JPH033608B2 - - Google Patents
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- Publication number
- JPH033608B2 JPH033608B2 JP61093585A JP9358586A JPH033608B2 JP H033608 B2 JPH033608 B2 JP H033608B2 JP 61093585 A JP61093585 A JP 61093585A JP 9358586 A JP9358586 A JP 9358586A JP H033608 B2 JPH033608 B2 JP H033608B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- titanium
- aqueous
- titanium oxide
- peroxide solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はクロマトグラフイー用充填剤及び触媒
として有用な高純度酸化チタンの空隙を有する繊
維構造体の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing a porous fibrous structure of high purity titanium oxide useful as a filler and catalyst for chromatography.
従来技術
従来の酸化チタンの繊維状体の製造法として
は、繊維状チタン酸カリウムを鉱酸例えば塩酸に
浸してカリウム成分を水素イオンで置換して、チ
タン酸に変え、さらに加熱して、チタンとする方
法が知られている。しかしこの方法では、カリウ
ムを完全に水素で置換するためには塩酸処理を十
分に行うことが必要である。そうすると繊維の形
状が崩れてしまう。また、カリウムや塩素を完全
に除くことが困難である等の欠点があつた。Prior Art The conventional method for producing fibrous titanium oxide is to soak fibrous potassium titanate in a mineral acid such as hydrochloric acid to replace the potassium component with hydrogen ions, converting it into titanic acid, and then heating it to form titanium oxide. There are known methods to do this. However, this method requires sufficient hydrochloric acid treatment to completely replace potassium with hydrogen. This will cause the fibers to lose their shape. Further, there were drawbacks such as difficulty in completely removing potassium and chlorine.
発明の目的
本発明は従来法における欠点を解消するために
行つたもので、その目的は極めて高純度の、しか
も所望の形状を有する酸化チタンの空隙を有する
繊維構造体を容易に製造出来る方法を提供するこ
とである。Purpose of the Invention The present invention was carried out in order to eliminate the drawbacks of conventional methods, and its purpose is to provide a method that can easily produce a fiber structure with extremely high purity and voids of titanium oxide having a desired shape. It is to provide.
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、過酸化水素化チタン水溶液或いは過酸化
水素化アルコキシチタン水溶液を縮合させて、粘
ちよう液乃至ゼリー状に変え、該液に所望の形状
を与え、これを凍結すると空隙を有する繊維構造
体となり、これをそのまま減圧乾燥して、450℃
以上に加熱すると、ほぼ元の形状を保つた高純度
酸化チタンの空隙を有する繊維構造体が容易に得
られることを究明出来た。この知見に基づいて本
発明を完成した。Structure of the Invention As a result of research to achieve the above object, the present inventor condensed an aqueous titanium hydrogen peroxide solution or an aqueous alkoxy titanium peroxide solution to form a sticky liquid or jelly, and obtained the liquid. is given the desired shape and frozen to form a fibrous structure with voids, which is then dried under reduced pressure at 450°C.
It has been found that heating to the above temperature makes it easy to obtain a fibrous structure with voids made of high purity titanium oxide that maintains almost its original shape. The present invention was completed based on this knowledge.
本発明の要旨
過酸化水素化チタン水溶液或いは過酸化水素化
アルコキシチタン水溶液を縮合させた粘ちよう液
乃至ゼリー状液で所望の形状物を作り、これを凍
結して、凍結体に変えて、該凍結体をそのまま減
圧乾燥した後、450℃以上に徐々に昇温すること
を特徴とする高純度酸化チタンの空隙を有する繊
維構造体の製造法である。Summary of the present invention A desired shape is made from a sticky liquid or a jelly-like liquid obtained by condensing an aqueous titanium hydrogen peroxide solution or an aqueous alkoxy titanium hydrogen peroxide solution, and this is frozen to turn it into a frozen body. This is a method for producing a fiber structure having voids made of high-purity titanium oxide, which is characterized in that the frozen body is dried under reduced pressure as it is, and then the temperature is gradually raised to 450° C. or higher.
