JP2008150232A - Metatitanic acid slurry for raw material of photocatalyst titanium oxide and method for producing the slurry - Google Patents
Metatitanic acid slurry for raw material of photocatalyst titanium oxide and method for producing the slurry Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002253 acid Substances 0.000 title claims abstract description 62
- 239000002002 slurry Substances 0.000 title claims abstract description 61
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 239000002994 raw material Substances 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000001699 photocatalysis Effects 0.000 claims abstract description 26
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 15
- 238000004062 sedimentation Methods 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 39
- 239000010936 titanium Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 abstract description 14
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000009283 thermal hydrolysis Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
本発明は、光触媒酸化チタンの原料として有用なメタチタン酸スラリー及びその製造方法に関するものである。 The present invention relates to a metatitanic acid slurry useful as a raw material for photocatalytic titanium oxide and a method for producing the same.
光触媒酸化チタンは、空気浄化など生活環境の清浄化や、環境汚染物質の分解処理等に利用されている。通常使用されるアナターゼ型の光触媒用酸化チタンは、例えば、メタチタン酸を前駆体として製造することができる（例えば、特許文献１〜５参照）。 Photocatalytic titanium oxide is used for purification of living environment such as air purification and decomposition treatment of environmental pollutants. The anatase-type photocatalyst titanium oxide that is usually used can be produced, for example, using metatitanic acid as a precursor (see, for example, Patent Documents 1 to 5).
弱いアナターゼ型の結晶性を示すメタチタン酸の製造方法は、酸化チタン工業の分野では周知である。典型的にはメタチタン酸は、硫酸チタニルの溶液を加熱加水分解することによって製造される。
しかしながら、メタチタン酸を前駆体として得られたアナターゼ型の光触媒用酸化チタンにおいて、当該酸化チタンの光触媒能とメタチタン酸の特性との相互関係については、これまで解明されておらず、不明であった。 However, in the anatase-type photocatalytic titanium oxide obtained using metatitanic acid as a precursor, the correlation between the photocatalytic ability of the titanium oxide and the properties of metatitanic acid has not been elucidated so far and is unknown. .
また、上記の特許文献に記載された光触媒用酸化チタンの光触媒能については、２−プロパノール、メチレンブルー、酢酸、アルデヒド等の分解や二酸化炭素生成速度で評価されているが、未だ実用レベルに達しているとは言い難く、光触媒能がさらに向上した酸化チタンの開発が望まれていた。 In addition, the photocatalytic ability of the titanium oxide for photocatalyst described in the above patent document has been evaluated by decomposition of 2-propanol, methylene blue, acetic acid, aldehyde, etc. and carbon dioxide production rate, but it has still reached a practical level. However, development of titanium oxide having further improved photocatalytic ability has been desired.
従って、本発明の目的は、各種光触媒能に優れた光触媒用酸化チタンを製造することが可能となる、光触媒用酸化チタンの前駆体としてのメタチタン酸スラリー及びその製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a metatitanic acid slurry as a precursor of titanium oxide for photocatalyst, which can produce various titanium oxides for photocatalysts, and a method for producing the same.
本発明者らは、酸化チタンの光触媒能とメタチタン酸の特性との相互関係について鋭意検討を重ねた結果、沈降速度が所定の範囲となるようなメタチタン酸スラリーを用いることにより、得られた酸化チタンの光触媒特性が優れたものとなることを見出し、本発明を完成させた。 As a result of intensive studies on the correlation between the photocatalytic ability of titanium oxide and the properties of metatitanic acid, the present inventors have obtained the oxidation obtained by using a metatitanic acid slurry that has a settling rate within a predetermined range. It was found that the photocatalytic properties of titanium were excellent, and the present invention was completed.
即ち、本発明に係る光触媒酸化チタン原料用メタチタン酸スラリーは、ＴｉＯ２として４０ｇ／Ｌ、及び温度を３０℃の条件に調整したときの沈降速度が１５〜３０ｍｍ／３０分であることを特徴とする。 That is, the metatitanic acid slurry for a photocatalytic titanium oxide raw material according to the present invention is characterized in that the settling rate is 15 to 30 mm / 30 minutes when the TiO 2 is 40 g / L and the temperature is adjusted to 30 ° C. To do.
また、前記メタチタン酸スラリーは、スラリー中のＦｅ２Ｏ３含有量がＴｉＯ２に対して５０質量ｐｐｍ以下であることが好ましい。 The metatitanic acid slurry preferably has an Fe 2 O 3 content of 50 mass ppm or less based on TiO 2 .
また、前記メタチタン酸スラリーは、乾燥後のＳＯ３含有量が０．５〜３．０質量％であることが好ましい。 Further, the metatitanic acid slurry is preferably SO 3 content after drying is 0.5 to 3.0 mass%.
更に、前記メタチタン酸スラリーは、乾燥後の比表面積が２８０を超え、かつ３６０ｍ２／ｇ以下であることが好ましく、３００〜３５０ｍ２／ｇであることが特に好ましい。 Furthermore, the metatitanic acid slurry, specific surface area after drying exceeds the 280, and is preferably 360 m 2 / g or less, particularly preferably 300~350m 2 / g.
また、本発明に係る光触媒酸化チタン原料用メタチタン酸スラリーの製造方法は、ＴｉＯ２濃度が２５０〜２７０ｇ／Ｌ、Ｔｉ３＋濃度がＴｉＯ２換算で３．０〜１０．０ｇ／Ｌの硫酸チタニル溶液に、別途作製したアナターゼシードをＴｉＯ２換算で硫酸チタニル溶液中のＴｉＯ２に対して３〜１０質量％添加し、沸点以上で加熱加水分解後、ろ過、洗浄して、その後スラリー化してｐＨ４〜７で中和洗浄することを特徴とする。 The manufacturing method of the titanium oxide photocatalyst feedstock metatitanic acid slurry according to the present invention, TiO 2 concentration 250~270g / L, Ti 3+ concentration titanyl sulphate solution 3.0~10.0g / L in terms of TiO 2 in, added separately 3-10 wt% the prepared anatase seeds in terms of TiO 2 with respect to TiO 2 in the titanyl sulfate solution, after thermal hydrolysis at above the boiling point, filtered, washed, and then slurried pH4~ 7 is neutralized and washed.
本発明の光触媒酸化チタン原料用メタチタン酸スラリーによれば、各種光触媒能に優れた光触媒用酸化チタンを提供することが可能となる。 According to the metatitanic acid slurry for a photocatalytic titanium oxide raw material of the present invention, it is possible to provide titanium oxide for a photocatalyst excellent in various photocatalytic activities.
（メタチタン酸スラリーの沈降速度）
本発明で重要なのは、メタチタン酸スラリーについて、ＴｉＯ２として４０ｇ／Ｌ、及び温度を３０℃に調整したときの沈降速度を１５〜３０ｍｍ／３０分の範囲にするということである。
(Settling speed of metatitanic acid slurry)
What is important in the present invention is that the metatitanic acid slurry has a settling rate of 15 to 30 mm / 30 minutes when TiO 2 is adjusted to 40 g / L and the temperature is adjusted to 30 ° C.
ここでいう沈降速度は、本発明のメタチタン酸スラリーを製造する際に、加水分解終了時のスラリーをＴｉＯ２として４０ｇ／Ｌに調整したスラリーを、グラフ用紙を貼り付けた１Ｌのメスシリンダーに１Ｌ採取し、採取直後から３０分後に測定される液面から沈降界面までの長さ(ｍｍ)として定義することができる。 Sedimentation rate referred to here, in making the metatitanic acid slurry of the present invention, 1L slurry at completion of the hydrolysis slurry was adjusted to 40 g / L as TiO 2, the graduated cylinder 1L pasted the graph paper It can be defined as the length (mm) from the liquid level to the sedimentation interface measured 30 minutes after collection.
沈降速度を１５〜３０ｍｍ／３０分とすることにより、メタチタン酸スラリーの乾燥後の比表面積が２８０を超え、かつ３６０ｍ２／ｇ以下と大きくなり、これから得られた酸化チタンの光触媒能が優れたものになる。ここで、沈降速度が１５ｍｍ／３０分未満の場合は、後の洗浄工程でろ過性が悪く、鉄等の不純物含有量の増加原因となって好ましくない。一方、３０ｍｍ／３０分を超える場合は、生成粒子が大きく所望の光触媒特性が得られなくなり、好ましくない。 By setting the sedimentation rate to 15 to 30 mm / 30 minutes, the specific surface area after drying of the metatitanic acid slurry exceeds 280 and is increased to 360 m 2 / g or less, and the photocatalytic ability of the titanium oxide obtained from this is excellent. Become a thing. Here, when the sedimentation rate is less than 15 mm / 30 minutes, filterability is poor in the subsequent washing step, which is not preferable because it causes an increase in the content of impurities such as iron. On the other hand, if it exceeds 30 mm / 30 minutes, the generated particles are large and the desired photocatalytic properties cannot be obtained, which is not preferable.
また、沈降速度を１５〜３０ｍｍ／３０分の範囲にすることにより、このメタチタン酸スラリーを硝酸や塩酸等の鉱酸で解膠処理を施してｐＨ１．０でＴｉＯ２濃度が２５０ｇ／Ｌの光触媒用ゾルとした場合に、７００ｎｍでの光透過率が６０％以上となる。これは凝集粒子がなく、粒子が微細であることに加えて粒度分布がシャープであることを示しており、当該ゾルを光触媒塗料にして各種基体に塗布したときに、例えばメルカプタンの様な比較的大きな有害分子を補足して分解しやすいという効果を奏する。 In addition, by setting the sedimentation rate in the range of 15 to 30 mm / 30 minutes, the metatitanic acid slurry is peptized with a mineral acid such as nitric acid or hydrochloric acid to obtain a photocatalyst having a pH of 1.0 and a TiO 2 concentration of 250 g / L. When the sol is used, the light transmittance at 700 nm is 60% or more. This indicates that there is no agglomerated particles and that the particle size is fine in addition to the fine particles, and when the sol is applied to various substrates as a photocatalyst paint, it is relatively free from, for example, mercaptans. It has the effect of being easily decomposed by capturing large harmful molecules.
（メタチタン酸スラリーのＦｅ２Ｏ３含有量、ＳＯ３含有量）
本発明の光触媒酸化チタン原料用メタチタン酸スラリーは、スラリー中のＦｅ２Ｏ３含有量がＴｉＯ２に対して５０質量ｐｐｍ以下であることが好ましい。Ｆｅ２Ｏ３含有量を前記の範囲で制御することで、光触媒用酸化チタンとしたときの光触媒能が優れたものとなる。
(Fe 2 O 3 content of metatitanic acid slurry, SO 3 content)
In the metatitanic acid slurry for a photocatalytic titanium oxide raw material of the present invention, the content of Fe 2 O 3 in the slurry is preferably 50 mass ppm or less with respect to TiO 2 . By controlling the content of Fe 2 O 3 within the above range, the photocatalytic ability when used as a photocatalyst titanium oxide is excellent.
また、本発明の光触媒酸化チタン原料用メタチタン酸スラリーは、乾燥後のＳＯ３含有量が０．５〜３．０質量％であることが好ましい。この範囲のＳＯ３含有量であれば、例えば光触媒用塗料組成物にする場合に分散性が向上するため、当該塗料組成物を各種基体に塗布した光触媒体は均一で優れた光触媒能を有する。ここでいう乾燥とは、顔料の水分含有量が１５％以下のものをいう。 Further, the titanium oxide photocatalyst feedstock metatitanic acid slurry of the present invention preferably SO 3 content after drying is 0.5 to 3.0 mass%. When the SO 3 content is in this range, for example, when a coating composition for a photocatalyst is used, the dispersibility is improved. Therefore, the photocatalyst coated with the coating composition on various substrates has a uniform and excellent photocatalytic ability. Drying here means that the water content of the pigment is 15% or less.
（光触媒酸化チタン原料用メタチタン酸スラリーの製造方法）
本発明の光触媒酸化チタン原料用メタチタン酸スラリーは、代表的には、ＴｉＯ２濃度が２５０〜２７０ｇ／Ｌ、Ｔｉ３＋濃度がＴｉＯ２換算で３．０〜１０．０ｇ／Ｌの硫酸チタニル溶液に、別途作成したアナターゼシードをＴｉＯ２換算で硫酸チタニル溶液中のＴｉＯ２に対して３〜１０質量％添加し、沸点以上で加熱加水分解後、ろ過、洗浄して、その後スラリー化してｐＨ４〜７で中和洗浄することによって製造することができる。
(Method for producing metatitanic acid slurry for photocatalytic titanium oxide raw material)
The metatitanic acid slurry for a photocatalytic titanium oxide raw material of the present invention is typically a titanyl sulfate solution having a TiO 2 concentration of 250 to 270 g / L and a Ti 3+ concentration of 3.0 to 10.0 g / L in terms of TiO 2. were added separately from 3 to 10 wt% with respect to TiO 2 in the titanyl sulfate solution anatase seeds created in terms of TiO 2, after thermal hydrolysis at above the boiling point, filtered, washed, and then slurried pH4~7 Can be produced by neutralization washing.
硫酸チタニル溶液は、イルメナイト鉱石やチタンスラグを硫酸と反応させ、Ｔｉ、Ｆｅなどを水可溶性の硫酸塩に変えるという公知の方法によって製造される。 The titanyl sulfate solution is produced by a known method of reacting ilmenite ore or titanium slag with sulfuric acid to convert Ti, Fe, etc. into water-soluble sulfate.
硫酸チタニル中のＴｉＯ２濃度は、２５０〜２７０ｇ／Ｌ、好ましくは２５５〜２６５ｇ／Ｌである。２５０ｇ／Ｌ未満であると、分解生成物の粒度分布が悪くなるため好ましくない。また、２７０ｇ／Ｌを超えると、生成粒子が大きくなるため好ましくない。Ｔｉ３＋はＴｉＯ２換算で３．０〜１０．０ｇ／Ｌ、好ましくは３．０〜５．０ｇ／Ｌである。Ｔｉ３＋がＴｉＯ２換算で３．０ｇ／Ｌ未満であると、後の洗浄工程に鉄等の不純分が減少し難いため好ましくなく、また、１０．０ｇ／Ｌを超えると、加水分解収率が低下するので好ましくない。 The TiO 2 concentration in titanyl sulfate is 250 to 270 g / L, preferably 255 to 265 g / L. If it is less than 250 g / L, the particle size distribution of the decomposition product becomes worse, which is not preferable. On the other hand, if it exceeds 270 g / L, the generated particles are not preferable. Ti 3+ is 3.0 to 10.0 g / L, preferably 3.0 to 5.0 g / L in terms of TiO 2 . When Ti 3+ is less than 3.0 g / L in terms of TiO 2 , it is not preferred because impurities such as iron are less likely to decrease in the subsequent washing step, and when it exceeds 10.0 g / L, the hydrolysis yield Is unfavorable because it decreases.
次いで、製造された硫酸チタニル溶液に加水分解用核であるアナターゼシードを添加して加熱沸騰させて加水分解を行い、メタチタン酸スラリーを得る。 Next, anatase seeds, which are hydrolysis nuclei, are added to the manufactured titanyl sulfate solution and heated and boiled for hydrolysis to obtain a metatitanic acid slurry.
本発明で重要なのは、加水分解用核であるアナターゼシードの添加量を、ＴｉＯ２換算で硫酸チタニル溶液中のＴｉＯ２に対し、通常の０．１〜１質量％よりも増量して３〜１０質量％、好ましくは４〜６質量％とすることである。これにより、ＴｉＯ２として４０ｇ／Ｌ、温度を３０℃に調整したときの沈降速度が１５〜３０ｍｍ／３０分となるメタチタン酸スラリーが得られ、乾燥後の比表面積が２８０を超え、かつ３６０ｍ２／ｇ以下である微粒子になるため、これを原料とした酸化チタンは種々の光触媒能が向上したものとなる。 Importantly in this invention, the amount of anatase seeds is hydrolysis nuclear, to TiO 2 of titanyl sulfate solution in terms of TiO 2, and increased than the normal 0.1 to 1 wt% 3-10 It is made into mass%, Preferably it is 4-6 mass%. Thereby, a metatitanic acid slurry having a sedimentation rate of 15 to 30 mm / 30 minutes when the temperature is adjusted to 30 ° C. as TiO 2 is obtained, the specific surface area after drying exceeds 280, and 360 m 2. Therefore, titanium oxide using this as a raw material has improved various photocatalytic performances.
本発明でいうアナターゼシードとは、代表的には、Ｔｉ３＋を１質量％含むＴｉＯ２１４０〜１６０ｇ／Ｌ、Ｆｅ ２０〜４０ｇ／Ｌ、Ｈ２ＳＯ４ ２７０〜２９０ｇ／Ｌの硫酸チタニル溶液を２０℃以下に冷却してから、苛性ソーダ水溶液で中和して、Ｈ２ＳＯ４濃度(ｇ／Ｌ)／ＴｉＯ２濃度(ｇ／Ｌ)を０．５０〜０．５６とし、数時間かきまぜて清澄な液とした後、７０〜９０℃で１５〜６０分加温して得られたコロイド状溶液のことをいう。 The anatase seed referred to in the present invention is typically a titanyl sulfate solution of TiO 2 140 to 160 g / L, Fe 20 to 40 g / L, and H 2 SO 4 270 to 290 g / L containing 1% by mass of Ti 3+. After cooling to 20 ° C. or lower, neutralize with an aqueous caustic soda solution and adjust the H 2 SO 4 concentration (g / L) / TiO 2 concentration (g / L) to 0.50 to 0.56 and stir for several hours. This refers to a colloidal solution obtained by heating at 70 to 90 ° C. for 15 to 60 minutes after preparing a clear solution.
アナターゼシードが３質量％未満だと、メタチタン酸の比表面積が１５０〜２５０ｍ２／ｇとなって微粒化しないため好ましくない。また、１０質量％を超えてもこれ以上の微細化はできず、コスト的に好ましくない。 If the anatase seed is less than 3% by mass, the specific surface area of metatitanic acid is 150 to 250 m 2 / g, which is not preferable. Moreover, even if it exceeds 10 mass%, further refinement | miniaturization cannot be performed and it is not preferable in terms of cost.
加水分解して得られたメタチタン酸スラリーはＦｅ、Ｍｎ、Ｃｒ等の不純物元素を除去する目的で公知の方法でろ過、洗浄、及び中和洗浄を行うことが好ましい。一段洗浄後のメタチタン酸スラリーにＴｉＯ２に対して３〜７質量％の濃硫酸を添加して２段目の洗浄を行うことでＦｅ２Ｏ３含有量は２０ｐｐｍ迄低減できる。 The metatitanic acid slurry obtained by hydrolysis is preferably subjected to filtration, washing, and neutralization washing by a known method for the purpose of removing impurity elements such as Fe, Mn, and Cr. Fe 2 O 3 content can be reduced to 20 ppm by adding 3-7 mass% concentrated sulfuric acid with respect to TiO 2 to the metatitanic acid slurry after the first stage cleaning and performing the second stage cleaning.
中和時のｐＨを４．０〜７．０で行うことで、結果的に乾燥後のＳＯ３含有量を０．５〜３．０質量％にすることができる。このときの中和剤としては、アンモニア水、アンモニアガス、苛性ソーダ、苛性カリ、炭酸ソーダ、消石灰等があげられ、中でもアルカリ金属やアルカリ土類金属が残存しないという理由でアンモニア水が好ましい。 By performing the pH during neutralization at 4.0 to 7.0, the SO 3 content after eventually drying can be 0.5 to 3.0 mass%. Examples of the neutralizing agent at this time include ammonia water, ammonia gas, caustic soda, caustic potash, sodium carbonate, slaked lime, etc. Among them, ammonia water is preferable because no alkali metal or alkaline earth metal remains.
最終的に得られたメタチタン酸スラリーは、各種工程を経て光触媒用酸化チタン粉末、光触媒用酸化チタンゾル、あるいは光触媒用酸化チタン塗料組成物とすることができる。 The metatitanic acid slurry finally obtained can be made into a titanium oxide powder for photocatalyst, a titanium oxide sol for photocatalyst, or a titanium oxide coating composition for photocatalyst through various steps.
光触媒用酸化チタン粉末とする場合は、前記メタチタン酸スラリーをアルカリで硫酸根を除去し、鉱酸にてｐＨを６〜７の中性付近に調整し、ろ過、洗浄後、乾燥することで得られる。 In the case of titanium oxide powder for photocatalyst, it is obtained by removing the sulfate radical with alkali in the metatitanic acid slurry, adjusting the pH to 6 to 7 neutral with mineral acid, filtering, washing and drying. It is done.
光触媒用酸化チタンゾルとする場合は、前記の光触媒用酸化チタン粉末とする場合のろ過、洗浄後、リパルプして硝酸や塩酸で解膠処理を行うことで得られる。 When the titanium oxide sol for photocatalyst is used, it can be obtained by repulping and peptizing with nitric acid or hydrochloric acid after filtration and washing in the case of using the titanium oxide powder for photocatalyst.
光触媒用酸化チタン塗料組成物とする場合は、前記の光触媒用酸化チタンゾルとする場合の解膠処理後、アルカリで硫酸根を除去し、鉱酸にてｐＨを６〜７の中性付近に調整し、ろ過、洗浄、スラリー化後、塗料成分となるコロイダルシリカ等を任意の割合で混合し、機械分散することで得られる。 When the titanium oxide coating composition for photocatalyst is used, after the peptization treatment in the case of using the above-mentioned titanium oxide sol for photocatalyst, the sulfate radical is removed with alkali, and the pH is adjusted to near neutrality with mineral acid. Then, after filtration, washing, and slurrying, it can be obtained by mixing colloidal silica or the like as a coating component at an arbitrary ratio and mechanically dispersing it.
以下、実施例によって本発明を具体的に説明するが、以下の実施例は単に例示のために示すものであり、発明の範囲がこれらによって制限されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the following examples are merely shown for illustration, and the scope of the invention is not limited by these examples.
(メタチタン酸の製造)
［実施例１］
イルメナイト鉱石を硫酸に溶解して得られた硫酸チタニル溶液を、ＴｉＯ２として２６０ｇ／Ｌ、Ｔｉ３＋をＴｉＯ２換算で４．５ｇ／Ｌに調整し、アナターゼシードをＴｉＯ２に対して５．００質量％添加した後、蒸気を吹き込んで沸点で加熱加水分解を４時間行って、メタチタン酸スラリーを得、ろ過、洗浄して、その後スラリー化して、ＴｉＯ２に対して５質量％の濃硫酸を添加してアンモニア水にてｐＨ６で２時間保持して中和し、洗浄した。
(Production of metatitanic acid)
[Example 1]
A titanyl sulfate solution obtained by dissolving ilmenite ore in sulfuric acid was adjusted to 260 g / L as TiO 2 and Ti 3+ to 4.5 g / L in terms of TiO 2 , and the anatase seed was adjusted to 5.00 with respect to TiO 2 . after adding mass%, it performed 4 hours thermal hydrolysis at the boiling point by blowing steam, to obtain a metatitanic acid slurry, filtered, washed, and then slurried, concentrated sulfuric acid 5% by weight with respect to TiO 2 The mixture was added and neutralized by maintaining it at pH 6 for 2 hours with aqueous ammonia, followed by washing.
［実施例２］
実施例１において、アナターゼシードを３．００質量％に変更した以外は、実施例１と同様にしてメタチタン酸スラリーを得た。
[Example 2]
A metatitanic acid slurry was obtained in the same manner as in Example 1 except that the anatase seed was changed to 3.00% by mass in Example 1.
［実施例３］
実施例１において、アナターゼシードを７．００質量％に変更した以外は、実施例１と同様にしてメタチタン酸スラリーを得た。
[Example 3]
A metatitanic acid slurry was obtained in the same manner as in Example 1 except that the anatase seed was changed to 7.00% by mass in Example 1.
［実施例４］
実施例１において、加熱加水分解後のろ過から中和洗浄までの工程を３回繰り返した他は、実施例１と同様にしてメタチタン酸スラリーを得た。
[Example 4]
In Example 1, the metatitanic acid slurry was obtained like Example 1 except having repeated the process from filtration after heat hydrolysis to neutralization washing | cleaning 3 times.
［実施例５］
チタンスラグを硫酸に溶解して得られた硫酸チタニル溶液を、ＴｉＯ２として２７０ｇ／Ｌ、Ｔｉ３＋をＴｉＯ２換算で７．０ｇ／Ｌに調整し、アナターゼシードをＴｉＯ２に対して５．００質量％添加した後、蒸気を吹き込んで沸点で加熱加水分解を４時間行って、メタチタン酸スラリーを得、ろ過、洗浄して、その後スラリー化して、ＴｉＯ２に対して５質量％の濃硫酸を添加してアンモニア水にてｐＨ６で２時間保持して中和し、洗浄した。
[Example 5]
Titanyl sulfate solution obtained by dissolving titanium slag in sulfuric acid, 270 g / L as TiO 2, was adjusted to 7.0 g / L of Ti 3+ in terms of TiO 2, the anatase seeds against TiO 2 5.00 after adding mass%, it performed 4 hours thermal hydrolysis at the boiling point by blowing steam, to obtain a metatitanic acid slurry, filtered, washed, and then slurried, concentrated sulfuric acid 5% by weight with respect to TiO 2 The mixture was added and neutralized by maintaining it at pH 6 for 2 hours with aqueous ammonia, followed by washing.
［比較例１］
実施例１において、アナターゼシードを２．９０質量％に変更した以外は、実施例１と同様にしてメタチタン酸スラリーを得た。
[Comparative Example 1]
A metatitanic acid slurry was obtained in the same manner as in Example 1 except that the anatase seed in Example 1 was changed to 2.90% by mass.
［比較例２］
実施例１において、アナターゼシードを０．５０質量％に変更した以外は、実施例１と同様にしてメタチタン酸スラリーを得た。
[Comparative Example 2]
In Example 1, a metatitanic acid slurry was obtained in the same manner as in Example 1 except that the anatase seed was changed to 0.50% by mass.
［比較例３］
実施例１において、アナターゼシードを０．３５質量％に変更し、かつ、中和洗浄を行わなかった以外は、実施例１と同様にしてメタチタン酸スラリーを得た。
[Comparative Example 3]
In Example 1, a metatitanic acid slurry was obtained in the same manner as in Example 1 except that the anatase seed was changed to 0.35% by mass and neutralization washing was not performed.
実施例及び比較例で得られたメタチタン酸スラリーについて、以下の諸特性について測定した。 About the metatitanic acid slurry obtained by the Example and the comparative example, it measured about the following various characteristics.
(沈降速度)
加水分解終了時のメタチタン酸スラリーについて、ＴｉＯ２として４０ｇ／Ｌに調整したスラリーを、グラフ用紙を貼り付けた１Ｌのメスシリンダーに１Ｌ採取し、採取直後から３０分後の液面から沈降界面までの長さ(ｍｍ)を測定した。
(Settling velocity)
About the metatitanic acid slurry at the end of hydrolysis, 1 L of slurry adjusted to 40 g / L as TiO 2 is sampled in a 1 L graduated cylinder with graph paper attached, from the liquid level 30 minutes after collection to the sedimentation interface. The length (mm) of was measured.
(比表面積)
メタチタン酸スラリーをろ過し、１１０℃で２時間乾燥した後、マイクロメリティックス社製ジェミニ２３７５により測定した。
(Specific surface area)
The metatitanic acid slurry was filtered, dried at 110 ° C. for 2 hours, and then measured with Gemini 2375 manufactured by Micromeritics.
(Ｆｅ２Ｏ３含有量)
メタチタン酸スラリーを硫酸で溶解して前処理した後、日本ジャーレルアッシュ製 ＩＣＡＰ−５７５にて測定した。
(Fe 2 O 3 content)
The metatitanic acid slurry was dissolved in sulfuric acid and pretreated, and then measured with ICAP-575 manufactured by Nippon Jarrell Ash.
(ＳＯ３含有量)
メタチタン酸スラリーをろ過し、１１０℃で２時間乾燥した後、ＬＥＣＯ社製炭素・硫黄同時分析装置ＣＳ−２３０により測定した。実施例及び比較例で得られたメタチタン酸スラリーの諸特性を表１に示す。
(SO 3 content)
The metatitanic acid slurry was filtered, dried at 110 ° C. for 2 hours, and then measured with a carbon / sulfur simultaneous analyzer CS-230 manufactured by LECO. Table 1 shows various properties of the metatitanic acid slurry obtained in Examples and Comparative Examples.
(光触媒用酸化チタン粉末の製造)
実施例及び比較例で得られたメタチタン酸スラリーを、４００ｇ／Ｌの苛性ソーダでｐＨ９に調整後、４０℃で６時間撹拌保持して硫酸根を除去し、続けて６１％硝酸溶液でｐＨ６．５に調整し４０℃で１５分撹拌保持して、ろ過し純水で電気伝導度が１００μＳ／ｃｍとなるまで洗浄を行った。続けて、１１０℃で１時間乾燥し、さらに５００℃で１時間焼成して光触媒用酸化チタン粉末を得た。
(Production of titanium oxide powder for photocatalyst)
The metatitanic acid slurries obtained in Examples and Comparative Examples were adjusted to pH 9 with 400 g / L of caustic soda and then stirred and held at 40 ° C. for 6 hours to remove sulfate radicals, and subsequently pH 6.5 with 61% nitric acid solution. The mixture was stirred at 40 ° C. for 15 minutes, filtered, and washed with pure water until the electric conductivity reached 100 μS / cm. Subsequently, it was dried at 110 ° C. for 1 hour and further calcined at 500 ° C. for 1 hour to obtain a titanium oxide powder for photocatalyst.
(光触媒用酸化チタン粉末の評価１)
前記の光触媒用酸化チタン粉末を超音波分散機により水スラリー化し、Ａｌ基板上に塗布して粉体膜を形成した。これを内容積１２５ｍｌのガラス製バイアル瓶に入れ、ゴム栓をして、アセトアルデヒドガスを瓶内の濃度が１０００ｐｐｍになる量注入した。瓶の外からブラックライト紫外線を１．０ｍＷ／ｃｍ２で照射して、紫外線照射によるアセトアルデヒドガス濃度の１５、３０、４５、及び６０分後の変化を、ヤナコ製ガスクロマトグラフＧ−３８００（ＦＩＤ検出器）にて測定した。結果を表１に示す。
(Evaluation of titanium oxide powder for photocatalyst 1)
The titanium oxide powder for photocatalyst was water-slurried with an ultrasonic disperser and applied onto an Al substrate to form a powder film. This was put into a glass vial with an internal volume of 125 ml, sealed with a rubber stopper, and acetaldehyde gas was injected in such an amount that the concentration in the bottle became 1000 ppm. Irradiation of black light ultraviolet rays at 1.0 mW / cm 2 from the outside of the bottle, and changes in acetaldehyde gas concentration after 15, 30, 45, and 60 minutes due to ultraviolet irradiation were analyzed by Yanaco gas chromatograph G-3800 (FID detection). ). The results are shown in Table 1.
(光触媒用酸化チタン粉末の評価２)
前記の光触媒用酸化チタン粉末を超音波分散機により水スラリー化し、Ａｌ基板上に塗布して粉体膜を形成した。Ａｌ基板上に形成した粉体膜に、オクチルアルコ−ルをスプレ−で０．２ｍｇ／ｃｍ２なる量塗布した。塗布面積は１６０ｃｍ２で全塗布オクチルアルコ−ル量は３２ｍｇである。この油を塗布した粉体膜に雰囲気温度２０℃、相対湿度５０％でブラックライト紫外線を６．０ｍＷ／ｃｍ２で照射した。紫外線照射３０、６０、１２０、及び２４０分後の重量減少分をオクチルアルコ−ル分解量に相当するとしてオクチルアルコ−ル分解率を求めた。結果を表１に示す。
(Evaluation of photocatalytic titanium oxide powder 2)
The titanium oxide powder for photocatalyst was water-slurried with an ultrasonic disperser and applied onto an Al substrate to form a powder film. Octyl alcohol was applied to the powder film formed on the Al substrate in an amount of 0.2 mg / cm 2 with a spray. The coated area is 160 cm 2 and the total coated octyl alcohol amount is 32 mg. The oil-coated powder film was irradiated with black light ultraviolet rays at 6.0 mW / cm 2 at an atmospheric temperature of 20 ° C. and a relative humidity of 50%. The weight loss after 30, 60, 120 and 240 minutes of ultraviolet irradiation corresponded to the amount of octyl alcohol decomposition, and the octyl alcohol decomposition rate was determined. The results are shown in Table 1.
