside.
以上は、流路に対して、酸化チタン水質浄化体が浸漬される例を示したが、酸化チタンの浄化作用の恩恵を受けるためには、被洗浄液が酸化チタンの表面を流れ落ちていくようなものがよい。
図７は、表面流下を利用した酸化チタン水質浄化体を概略断面図により示している。
同図に示すものでは、それぞれ薄板形状とした酸化チタン１０ａ，１０ｂが互い違いに斜めに重なり合うように上下方向に重ねて形成されている。そして、互い違いとしたそれぞれの上面に紫外線を照射する。被浄化液体は、交互に酸化チタン１０ａ，１０ｂの表面に沿って徐々に下方に流れ落ちていく過程で、水質浄化作用を受けることになる。
互い違いにしない場合でも、酸化チタン１０ａを垂直面とし、被浄化液体の流量を調整しつつ、垂直面を流下させる過程で水質浄化作用を受けるようにしても良い。流量を調整する他、スプレーで噴霧して被洗浄液が酸化チタンに吹き付けるようなものも含まれる。
The above shows an example in which the titanium oxide water purification body is immersed in the flow path. However, in order to benefit from the purification action of titanium oxide, the liquid to be cleaned flows down the surface of the titanium oxide. Things are good.
FIG. 7 is a schematic cross-sectional view showing a titanium oxide water purification body utilizing surface flow.
In the figure, titanium oxides 10a and 10b each having a thin plate shape are formed so as to overlap each other in an up-and-down direction so as to be obliquely overlapped. Then, the upper surfaces of the staggered surfaces are irradiated with ultraviolet rays. The liquid to be purified is subjected to a water purification action in the process of gradually flowing downward along the surfaces of the titanium oxides 10a and 10b alternately.
Even when they are not staggered, the titanium oxide 10a may be used as a vertical surface, and the water purification operation may be performed in the process of flowing down the vertical surface while adjusting the flow rate of the liquid to be purified. In addition to adjusting the flow rate, there are also those in which the liquid to be cleaned is sprayed onto the titanium oxide by spraying.
水質浄化作用には紫外線（例えば波長３８０μｍ程度のもの）の照射が不可欠である。紫外線の光源は、ブラックライト、紫外線LEDもしくは殺菌灯がよい。
図８〜図１２は、水流を利用して発電し、発電した電力で紫外線灯を点灯させる照明器具を示している。図８は正面図により示しており、図９は断面の模式図により示しており、図１０は回転体を斜視図により示しており、図１１は電気回路図を示しており、図１２
は流路への配置状態を示している。
本照明器具２０は、本体２１が流路を仕切りつつ、中央の貫通口２２に水を誘導し、同貫通口２２内に備えられた筒状の回転体２３を水流によって回転させる。同回転体２３は筒状とした内側に水流を受けて回転させるための翼片２４を形成してあり、筒体の部分には交互に磁極を反転させた磁石２５を配置している。本体２１の貫通口２２の周りには誘導コイル２６を配置であるので、回転体２３とともに磁石２５が回転すると誘導コイル２６を横切る磁力線が変化して起電力を生じさせる。
Irradiation with ultraviolet rays (for example, having a wavelength of about 380 μm) is indispensable for the water purification action. The UV light source is preferably black light, UV LED or germicidal lamp.
FIGS. 8-12 has shown the lighting fixture which light-generates using a water flow and makes an ultraviolet lamp light with the generated electric power. 8 is a front view, FIG. 9 is a schematic cross-sectional view, FIG. 10 is a perspective view of the rotating body, FIG. 11 is an electric circuit diagram, and FIG.
Indicates an arrangement state in the flow path.
In this lighting fixture 20, the main body 21 divides the flow path, guides water to the central through-hole 22, and rotates the cylindrical rotating body 23 provided in the through-hole 22 by the water flow. The rotating body 23 is formed with a wing piece 24 for rotating by receiving a water flow inside a cylindrical shape, and magnets 25 having alternately reversed magnetic poles are arranged in the cylindrical body portion. Since the induction coil 26 is disposed around the through hole 22 of the main body 21, when the magnet 25 rotates together with the rotating body 23, the lines of magnetic force crossing the induction coil 26 change to generate an electromotive force.
このような発電機構では誘導コイル２６からは交流が発生するので、四つのＬＥＤ２７を誘導コイル２６に対してブリッジ回路を形成するように接続し、さらに充電電池２８へと接続する。すると、発電時に、整流しながら紫外線照明としてのＬＥＤ２７が点灯し、余分な電力は充電電池２８を充電するのに使用される。
図１２に示すように、流路３を横切るように照明器具２０を複数個配置し、その間に薄板形状とした酸化チタン１１を配置する。この場合、照明器具２０から照射される紫外線ができるだけ酸化チタン１１の表面に照射されやすいように入りくんだ配置とするとよい。照明器具２０の側ではＬＥＤ２７をたくさん配置することで、入りくんだ配置の酸化チタン１１の表面にできるだけ紫外線を照射させるようにすればよい。
発電機構は様々な変形例が可能であるし、充電電池の配置や、その有無を含めて、変更可能であることはいうまでもない。
In such a power generation mechanism, alternating current is generated from the induction coil 26, so that the four LEDs 27 are connected to the induction coil 26 so as to form a bridge circuit, and further connected to the rechargeable battery 28. Then, during power generation, the LED 27 as the ultraviolet illumination is turned on while rectifying, and the excess power is used to charge the rechargeable battery 28.