初めに過酸化水素化チタン水溶液を次の二方法
のいずれかによつて製造する。一つは、水素化チ
タンと過酸化水素水溶液の溶解反応を起こさせ
る、この時、また水素化チタンは過酸化水素の分
解反応および先に生じた過酸化水素化チタンの縮
合反応に触媒作用を持ち、両反応を促進する。溶
解反応を速やかに且つ優先させるために、通常入
手出来る塊状水素化チタンを非酸化性雰囲気下、
例えば水中で粉砕し、微粉末として使用すること
が必要である。過酸化水素濃度0.11％以上で溶解
出来るが、濃度が高いほど溶解速度は早くなるの
で30％程度が好ましい。二つは、アルコキシチタ
ンを過酸化水素水溶液に混合して、溶解反応を起
こして、過酸化水素化アルコキシチタン水溶液を
製造する、この時に、過酸化水素水中の水分によ
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％以上でよいが、30％程度が好ましい。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起こるので、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に例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、過酸化水素化チ
タン水溶液が製造される。このためには揮発性に
富むアルコール分を含む、メトキシチタン、エト
キシチタン、プロポキシチタンが好ましい。 First, a titanium hydrogen peroxide aqueous solution is produced by one of the following two methods. One is to cause a dissolution reaction between titanium hydride and an aqueous hydrogen peroxide solution, and at this time, titanium hydride also catalyzes the decomposition reaction of hydrogen peroxide and the condensation reaction of titanium hydride that occurred previously. and promote both reactions. In order to speed up and give priority to the dissolution reaction, commonly available bulk titanium hydride was prepared under a non-oxidizing atmosphere.
For example, it is necessary to grind it in water and use it as a fine powder. Hydrogen peroxide can be dissolved at a concentration of 0.11% or more, but the higher the concentration, the faster the dissolution rate, so a hydrogen peroxide concentration of about 30% is preferable. The second is to mix alkoxytitanium with a hydrogen peroxide aqueous solution and cause a dissolution reaction to produce an alkoxytitanium peroxide aqueous solution. At this time, the alkoxytitanium is hydrolyzed by the water in the hydrogen peroxide solution. In order to avoid this, the higher the concentration of hydrogen peroxide, the better.
It may be 0.1% or more, but about 30% is preferable. Furthermore, at high temperatures, hydrogen peroxide and alkoxy titanium peroxide decompose, so in order to suppress the temperature rise due to the heat of reaction, the hydrogen peroxide aqueous solution is mixed at 50°C or lower, preferably while cooling with ice water.
It is necessary to dissolve it. When the aqueous alkoxy titanium peroxide solution obtained by this method is depressurized to 10 -2 to 10 -3 torr using, for example, an oil rotary pump,
Displaced by hydrogen peroxide, the liberated alcohol and some alcohol oxidation products such as ketones or aldehydes are distilled off together with water and free hydrogen peroxide to form an aqueous titanium peroxide solution. Manufactured. For this purpose, methoxytitanium, ethoxytitanium, and propoxytitanium containing highly volatile alcohol content are preferred.
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。 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.
得られた過酸化水素化アルコキシチタン水溶液
および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、室温以上では、最初に遊離
の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
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。 The resulting 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. , the viscosity 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.
ゼリーに所定の形状を与えたまま例えば液体窒
素等で急速に凍結すると、縮合過酸化水素化チタ
ンの空隙を有する繊維構造体（蜂の巣状、繊維網
目状）と微細状固体水分が混じた凍結体となる、
これをそのまま減圧して、外形の保たれたままを
取り出し、これを徐々に昇温していくと、その形
状を保つたまま、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℃以上でほぼ原の形状を保つた高純度の酸化
チタンの空隙を有する繊維構造体となる。 When the jelly is rapidly frozen in liquid nitrogen while being given a predetermined shape, a frozen body is formed that is a mixture of a fibrous structure (honeycomb shape, fiber network shape) with voids of condensed titanium hydrogen peroxide and fine solid water. becomes,
When this is depressurized and taken out with its outer shape maintained, and the temperature is gradually raised, dehydration and endotherm occur at approximately 100℃ while maintaining the shape.
Dehydration, deoxidation and exotherm occur at approximately 250-320℃,
It becomes a fibrous structure with voids made of high-purity titanium oxide that maintains almost its original shape at temperatures above 450°C.
発明の効果
本発明の方法によると高純度酸化チタンの製造
原料として過酸化水素チタン水溶液、或いはこの
縮合物を使用するため、チタン、水素、および酸
素以外の元素を含まないので、従来法と異なつ
て、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、極めて高純度の酸化チタンが得られる。また
ゼリー状の所定の形状物を凍結によつて、空隙を
有する繊維構造体を形成させ、凍結体を原形のま
ま減圧乾燥して、所望の外形をした高純度の酸化
チタンの空隙を有する繊維構造体が得られる優れ
た効果がある。Effects of the Invention The method of the present invention uses an aqueous titanium hydrogen peroxide solution or its condensate as a raw material for producing high-purity titanium oxide, and therefore does not contain any elements other than titanium, hydrogen, and oxygen, which is different from conventional methods. Therefore, impurities are not generated from the raw material itself, and there is no need to add a decomposing agent to the raw material, just thermal decomposition is required, so contamination with impurities can be avoided and titanium oxide of extremely high purity can be obtained. . In addition, a fibrous structure with voids is formed by freezing a jelly-like product with a predetermined shape, and the frozen structure is dried under reduced pressure in its original shape to create fibers with voids made of high-purity titanium oxide with a desired external shape. There is an excellent effect that a structure can be obtained.