(光触媒用酸化チタンゾルの評価１)
実施例及び比較例で得られたメタチタン酸スラリーを、４００ｇ／Ｌの苛性ソーダでｐＨ９に調整後、４０℃で６時間撹拌保持して硫酸根を除去し、続けて６１％硝酸溶液でｐＨ６．５に調整し４０℃で１５分撹拌保持してろ過し、純水で電気伝導度が１００μＳ／ｃｍとなるまで洗浄を行った。続けて、純水でスラリー化してＴｉＯ２濃度を２５０ｇ／Ｌに調整した後、６１％硝酸溶液でｐＨ１．０に調整して解膠処理し、光触媒用酸化チタンゾルを得た。このゾルを１ｍｍの石英セルに入れ、日本分光製分光光度計Ｕｂｅｓｔ−５０にて７００ｎｍの光透過率を測定した。結果を表１に示す。
(Evaluation of photocatalytic titanium oxide sol 1)
The metatitanic acid slurries obtained in Examples and Comparative Examples were adjusted to pH 9 with 400 g / L of caustic soda and then stirred and held at 40 ° C. for 6 hours to remove sulfate radicals, and subsequently pH 6.5 with 61% nitric acid solution. The mixture was stirred at 40 ° C. for 15 minutes, filtered, and washed with pure water until the electric conductivity reached 100 μS / cm. Subsequently, the slurry was made into a slurry with pure water to adjust the TiO 2 concentration to 250 g / L, and then adjusted to pH 1.0 with a 61% nitric acid solution and peptized to obtain a titanium oxide sol for photocatalyst. This sol was placed in a 1 mm quartz cell, and the light transmittance at 700 nm was measured with a spectrophotometer Ubest-50 manufactured by JASCO Corporation. The results are shown in Table 1.
表１の結果より、実施例１〜５により得られたメタチタン酸スラリーは、酸化チタン粉末とした場合に、比較例１〜３により得られたものと比較してアルデヒド分解率、オクチルアルコール分解率に優れ、かつ酸化チタンゾルとした場合にも光透過率に優れていることが分かった。 From the results in Table 1, when the metatitanic acid slurry obtained in Examples 1 to 5 is a titanium oxide powder, the aldehyde decomposition rate and the octyl alcohol decomposition rate are compared with those obtained in Comparative Examples 1 to 3. In addition, it was found that even when a titanium oxide sol was used, the light transmittance was excellent.
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| JP2010022785A (en) * | 2008-07-22 | 2010-02-04 | Shinwa Corp | Deodorizing filter |
| WO2014196462A1 (en) * | 2013-06-04 | 2014-12-11 | 石原産業株式会社 | Lithium titanate, production method for same, and electrical storage device employing same |
| JP2019531185A (en) * | 2016-10-04 | 2019-10-31 | アールエイチ−イメージング システムズ インコーポレイテッド | Iron-doped titanium dioxide nanocrystals and their use as photocatalysts |
| CN114014355A (en) * | 2021-09-16 | 2022-02-08 | 攀枝花学院 | Method for purifying and deironing industrial metatitanic acid |
| CN114162857A (en) * | 2021-12-10 | 2022-03-11 | 长沙华希新材料有限公司 | Titanium dioxide for hard alloy and preparation method thereof |
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| JP2010022785A (en) * | 2008-07-22 | 2010-02-04 | Shinwa Corp | Deodorizing filter |
| WO2014196462A1 (en) * | 2013-06-04 | 2014-12-11 | 石原産業株式会社 | Lithium titanate, production method for same, and electrical storage device employing same |
| JPWO2014196462A1 (en) * | 2013-06-04 | 2017-02-23 | 石原産業株式会社 | Lithium titanate, method for producing the same, and power storage device using the same |
| US9966599B2 (en) | 2013-06-04 | 2018-05-08 | Ishihara Sangyo Kaisha, Ltd. | Process for manufacturing lithium titanium oxides |
| JP2019531185A (en) * | 2016-10-04 | 2019-10-31 | アールエイチ−イメージング システムズ インコーポレイテッド | Iron-doped titanium dioxide nanocrystals and their use as photocatalysts |
| CN114014355A (en) * | 2021-09-16 | 2022-02-08 | 攀枝花学院 | Method for purifying and deironing industrial metatitanic acid |
| CN114014355B (en) * | 2021-09-16 | 2023-07-25 | 攀枝花学院 | Industrial meta-titanic acid purifying and deironing method |
| CN114162857A (en) * | 2021-12-10 | 2022-03-11 | 长沙华希新材料有限公司 | Titanium dioxide for hard alloy and preparation method thereof |
| CN114162853A (en) * | 2021-12-10 | 2022-03-11 | 长沙华希新材料有限公司 | Hydrolysis process for preparing metallurgical titanium dioxide for hard alloy |
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