As shown in FIG. 12, a plurality of lighting fixtures 20 are disposed so as to cross the flow path 3, and the titanium oxide 11 having a thin plate shape is disposed therebetween. In this case, the arrangement may be such that the ultraviolet rays emitted from the luminaire 20 are as easy as possible to irradiate the surface of the titanium oxide 11 as much as possible. By arranging a large number of LEDs 27 on the side of the luminaire 20, it is only necessary to irradiate the surface of the titanium oxide 11 in a complicated arrangement with ultraviolet rays as much as possible.
It goes without saying that the power generation mechanism can be modified in various ways and can be changed including the arrangement of the rechargeable battery and the presence or absence thereof.
［評価試験１］
日照による焼成スポンジチタンの触媒作用のインジゴカルミン脱色を指標とした確認
[Evaluation Test 1]
Confirmation of catalytic action of calcined sponge titanium by sunshine using indigo carmine decolorization as an index
１−１．実験目的
焼成スポンジチタンが、日照下で酸化触媒作用を有することを確認する。
1-1. The purpose of the experiment To confirm that the calcined sponge titanium has an oxidation catalytic action under sunlight.
１−２．概要
インジゴカルミン水溶液に焼成スポンジチタンを投入して太陽光に曝露し、吸光度によりインジゴカルミンの分解による脱色を評価した。密閉の有無をはじめとする諸条件の異なる二種類の実験を行った。結果、両実験において焼成スポンジチタンは日照下でインジゴカルミン脱色効果を示し、二種類の焼成スポンジチタンのうちでは粒系の小さいものがより大きな脱色効果を示した。
1-2. Outline We put calcined sponge titanium into an indigo carmine solution, exposed to sunlight, and evaluated the decolorization due to decomposition of indigo carmine by absorbance. Two types of experiments were conducted under different conditions including the presence or absence of sealing. As a result, in both experiments, the calcined sponge titanium showed an indigo carmine decolorization effect under sunlight, and among the two types of calcined sponge titanium, the smaller ones showed a greater decolorization effect.
１−３．実験手順
焼成チタン実験を行った。両者 は密閉の有無、 ”密閉無し実験 ”、”密閉有り実験 ”と称する。
また、焼成スポンジチタンのうち粒径が大きいもを ”大スポンジチタン”、小さいものを ”小スポンジチタン ”と称する。
一例として、粒径が１５ｍｍ以上を大スポンジチタンと呼び、粒径が１５ｍｍ未満を小スポンジチタンと呼ぶ。
1-3. Experimental Procedure A calcined titanium experiment was conducted. Both are referred to as the presence or absence of sealing, “experiment without sealing”, and “experiment with sealing”.
Of the sintered sponge titanium, one having a large particle size is referred to as “large sponge titanium”, and the small one is referred to as “small sponge titanium”.
As an example, a particle size of 15 mm or more is referred to as large sponge titanium, and a particle size of less than 15 mm is referred to as small sponge titanium.
１−４．共通事項
インジゴカルミン水溶液を調製し、これに大小各スポンジチタンを投入、もしくはインジゴカルミン水溶液のみにて太陽光へ曝露し、適宜インジゴカルミンの脱色（分解）率を評価した。インジゴカルミンの脱色率は、インジゴカルミン水溶液の波長595 nmでの吸光度（OD595）と検量線より算出された。これにより、スポンジチタン添加によるインジゴカルミン脱色率への影響を比較した。焼成スポンジチタン添加により生じた脱色は触媒効果による酸化分解によると考えられるので、これにより焼成スポンジチタンの触媒効果を評価した。
1-4. Common subject matter
An indigo carmine aqueous solution was prepared, and each of the large and small sponge titanium was added thereto or exposed to sunlight only with the indigo carmine aqueous solution, and the decolorization (decomposition) rate of the indigo carmine was appropriately evaluated. The decolorization rate of indigo carmine was calculated from the absorbance (OD 595 ) at a wavelength of 595 nm of an indigo carmine aqueous solution and a calibration curve. Thereby, the influence on the indigo carmine decoloration rate by sponge titanium addition was compared. The decolorization caused by the addition of calcined sponge titanium is considered to be due to the oxidative decomposition due to the catalytic effect, and thus the catalytic effect of the calcined sponge titanium was evaluated.