また酸化チタン中に僅小量の炭素分が含有が許
されるならば、分子量の小さいアルコキシチタン
即ちメトキシチタン、エトキシチタン、プロポキ
シチタンを用いた過酸化水素化アルコキシチタン
水溶液がそのまま利用出来る。 Furthermore, if titanium oxide is allowed to contain a small amount of carbon, an aqueous solution of alkoxytitanium peroxide hydrogenated using alkoxytitanium with a small molecular weight, ie, methoxytitanium, ethoxytitanium, or propoxytitanium, can be used as is.
実施例 １
8.22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、その上に30mlの30％高純度過酸化
水素水溶液を加えて、徐々に撹拌して均一な蜜柑
色の過酸化水素化イソプロポキシチタン水溶液と
した。これに純水10mlを加えて希釈して、念のた
めろ過をして不溶解物をないようにしてから、こ
のろ液を50℃で７分間保つて、ゲル化させて、こ
れを直径約８mmの球状とした後、液体窒素中に投
入して、凍結させて、凍結状態下で減圧して、
2.26グラムの淡黄色の微細な空隙を含んだ淡黄色
の繊維構造体を得た。これを空気中で、毎分２℃
の速度で500℃まで昇温して、表面積24m2／ｇ、
微細な空隙を含んだ無色の酸化チタン繊維構造体
を得た。これの電子顕微鏡写真を示す。Example 1 Put 8.22 grams of titanium tetraisopropoxy into a beaker, and while cooling the beaker by immersing it in ice water, add 30 ml of 30% high-purity hydrogen peroxide aqueous solution thereon, and gradually stir. A uniform tangerine-colored aqueous solution of hydrogenated isopropoxytitanium was obtained. Add 10ml of pure water to dilute it, filter it just to make sure there are no undissolved substances, and keep this filtrate at 50℃ for 7 minutes to gel it. After making it into a sphere of 8 mm, it was put into liquid nitrogen, frozen, and the pressure was reduced under the frozen state.
A pale yellow fibrous structure containing 2.26 grams of pale yellow fine voids was obtained. This is carried out in air at 2°C per minute.
Raise the temperature to 500℃ at a rate of 24m 2 /g,
A colorless titanium oxide fiber structure containing fine voids was obtained. An electron micrograph of this is shown.
なお、水素化チタンに過酸化水素水溶液を添加
して得た過酸化水素チタン水溶液を使用しても前
記と同様に微細な空隙を含んだ無色の酸化チタン
繊維構造体が得られる。 Note that even if an aqueous titanium hydrogen peroxide solution obtained by adding an aqueous hydrogen peroxide solution to titanium hydride is used, a colorless titanium oxide fiber structure containing fine voids can be obtained in the same manner as described above.
図面は本発明の方法で得られた酸化チタン繊維
構造体の電子顕微鏡写真を示す。
The drawing shows an electron micrograph of a titanium oxide fiber structure obtained by the method of the present invention.
Claims (1)
アルコキシチタン水溶液を縮合させた粘ちよう液
乃至ゼリー状液で所望の形状物を作り、これを凍
結して凍結体に変えて、該凍結体を減圧乾燥した
後、450℃以上に徐々に昇温することを特徴とす
る高純度酸化チタンの空隙を有する繊維構造体の
製造法。1. Create a desired shape using a sticky liquid or jelly-like liquid obtained by condensing an aqueous titanium hydrogen peroxide solution or an aqueous alkoxy titanium hydrogen peroxide solution, freeze this to turn it into a frozen body, and turn the frozen body into a frozen body. A method for producing a fiber structure having voids made of high-purity titanium oxide, which is characterized by drying under reduced pressure and then gradually raising the temperature to 450°C or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61093585A JPS62252320A (en) | 1986-04-23 | 1986-04-23 | Production of fibrous structure of high-purity titanium oxide having void |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61093585A JPS62252320A (en) | 1986-04-23 | 1986-04-23 | Production of fibrous structure of high-purity titanium oxide having void |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62252320A JPS62252320A (en) | 1987-11-04 |
| JPH033608B2 true JPH033608B2 (en) | 1991-01-21 |
Family
ID=14086358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61093585A Granted JPS62252320A (en) | 1986-04-23 | 1986-04-23 | Production of fibrous structure of high-purity titanium oxide having void |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62252320A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ305801B6 (en) * | 2011-07-18 | 2016-03-23 | Ústav anorganické chemie AV ČR, v.v.i. | Process for preparing photocatalycally active material with foamy structure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5426997A (en) * | 1977-08-03 | 1979-02-28 | Murata Manufacturing Co | Method of making high purity oxide |
-
1986
- 1986-04-23 JP JP61093585A patent/JPS62252320A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62252320A (en) | 1987-11-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |