JPH0369842B2 - - Google Patents
Info
- Publication number
- JPH0369842B2 JPH0369842B2 JP9358386A JP9358386A JPH0369842B2 JP H0369842 B2 JPH0369842 B2 JP H0369842B2 JP 9358386 A JP9358386 A JP 9358386A JP 9358386 A JP9358386 A JP 9358386A JP H0369842 B2 JPH0369842 B2 JP H0369842B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- hydrogen peroxide
- solution
- aqueous
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- DJGLQWCKPYQFJG-UHFFFAOYSA-N hydrogen peroxide;titanium Chemical compound [Ti].OO DJGLQWCKPYQFJG-UHFFFAOYSA-N 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- -1 alkoxy titanium Chemical compound 0.000 description 7
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- NDSXSCFKIAPKJG-UHFFFAOYSA-N CC(C)O[Ti] Chemical class CC(C)O[Ti] NDSXSCFKIAPKJG-UHFFFAOYSA-N 0.000 description 1
- RCZPHVPIOWNERS-UHFFFAOYSA-N CCCO[Ti] Chemical compound CCCO[Ti] RCZPHVPIOWNERS-UHFFFAOYSA-N 0.000 description 1
- ZBZXIGONWYKEMZ-UHFFFAOYSA-N CCO[Ti] Chemical compound CCO[Ti] ZBZXIGONWYKEMZ-UHFFFAOYSA-N 0.000 description 1
- FLTYUJMFMHOICO-UHFFFAOYSA-N CO[Ti] Chemical compound CO[Ti] FLTYUJMFMHOICO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明は高純度酸化チタンの粉末、膜、繊維構
造体を作るのに有用な高純度過酸化水素化チタン
水溶液の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a high-purity titanium hydrogen peroxide aqueous solution useful for producing high-purity titanium oxide powder, membranes, and fibrous structures.
従来技術
従来の水酸化チタン又は酸化チタンの製造法と
しては、塩化チタン、硫酸チタン或いはアルコキ
シチタン等のチタン塩を原料に用い、加水分解す
る方法、又は酸化するる方法、もしくは両者の併
用が知られている。これらの方法によると水酸化
チタン或いは酸化チタンの生成の場に於いて、不
純分の原因となる成分即ち硫酸塩、塩化物、塩
素、或いはアルコールのいずれかが存在してい
る。そのため、これらの物質は生成物に取り込ま
れて、水酸化チタン又は酸化チタンを不純にして
いた。Prior Art Conventional methods for producing titanium hydroxide or titanium oxide include a method of hydrolyzing or oxidizing titanium salts such as titanium chloride, titanium sulfate, or alkoxy titanium as a raw material, or a combination of both. It is being According to these methods, components that cause impurities, such as sulfate, chloride, chlorine, or alcohol, are present in the production of titanium hydroxide or titanium oxide. Therefore, these substances were incorporated into the product and made the titanium hydroxide or titanium oxide impure.
また過酸化水素化チタン水溶液としては塩化チ
タン水溶液、或いは硫酸チタン水溶液、に過酸化
水素水溶液を加えたものが知られているが、これ
らを分解しても前記と同じ理由で不純生成物が得
られる。 Furthermore, titanium hydrogen peroxide aqueous solutions include titanium chloride aqueous solutions or titanium sulfate aqueous solutions to which hydrogen peroxide aqueous solutions are added, but even if these are decomposed, impure products are obtained for the same reason as mentioned above. It will be done.
発明の目的
本発明は従来法における欠点を改善するために
行つたものである。第一の目的は生成物中の不純
物の原因となる成分を含まない原料としての高純
度の過酸化水素化チタン水溶液の製造法を提供し
て、水酸化チタンおよび酸化チタンを、極めて高
純度に、しかも容易に得ようとすることである。
第二の目的は高純度の過酸化水素化チタン水溶液
の製造法を提供して、原料液体から固体形成を徐
徐に行わせて、固体を繊維状或いは膜状にしかも
高純度に酸化チタンをより容易に得ようとするこ
とである。OBJECT OF THE INVENTION The present invention has been made to improve the drawbacks of conventional methods. The first purpose is to provide a method for producing a high-purity titanium peroxide aqueous solution as a raw material that does not contain components that cause impurities in the product, and to produce titanium hydroxide and titanium oxide with extremely high purity. , and it is something that can be easily obtained.