１−５．密閉無し実験
インジゴカルミンを濃度5000 mg/LにてMilliQ水に溶解し、直径100mmのプラスチック製シャーレ（φ95×15 mm）3枚に各25.0 mlにて分注した。1枚に大スポンジチタン50 g、1枚に小スポンジチタン50 gを加え1枚はスポンジチタン無しとした。スポンジチタン添加直後を経過時間0 hourとし、適宜各インジゴカルミン溶液の一部を採取・希釈し波長595 nmでの吸光度（OD595）を測定した。
日照時はシャーレ蓋を外し、直射日光でインジゴカルミン水溶液及び焼成スポンジチタンを処理した。水分の蒸発は重量の減少から推定し、MilliQ水を添加し混合することで補正した。日照時以外はシャーレに蓋をし、室内に保管した。
脱色率は、各時点において式(1) により、その時点でのスポンジチタン無しを基準（0%）として算出した。
日光下における検体の外観を図１３に示す。図１３は、左からスポンジチタン無し、大スポンジチタン添加、小スポンジチタン添加を示す。
1-5. Experiment without sealing Indigo carmine was dissolved in MilliQ water at a concentration of 5000 mg / L, and dispensed into 3 plastic petri dishes (φ95 × 15 mm) with a diameter of 100 mm at 25.0 ml each. One large sponge titanium 50 g and one small sponge titanium 50 g were added, and one sheet had no sponge titanium. Immediately after the addition of sponge titanium, the elapsed time was 0 hour, and a part of each indigo carmine solution was appropriately collected and diluted, and the absorbance (OD 595 ) at a wavelength of 595 nm was measured.
During sunlight, the petri dish lid was removed and the indigo carmine aqueous solution and the sintered sponge titanium were treated with direct sunlight. Water evaporation was estimated from weight loss and corrected by adding MilliQ water and mixing. The petri dish was covered and stored indoors except during sunshine.
The decolorization rate was calculated according to the formula (1) at each time point with no sponge titanium at that time as a reference (0%).
The appearance of the specimen in sunlight is shown in FIG. FIG. 13 shows, from the left, no sponge titanium, large sponge titanium addition, and small sponge titanium addition.
１−６．密閉有り実験
インジゴカルミンを濃度20 mg/LにてMilliQ水に溶解し、本溶液をポリプロピレン製遠沈管（容量50 ml、φ29×115 mm、スクリューキャップ付き）6本に各30.0 mlにて分注した。これらを大スポンジチタン添加、小スポンジチタン添加、スポンジチタン無し各2本とし、それぞれ1本を日照無し、1本を日照有りとした。スポンジチタン添加量は大・小とも30 gとした。
スポンジチタン添加直後を経過時間0 hourとし、経過時間2 hour及び4 hourにて各インジゴカルミン溶液の一部を採取し波長595 nmでの吸光度（OD595）を測定しこれの減少より脱色率を算出した。日照時もキャップを密閉したままとし、ポリプロピレン製側壁を透過した太陽光をインジゴカルミン水溶液及びスポンジチタンへ照射した。日照無しの検体は、室内暗所にて保管した。
脱色率は、各時点において式(2) により、同時点での日照無しを0%として算出した。
日照下における検体の外観を図１４に示す。図１４は、上段：日照無し、下段：日照有り、有り、いずれも左からスポンジチタン無し、大スポンジチタン添加、小スポンジチタン添加、4 hour経過後を示す。
1-6. Sealed experiment Indigo carmine was dissolved in MilliQ water at a concentration of 20 mg / L, and this solution was dispensed into 6 centrifuge polypropylene tubes (capacity 50 ml, φ29 x 115 mm, with screw caps) at 30.0 ml each. did. These were large sponge titanium added, small sponge titanium added, and two without sponge titanium, one with no sunshine and one with sunshine. The amount of titanium sponge added was 30 g, both large and small.
Immediately after the addition of sponge titanium, the elapsed time is 0 hour, a portion of each indigo carmine solution is sampled at the elapsed time of 2 hours and 4 hours, and the absorbance at a wavelength of 595 nm (OD 595 ) is measured. Calculated. The cap was kept sealed during sunshine, and sunlight transmitted through the polypropylene side wall was irradiated to the indigo carmine aqueous solution and sponge titanium. Samples without sunshine were stored in a dark room.
The decolorization rate was calculated by the formula (2) at each time point with no sunshine at the same time as 0%.
The appearance of the specimen under sunlight is shown in FIG. FIG. 14 shows the upper row: no sunshine, the lower row: with sunshine, with all, from the left without sponge titanium, large sponge titanium added, small sponge titanium added, after 4 hours.
１−７．実験結果および考察
（密閉無し実験）
結果を図１５に示す。実験はスポンジチタン添加後、経過時間添加後、経過時間71 hourまで行った。41 hourから47 hour、65 hourから71 hourに日照を行った。スポンジチタン添加無しでのOD595の目立った減少は見られなかった。
室内への保管では40 hour以上経過後も脱色は見られなかったが、日光に曝露すると脱色が生じた。小スポンジチタンでより大きな脱色効果が生じた。
1-7. Experimental results and discussion (non-sealing experiment)
The results are shown in FIG. The experiment was performed up to 71 hours after the addition of sponge titanium and after the addition of elapsed time. Sunlight was applied from 41 hour to 47 hour and from 65 hour to 71 hour. There was no noticeable reduction in OD 595 without the addition of sponge titanium.