The second purpose is to provide a method for producing a high-purity titanium hydrogen peroxide aqueous solution, by gradually forming a solid from a raw material liquid, making the solid into a fibrous or film-like form, and producing highly pure titanium oxide. It's about trying to get it easily.
発明の構成
本発明者は、前記目的を達成するために研究し
た結果、アルコキシチタンを過酸化水素水溶液に
溶解し、該溶液を減圧蒸留すると高純度の水酸化
チタン並びに酸化チタンの製造原料として好適な
高純度の過酸化水素化チタン水溶液が得られるこ
とを究明できた。高純度の過酸化水素化チタン水
溶液から繊維状或いは膜状にしかも高純度に酸化
チタンを容易に得られることを究明できた。Structure of the Invention As a result of research to achieve the above object, the present inventor discovered that alkoxy titanium is dissolved in an aqueous hydrogen peroxide solution and the solution is distilled under reduced pressure, which is suitable as a raw material for producing high-purity titanium hydroxide and titanium oxide. It was found that a highly pure titanium hydrogen peroxide aqueous solution could be obtained. It has been found that highly pure titanium oxide can be easily obtained in the form of fibers or films from an aqueous solution of titanium hydrogen peroxide.
これらの知見に基いて本発明を完成した。 The present invention was completed based on these findings.
本発明の要旨
アルコキシチタンを過酸化水素化水溶液に溶解
して得た水溶液を減圧蒸留して、有機分を除去す
ることを特徴とする高純度過酸化水素化チタン水
溶液の製造法にある。Summary of the Invention A method for producing a high purity titanium hydrogen peroxide aqueous solution is provided, which comprises dissolving alkoxy titanium in an aqueous hydrogen peroxide solution and distilling the aqueous solution obtained under reduced pressure to remove organic components.
本発明で使用するアルコキシチタンは過酸化水
素によつて置換されて生成するアルコールが揮発
性に富むことが好ましく、例えばメトキシチタ
ン、エトキシチタン、プロポキシチタンがある、
しかし場合によりそれらより炭素数の大なるアル
コキシチタンでもさしつかえない。本発明で使用
する過酸化水素水溶液は市販品でもよいが、これ
には多種の純度品があり、最も好ましくは安定剤
の入つていない最高純度品であるが、これに限る
ものではない。アルコキシチタンを過酸化水素水
溶液と混合して溶解するさいに、過酸化水素水溶
液中の水分による、アルコキシチタンの加水分解
を避けるためには過酸化水素の濃度は高いものほ
ど望ましく、0.1％以上，20％乃至30％程度が好
ましく、更に高濃度になると溶解度が低下する。
また、高温になると過酸化水素および過酸化水素
化アルコキシチタンの分解が激しく起こり不都合
であり、溶解反応熱による温度上昇を抑えるため
に、50℃以下、好ましくは氷水で冷却しながら過
酸化水素水溶液を混合して、溶解することが必要
である。この方法で得られた過酸化水素化アルコ
キシチタン水溶液を10-2ないし10-3torrにたとえ
ば油回転ポンプで減圧すると、過酸化水素によつ
て置換されて、遊離したアルコールおよび若干量
のアルコールの酸化生成物のケトン或いはアルデ
ヒド等、が水および遊離の過酸化水素と共に、蒸
留除去されて、高純度過酸化水素化チタン水溶液
が製造される。 The alkoxy titanium used in the present invention is preferably substituted with hydrogen peroxide so that the alcohol produced is highly volatile, such as methoxy titanium, ethoxy titanium, and propoxy titanium.
However, in some cases, alkoxy titanium having a larger number of carbon atoms may be used. The aqueous hydrogen peroxide solution used in the present invention may be a commercially available product, but there are various purity products, and the most preferred is the highest purity product that does not contain a stabilizer, but it is not limited thereto. When alkoxytitanium is mixed and dissolved with an aqueous hydrogen peroxide solution, in order to avoid hydrolysis of the alkoxytitanium due to water in the aqueous hydrogen peroxide solution, the concentration of hydrogen peroxide is preferably as high as 0.1% or more. Approximately 20% to 30% is preferable, and higher concentrations result in lower solubility.
In addition, at high temperatures, hydrogen peroxide and alkoxytitanium peroxide decompose violently, which is inconvenient. Therefore, in order to suppress the temperature rise due to the heat of dissolution reaction, aqueous hydrogen peroxide solution should be prepared at a temperature below 50°C, preferably while cooling with ice water. It is necessary to mix and dissolve. When the pressure of the aqueous alkoxy titanium peroxide solution obtained in this manner is reduced to 10 -2 to 10 -3 torr using, for example, an oil rotary pump, hydrogen peroxide is substituted, and liberated alcohol and a small amount of alcohol are removed. Oxidation products such as ketones or aldehydes are distilled off together with water and free hydrogen peroxide to produce a high purity titanium hydrogen peroxide aqueous solution.
得られた過酸化水素化アルコキシチタン水溶液
並びに高純度過酸化水素化チタン水溶液は冷温下
では準安定であるが、常温以上では最初に遊離過
酸化水素を分解して多量の酸素ガスを放出する、
同時に高過酸化水素化チタンは低過酸化水素化チ
タンに変化し色調の蜜柑色が時間と共に薄くな
り、続いて低過酸化水素化チタンの縮合が起こ
り、縮合度を徐々に増して行き、粘ちよう性が増
加して行き、ゼリー状になる。一般的には、室温
度下では数時間から数日間、或いは100℃下では
数分間から数時間にわたつて、この状態が続く。
遂には縮合低過酸化水素化チタンを沈降する、最
終的には沈降物は水酸化チタンに変化する。ゼリ
ー中のコロイド粒子は乾燥或いは凍結によつて凝
集する、また、疎水性になる。 The obtained aqueous alkoxy titanium peroxide solution and high-purity titanium hydrogen peroxide aqueous solution are metastable at cold temperatures, but at room temperature or higher, free hydrogen peroxide is first decomposed and a large amount of oxygen gas is released.
At the same time, high hydrogen peroxide titanium changes to low hydrogen peroxide titanium, and the orange color tone becomes lighter over time, followed by condensation of low hydrogen peroxide titanium, gradually increasing the degree of condensation, and increasing the viscosity. The consistency increases and becomes jelly-like. Generally, this state continues for several hours to several days at room temperature, or for several minutes to several hours at 100°C.
Finally, the condensed low hydrogen peroxide titanium is precipitated, and the precipitate is finally converted to titanium hydroxide. Colloidal particles in a jelly aggregate and become hydrophobic upon drying or freezing.
低濃度、低縮合度のゲル液を固体上に塗布し
て、これを室温下で風乾すると液は均一な固体被
膜となる。 When a gel solution with a low concentration and degree of condensation is applied onto a solid and air-dried at room temperature, the solution becomes a uniform solid film.
ゲルを急速に凍結すると、コロイド粒と固体の
水が微細に混じた凍結体となる、それをそのまま
減圧乾燥すると固体の水の占めていた部分が空隙
となる、その空隙の形状は固体の水の成長を示し
ている、残部として、立体構造体（蜂の巣状、繊
維状）が出来る。ゲルを徐々に凍結すると粗粒或
いは粗大片となる。 When gel is rapidly frozen, it becomes a frozen solid that is a fine mixture of colloidal particles and solid water.If it is dried under reduced pressure, the portion occupied by solid water becomes voids, and the shape of the voids is similar to that of solid water. The remaining part shows the growth of three-dimensional structures (honeycomb-like, fibrous-like). When the gel is gradually frozen, it becomes coarse particles or coarse pieces.
乾燥縮合低過酸化水素化チタンを徐々に昇温し
ていくと、約100℃で脱水、吸熱が生じ、約250〜
320℃で脱水、脱酸素および発熱が生じ、450℃以
上で形状を保つた酸化チタンとなる。急速に加熱
すると、脱ガスによつて以前の形状は壊れて粉状
となる。 When the temperature of dry condensed low hydrogen peroxide titanium is gradually raised, dehydration and endotherm occur at about 100℃, and the temperature rises to about 250℃.
Dehydration, deoxidation, and heat generation occur at 320°C, and titanium oxide retains its shape at 450°C or higher. When heated rapidly, degassing causes the former shape to collapse and become powdery.
発明の効果
本発明の方法によると次のような優れた効果が
ある。Effects of the Invention The method of the present invention has the following excellent effects.
１ 高純度酸化チタンの製造原料としての高純度
の酸化チタンが得られる。該原料中にチタン、
水素および酸素以外の元素を含まないので、原
料自体から不純物を発生しない。また該原料に
分解剤を加える必要がなく、ただ熱的に分解す
るだけでよいので、不純物の混入が避けられ
て、高純度品が得られる。1. High purity titanium oxide is obtained as a raw material for producing high purity titanium oxide. Titanium in the raw material,
Since it does not contain any elements other than hydrogen and oxygen, the raw material itself does not generate impurities. Further, since there is no need to add a decomposing agent to the raw material and only thermal decomposition is required, contamination with impurities can be avoided and a highly pure product can be obtained.
２ 原料液体から固体形成を徐々に行わせて、固
体を繊維状或いは膜状にしかも高純度に酸化チ
タンをより容易に得られる。2. By gradually forming a solid from a raw material liquid, it is possible to easily obtain titanium oxide in the form of a fiber or film with high purity.
実施例 １
0.522グラムのテトライソプロポキシチタンを
ビーカーに入れて、このビーカーを氷水中に浸し
て冷却しながら、この上に５mlの30％高純度過酸
化水素水溶液を加えて、徐々に撹拌しながら均一
な蜜柑色の過酸化水素化イソプロポキシチタン水
溶液を得た。この水溶液を減圧して、イソプロパ
ノールを除去して、高純度過酸化水素化チタン水
溶液を得た。Example 1 Put 0.522 grams of titanium tetraisopropoxy into a beaker, and while cooling the beaker by immersing it in ice water, add 5 ml of 30% high-purity hydrogen peroxide aqueous solution thereon, and gradually stir the mixture. A homogeneous tangerine-colored aqueous solution of hydrogenated isopropoxytitanium was obtained. This aqueous solution was depressurized to remove isopropanol to obtain a high purity titanium hydrogen peroxide aqueous solution.
Claims (1)
し、該溶液を減圧蒸留して、アルコキシチタン中
のアルコキシル基を揮発性の有機物に変えて、こ
れを除去することを特徴とする高純度過酸化水素
化チタン水溶液の製造法。1 High-purity hydrogen peroxide production characterized by dissolving alkoxytitanium in an aqueous hydrogen peroxide solution and distilling the solution under reduced pressure to convert the alkoxyl groups in alkoxytitanium into volatile organic substances and remove them. Method for producing titanium aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9358386A JPS62252301A (en) | 1986-04-23 | 1986-04-23 | Production of aqueous solution of titanium hydroperoxide of high purity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9358386A JPS62252301A (en) | 1986-04-23 | 1986-04-23 | Production of aqueous solution of titanium hydroperoxide of high purity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62252301A JPS62252301A (en) | 1987-11-04 |
| JPH0369842B2 true JPH0369842B2 (en) | 1991-11-05 |
Family
ID=14086297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9358386A Granted JPS62252301A (en) | 1986-04-23 | 1986-04-23 | Production of aqueous solution of titanium hydroperoxide of high purity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62252301A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2350841B (en) * | 1999-06-08 | 2001-12-19 | Kansai Paint Co Ltd | Inorganic film-forming coating composition, preparation method therof and inorganic film-forming method |
| US6733580B2 (en) * | 1999-06-08 | 2004-05-11 | Kansei Paint Co., Ltd | Inorganic film-forming coating composition, preparation method thereof and inorganic film-forming method |
| JP3122432B1 (en) * | 1999-07-05 | 2001-01-09 | モリオキ産業株式会社 | Method for producing solution for forming titanium oxide film |
| CN101831728B (en) * | 2010-04-12 | 2012-05-23 | 南京理工大学 | Method for preparing nano-crystalline photocatalysis titanium dioxide fiber |
-
1986
- 1986-04-23 JP JP9358386A patent/JPS62252301A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62252301A (en) | 1987-11-04 |
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