When stored indoors, no decolorization was observed after more than 40 hours, but decolorization occurred when exposed to sunlight. Smaller sponge titanium produced a greater decolorization effect.
（密閉有り実験）
結果を図１６に示す。実験はスポンジチタン添加後、経過時間4 hoursまで行い、スポンジチタン添加後、経過時間0、2、4 hourに測定を行った。
スポンジチタン添加無しでは、太陽光を照射してもほとんど脱色が起こらなかったのに対し、大・小スポンジチタン添加では急速な脱色が起きた。密閉無し実験と同様に、大スポンジチタンと小スポンジチタンでは後者の方が効果は大きかった。
(Experiment with sealing)
The results are shown in FIG. The experiment was conducted up to 4 hours after the addition of sponge titanium, and the measurements were made at 0, 2, and 4 hours after the addition of sponge titanium.
Without the addition of sponge titanium, decolorization hardly occurred even when irradiated with sunlight, whereas when large or small sponge titanium was added, rapid decolorization occurred. As with the non-sealing experiment, the latter was more effective for large sponge titanium and small sponge titanium.
以上の結果より、焼成されたスポンジチタンへ太陽光が曝露されることによりインジゴカルミン脱色作用が得られた。また、大小スポンジチタンの効果の比較においては小スポンジチタンの作用が大きかった。
インジゴカルミン脱色作用これは、高い信頼度でスポンジチタン表面の酸化被膜（酸化チタン）による酸化触媒活性を有することが確認された。
From the above results, indigo carmine decolorization action was obtained by exposing sunlight to the fired sponge titanium. Moreover, in the comparison of the effect of large and small sponge titanium, the action of small sponge titanium was large.
Indigo carmine decolorization action This was confirmed to have an oxidation catalytic activity by an oxide film (titanium oxide) on the surface of titanium sponge with high reliability.
［評価試験２］
焼成スポンジチタンと酸化チタン触媒塗料塗布スポンジチタンの比較
[Evaluation Test 2]
Comparison between calcined sponge titanium and titanium sponge coated with titanium oxide catalyst paint
２−１．実験目的
焼成によりスポンジチタンへ付与される酸化効果を、市販の酸化チタン塗料塗布によるそれと比較する。また繰り返し同一のスポンジチタンを用いた実験により、付与される触媒効果の耐久性を比較する。
2-1. Experimental purpose The oxidation effect imparted to sponge titanium by baking is compared with that obtained by applying a commercially available titanium oxide paint. In addition, the durability of the applied catalytic effect is compared by repeatedly using the same sponge titanium.
２−２．概要
50 mlファルコンチューブに分注したインジゴカルミン水溶液に、3種類の異なる処理を施されたスポンジチタンを投入した場合、及び何も投入しない場合の4種の条件における、日光照射下での脱色の早さを比較した。ペレットには、未処理（洗浄のみ）、焼成したペレット、および市販の酸化チタン塗料を塗布したペレットを用いた。これにより、インジゴカルミンの分解脱色を指標として触媒効果（酸化分解効果）を計測・比較した。
また実験を同一のペレットを繰り返し用いて3回行い、焼成、もしくは塗料塗布により付与される触媒効果の耐久性の比較を試みた。結果、焼成で付与される効果は酸化チタン塗布によるそれに劣るが耐久性ではこれを上回る可能性が示唆された。
2-2. Overview
Indigo carmine aqueous solution dispensed into 50 ml Falcon tubes, when sponge titanium treated with 3 different treatments was added and when no charge was added, decoloration under sunlight was accelerated under 4 conditions. Compared. As the pellets, untreated (cleaning only), fired pellets, and pellets coated with a commercially available titanium oxide paint were used. As a result, the catalytic effect (oxidative decomposition effect) was measured and compared using the decomposition and decolorization of indigo carmine as an index.
In addition, the experiment was repeated three times using the same pellet repeatedly, and an attempt was made to compare the durability of the catalytic effect imparted by firing or coating. As a result, it was suggested that the effect imparted by firing was inferior to that of titanium oxide coating, but the durability could exceed this.
２−３．実験手順
２−３−１．スポンジチタン処理
スポンジチタンを希硝酸にて洗浄・乾燥した。未処理チタンによる処理では、これをそのまま用いた。
焼成スポンジチタンによる実験では、洗浄・乾燥後のスポンジチタンを「陶職人」（クマザキエイム株式会社製造）を用いて、700℃にて約4 hour処理したものを用いた。焼成により、スポンジチタン外観は青金色に変化した。
酸化チタン塗布では、洗浄・乾燥後のスポンジチタンに市販の酸化チタン塗料（「セブンチタニック」、セブンケミカル株式会社製造）を用いた。
2-3. Experimental procedure 2-3-1. Sponge titanium treatment Sponge titanium was washed with diluted nitric acid and dried. This was used as it was in the treatment with untreated titanium.
In the experiment using the sintered sponge titanium, the cleaned and dried sponge titanium was treated at 700 ° C. for about 4 hours using “Ceramic craftsman” (manufactured by Kumazaki Aim Co., Ltd.). As a result of firing, the appearance of titanium sponge changed to a blue-gold color.
In the titanium oxide coating, a commercially available titanium oxide paint ("Seven Titanic" manufactured by Seven Chemical Co., Ltd.) was used for the sponge titanium after washing and drying.
２−３−２．インジゴカルミン脱色実験
インジゴカルミンを濃度20 mg/LにてMilliQ水に溶解し、各処理のスポンジチタンを投入、もしくはインジゴカルミン水溶液のみにて太陽光へ曝露し、1 hour毎にインジゴカルミン水溶液の波長595 nmでの吸光度（OD595）を測定した。本溶液をポリプロピレン製遠沈管（容量50 ml、φ29×115 mm、スクリューキャップ付き）6本に各30.0 mlにて分注した。インジゴカルミン溶液の添加量は、スポンジチタン添加無で50 ml、各スポンジチタン添加時は42 mlとし、スポンジチタンと合わせた体積を約50 mlとした。
これらをキャップを閉めた状態でスポンジチタン添加直後を経過時間0 hourとし、経過時間5 hourまで1 hourごとに0.4 mlを採取し波長595 nmでの吸光度（OD595）を吸光光度計(Multiskan FC、Thermo Fisher Scientific Inc。)測定し、これを用いて式(1)により脱色率を算出した。
脱色率は、各時点において式(3)となる。
これにより、スポンジチタン添加によるインジゴカルミン脱色率への影響を比較した。焼成スポンジチタン添加により生じた脱色は触媒効果による酸化分解によると考えられるので、これにより焼成スポンジチタンの触媒効果を評価した。
2-3-2. Indigo Carmine Decolorization Experiment Dissolve indigo carmine in MilliQ water at a concentration of 20 mg / L, add sponge titanium for each treatment, or expose to sunlight only with an indigo carmine aqueous solution, and the wavelength of the indigo carmine aqueous solution every hour. Absorbance at 595 nm (OD 595 ) was measured. This solution was dispensed into 6 centrifuge tubes made of polypropylene (capacity 50 ml, φ29 × 115 mm, with screw cap) at 30.0 ml each. The amount of the indigo carmine solution added was 50 ml without adding sponge titanium, 42 ml when adding each sponge titanium, and the combined volume with sponge titanium was about 50 ml.
With these caps closed, immediately after adding sponge titanium, the elapsed time was 0 hour, and 0.4 ml was collected every hour until the elapsed time was 5 hours, and the absorbance at a wavelength of 595 nm (OD 595 ) was measured with an absorptiometer (Multiskan FC , Thermo Fisher Scientific Inc.), and using this, the decolorization rate was calculated by equation (1).
The decolorization rate is expressed by Equation (3) at each time point.
Thereby, the influence on the indigo carmine decoloration rate by sponge titanium addition was compared. The decolorization caused by the addition of calcined sponge titanium is considered to be due to the oxidative decomposition due to the catalytic effect, and thus the catalytic effect of the calcined sponge titanium was evaluated.
２−４．実験結果および考察
結果を図１６に示す。”ペレット無し”、”未処理（ペレット）”、”焼成（ペレット）”及び”塗料（ペレット）”の4種の条件それぞれの1回目、2回目及び3回目、計12種類の処理における日照時間に伴う脱色率を示している。
”ペレット無し”、”未処理”ではインジゴの脱色は僅かであった。”焼成”、”塗料”ペレットでは日光への曝露に伴い明らかな脱色が生じ、これらの処理によりスポンジチタンに触媒効果が付与されたことが確認された。
脱色の進行は”塗料”の場合において”焼成”のそれより大きく、焼成により付与される触媒効果はチタン塗料のそれには及ばなかった。
しかし”塗料”の場合は2回目にて脱色効果が僅かに低かったのに対し、”焼成”では2回目においてより大きな脱色率が得られている。これは実験2回目の日射量が1回目のそれより大きかったことによると考えられる。しかし”塗料”では2回目における脱色率は1回目とほぼ同程度となり、ペレットの触媒効果は低下したことが示唆された。ただ、3回目の実験では、両条件とも2回目からの変化はほぼ見られなかった。
以上より、現時点での焼成スポンジチタンの触媒効果は市販の酸化チタン触媒塗料に及ばなかった。ただ、本研究で検討する方法では焼成のみで酸化チタン生成が可能なため、維持を含めた経済性では酸化チタン触媒塗料に優位性がある可能性がある。
2-4. The experimental results and discussion results are shown in FIG. Sunlight duration in 12 types of treatment, 1st time, 2nd time and 3rd time for each of the four conditions of “no pellet”, “untreated (pellet)”, “fired (pellet)” and “paint (pellet)” Shows the decolorization rate.
Indigo decolorization was slight in “no pellet” and “untreated”. In the “fired” and “paint” pellets, clear discoloration occurred upon exposure to sunlight, and it was confirmed that the catalytic effect was imparted to the sponge titanium by these treatments.
The progress of decolorization was greater in the case of “paint” than that of “calcination”, and the catalytic effect imparted by calcination did not reach that of titanium paint.
However, in the case of “paint”, the decolorization effect was slightly lower in the second time, whereas in “baking”, a larger decolorization rate was obtained in the second time. This is thought to be because the amount of solar radiation in the second experiment was larger than that in the first. However, in the case of “paint”, the decolorization rate in the second time was almost the same as in the first time, suggesting that the catalytic effect of the pellet was reduced. However, in the third experiment, there was almost no change from the second in both conditions.
From the above, the catalytic effect of the fired titanium sponge at the present time did not reach that of commercially available titanium oxide catalyst paints. However, since the method examined in this study can generate titanium oxide only by firing, there is a possibility that the titanium oxide catalyst coating is superior in terms of economy including maintenance.
［評価試験３］
スポンジチタンの長期水浸による酸化触媒効果への影響測定
[Evaluation Test 3]
Measurement of the effect of long-term water immersion of sponge titanium on oxidation catalyst effect
３−１．実験目的
より簡便な酸化チタン生成方法として、水中での長期的な保管による酸化を検討した。水中は想定される用途におけるスポンジチタンの状態でもあるため、これが可能であればメンテナンスフリー、もしくはそれに近い処理が可能となる。
3-1. Experimental purpose As a simpler method for producing titanium oxide, oxidation by long-term storage in water was investigated. Underwater is also a state of sponge titanium for the intended use, and if this is possible, maintenance-free or close processing is possible.
３−２．概要
スポンジチタンの水中での長期的（数か月）な保管による酸化分解能への影響を測定した。
また、チタンと比較しよりイオン化傾向の高い金属（アルミニウム）と共に水浸することで、酸化チタン生成を促進できる可能性があるため、これについても検証した。
3-2. Summary The effects of long-term (several months) storage of sponge titanium on water were measured.
Moreover, since it may be able to accelerate | stimulate titanium oxide production | generation by water immersion with the metal (aluminum) with a higher ionization tendency compared with titanium, this was also verified.
３−３．実験手順
３−３−１．スポンジチタン前処理
スポンジチタンを目開き9.5 mmのふるいを用いて粒径の大きいものを除去し、希硝酸（69 %m/mを29倍volのMilli-Q水）に数分水浸、Milli-Q水で濯ぎ洗浄した。その後4.75 mmのふるいにて粒径の小さいものを除去し乾燥した。
3-3. Experimental procedure 3-3-1. Titanium sponge pretreatment Sponge titanium was removed using a 9.5 mm sieve to remove large particles, and immersed in dilute nitric acid (69% m / m 29 times vol Milli-Q water) for several minutes. Milli -Q rinsed with water. Thereafter, a small particle size was removed with a 4.75 mm sieve and dried.
３−３−２．スポンジチタン焼成
前処理後のスポンジチタン約5.0kgを直径18.0cm高さ6.0cmの陶製蒸発皿の底に均一に敷き詰め、余熱した酸化焼成用電気窯（「陶職人ＩＩ」、クマザキエイム株式会社製造）を用いて600℃、2 hour焼成した。
3-3-2. Sponge titanium firing Approximately 5.0 kg of pre-treated sponge titanium was spread evenly on the bottom of a ceramic evaporating dish with a diameter of 18.0 cm and a height of 6.0 cm, and preheated electric kiln for oxidation firing (manufactured by “Ceramic Artisan II”, manufactured by Kumazaki Aim Co., Ltd.) Was calcined at 600 ° C. for 2 hours.
３−３−３．水浸
焼成、および未処理のスポンジチタン450.0gを透明蓋付樹脂製角型ケース（363×263×50 mm）の底に広げ、スポンジチタンが完全に水没する(水深2 cm)ようMilli-Q水を加え、ケース蓋（透明樹脂製）を閉じ露天下に保管した。
高イオン化傾向金属（アルミニウム）との水浸による酸化促進
ケース底全体にアルミニウム箔を敷いた状態で水浸を行った。
3-3-3. Milli-Q so that the sponge titanium is completely submerged (water depth 2 cm) by spreading 450.0 g of water-baked and untreated sponge titanium on the bottom of a plastic square case with transparent lid (363 x 263 x 50 mm) Water was added, the case lid (made of transparent resin) was closed and stored under the open air.
Oxidation promotion by water immersion with highly ionized metal (aluminum) The case was immersed in an aluminum foil laid on the entire bottom.
３−３−４．長期水浸
アルミニウム有、無両条件とも、12月初旬から2月初旬までの約二か月間、上記の状態で露天下に保管した。
3-3-4. Long-term water immersion Both with and without aluminum were stored under the above conditions for about two months from the beginning of December to the beginning of February.
３−３−５．酸化触媒能（インジゴカルミン脱色効果）測定
インジゴカルミンを濃度25.0mg/LにてMilliQ水に溶解し、スポンジチタンを投入して太陽光へ曝露した。スポンジチタンは35.0g（水分を含んだ状態）とし、これに35.0mlのインジゴカルミン水溶液を加えた。全体の体積は50 mlとなった。容器としてポリプロピレン製遠沈管（容量50 ml、φ29×115 mm、スクリューキャップ付き）を用い、透明な側壁を通しインジゴ水溶液及びスポンジチタンを日光に曝露した。
コントロールとして、インジゴカルミン水溶液50 mlのみを分注した場合についても測定を行った。
スポンジチタン添加直後を経過時間0 hourとし、5 hour経過後まで1 hourごとに一部を採取して波長595 nmでの吸光度（OD595）を測定し、これを用いて式(1)により脱色率を算出した。
脱色率は、各時点において式(4)である。
これにより、スポンジチタン添加によるインジゴカルミン脱色率への影響を比較した。焼成スポンジチタン添加により生じた脱色は触媒効果による酸化分解によると考えられるので、これにより焼成スポンジチタンの触媒効果を評価した。
3-3-5. Measurement of oxidation catalytic ability (indigo carmine decolorization effect) Indigo carmine was dissolved in MilliQ water at a concentration of 25.0 mg / L, and sponge titanium was added to expose it to sunlight. The sponge titanium was 35.0 g (containing water), and 35.0 ml of indigo carmine aqueous solution was added thereto. The total volume was 50 ml. A polypropylene centrifuge tube (capacity 50 ml, φ29 × 115 mm, with screw cap) was used as a container, and an indigo aqueous solution and titanium sponge were exposed to sunlight through a transparent side wall.
As a control, measurement was also performed when only 50 ml of an indigo carmine solution was dispensed.
Immediately after the addition of sponge titanium, the elapsed time is 0 hour, and a portion is collected every 1 hour until 5 hours have passed, and the absorbance at a wavelength of 595 nm (OD 595 ) is measured. The rate was calculated.
The decolorization rate is expressed by equation (4) at each time point.
Thereby, the influence on the indigo carmine decoloration rate by sponge titanium addition was compared. The decolorization caused by the addition of calcined sponge titanium is considered to be due to the oxidative decomposition due to the catalytic effect, and thus the catalytic effect of the calcined sponge titanium was evaluated.
３−４．結果
焼成スポンジチタン、未処理スポンジチタンによる実験結果を図１７に示す。
水浸＋は先述の水浸を行ったスポンジチタン、水浸−は乾燥状態で室内保管したスポンジチタンを示す。またアルミ＋は水浸時底面にアルミニウム箔を敷いたスポンジチタン、アルミ-はそれを行わなかったものを示す。水浸−ではアルミニウム箔は使用していない。
焼成スポンジチタンの結果において、”水浸＋アルミ＋”で2 hour経過時OD595測定後ミスにより検体を失ってしまったため、”水浸＋アルミ＋2”として2 hour経過時点から再度測定開始している。
焼成スポンジチタンでは”水浸−“が最も高い脱色効果を示し、”水浸＋アルミ−“および”水浸＋アルミ＋”との比較から、アルミニウム箔の有無にかかわらず長期の水浸によりスポンジチタンの酸化触媒能は低下した。
未処理スポンジチタンでは、”水浸＋アルミ−“、”水浸＋アルミ＋”での脱色率の上昇はいずれもきわめて小さかった。
これらの結果より、意図された水溶液系への水浸、及びそれと高イオン化傾向金属との併用によるスポンジチタン酸化は本実験条件では達成できないことが示された。
3-4. Result The experimental result by baking sponge titanium and untreated sponge titanium is shown in FIG.
Water immersion + indicates sponge titanium that has been immersed in water, and water immersion− indicates sponge titanium that has been stored indoors in a dry state. Aluminum + indicates sponge titanium with aluminum foil laid on the bottom when immersed in water, and aluminum-indicates that this was not done. In the water immersion, aluminum foil is not used.
In the result of sintered sponge titanium, the sample was lost due to an error after OD 595 measurement for 2 hours with “water immersion + aluminum +”, so start measurement again after 2 hours as “water immersion + aluminum +2”. Yes.
In the case of fired sponge titanium, “water immersion-” shows the highest decoloring effect. Compared with “water immersion + aluminum-” and “water immersion + aluminum +”, sponge was obtained by long-term water immersion regardless of the presence of aluminum foil. The oxidation catalytic ability of titanium decreased.
In the untreated sponge titanium, the increase in the decolorization rate in “water immersion + aluminum−” and “water immersion + aluminum +” was extremely small.
From these results, it was shown that sponge titanium oxidation by the intended water immersion and combined use with a highly ionized metal cannot be achieved under the present experimental conditions.
なお、本発明は前記実施例に限られるものでないことは言うまでもない。当業者であれば言うまでもないことであるが、
・前記実施例の中で開示した相互に置換可能な部材および構成等を適宜その組み合わせを変更して適用すること
・前記実施例の中で開示されていないが、公知技術であって前記実施例の中で開示した部材および構成等と相互に置換可能な部材および構成等を適宜置換し、またその組み合わせを変更して適用すること
・前記実施例の中で開示されていないが、公知技術等に基づいて当業者が前記実施例の中で開示した部材および構成等の代用として想定し得る部材および構成等と適宜置換し、またその組み合わせを変更して適用すること
は本発明の一実施例として開示されるものである。
Needless to say, the present invention is not limited to the above embodiments. It goes without saying for those skilled in the art,
-Applying the combination of the mutually replaceable members and configurations disclosed in the above-described embodiments as appropriate-The above-described embodiments are not disclosed in the above-described embodiments, but are publicly known techniques. The members and structures that can be mutually replaced with the members and structures disclosed in the above are appropriately replaced, and the combination is changed and applied. It is an embodiment of the present invention that a person skilled in the art appropriately replaces the members and configurations that can be assumed as substitutes for the members and configurations disclosed in the above-described embodiments, and changes the combination to apply. It is disclosed as.
１…スポンジチタン、２…チタン、３…流路、４…底、５…壁面、６ａ，６ｂ…堰板（邪魔板）、８…金属チタン、９…収容容器、１０ａ，１０ｂ…酸化チタン、１１…酸化チタン、２０…照明器具、２１…本体、２２…貫通口、２３…回転体、２４…翼片、２５…磁石、２６…誘導コイル、２７…ＬＥＤ、２８…充電電池。 DESCRIPTION OF SYMBOLS 1 ... Sponge titanium, 2 ... Titanium, 3 ... Channel, 4 ... Bottom, 5 ... Wall surface, 6a, 6b ... Dam plate (baffle plate), 8 ... Metal titanium, 9 ... Container, 10a, 10b ... Titanium oxide, DESCRIPTION OF SYMBOLS 11 ... Titanium oxide, 20 ... Lighting fixture, 21 ... Main body, 22 ... Through-hole, 23 ... Rotating body, 24 ... Wing piece, 25 ... Magnet, 26 ... Induction coil, 27 ... LED, 28 ... Rechargeable battery
以上のようにして、多孔質のチタンを得た後、本発明の酸化チタン水質浄化体を製造するには、当該多孔質状態で薄板形状にし、その後、チタン表面を酸化させる。例えば、当該スポンジチタンの状態で同チタンをスライス切削した後に、チタン表面を酸化させる。スポンジチタンを溶解させて薄板形状や砂利状等の任意の形状に成形した後に、チタン表面を酸化させてもよい。
４．酸化工程：薄板形状になった板材のチタンを６００℃〜８００℃に加熱し、焼きなましする。これにより、薄板形状とした多孔質状のチタン表面に酸化膜が形成される。
As described above, after obtaining porous titanium, in order to produce the titanium oxide water purification body of the present invention, a thin plate is formed in the porous state, and then the titanium surface is oxidized. For example, the titanium surface is oxidized after slicing and cutting the titanium in the state of the sponge titanium. The titanium surface may be oxidized after the sponge titanium is dissolved and formed into an arbitrary shape such as a thin plate shape or gravel shape.
4). Oxidation step: Titanium of the thin plate is heated to 600 ° C. to 800 ° C. and annealed. Thereby, an oxide film is formed on the porous titanium surface having a thin plate shape.
Claims (12)
つつ収容して薄板状に形成されることを特徴とする請求項７に記載の酸化チタン水質浄化体の製造方法。 Porous gravel-like titanium produced when crushing sponge titanium formed by the vacuum melting method is oxidized in the gravel-like state, and then in a gravel-like state in a container made of a translucent material. The method for producing a titanium oxide water purifier according to claim 7, wherein the titanium oxide water purification body is accommodated while being separated and formed into a thin plate shape.
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|---|---|---|---|---|
| JP2018140380A (en) * | 2017-02-28 | 2018-09-13 | エムキューダブリュー カンパニー リミテッド | Flowing water purifier |
| JP2020010659A (en) * | 2018-07-20 | 2020-01-23 | 株式会社ワコーシステムコントロール | Sterilization method and device of culture solution |
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| JP3087669U (en) * | 2002-01-31 | 2002-08-16 | ジェイ・ティ・メタル株式会社 | Purifier |
| JP2004195435A (en) * | 2002-12-20 | 2004-07-15 | Shinei:Kk | Water cleaning agent and method of cleaning water using the same |
| JP4534144B2 (en) * | 2005-02-28 | 2010-09-01 | 財団法人電力中央研究所 | Purification device |
| JP5069963B2 (en) * | 2007-07-18 | 2012-11-07 | 株式会社 オノモリ | Cutting piece of titanium material with titanium dioxide coating on the surface |
| JP5197766B2 (en) * | 2009-06-01 | 2013-05-15 | 新日鐵住金株式会社 | Titanium-based material having visible light responsiveness and excellent photocatalytic activity and method for producing the same |
| JP2012081427A (en) * | 2010-10-13 | 2012-04-26 | Sharp Corp | Sterilizer and water purifier equipped therewith |
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| JP2018140380A (en) * | 2017-02-28 | 2018-09-13 | エムキューダブリュー カンパニー リミテッド | Flowing water purifier |
| JP2020010659A (en) * | 2018-07-20 | 2020-01-23 | 株式会社ワコーシステムコントロール | Sterilization method and device of culture solution |
| JP7204175B2 (en) | 2018-07-20 | 2023-01-16 | 株式会社ワコーシステムコントロール | Method and apparatus for sterilizing culture medium |
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