JPS6036304A - Apparatus for purification of reagent - Google Patents

Abstract

PURPOSE:To facilitate the peeling and recovery of sublimed and purified reagent, by using a quartz glass tube furnished with corrosion-resistant inner vessel as the raw reagent container of a vacuum sublimative purification apparatus of a fluoride for the raw material of fluoride glass fiber. CONSTITUTION:The inner vessel 3 made of platinum cylinder is placed in a quartz glass support tube 2 of a sublimative purification apparatus, and the vessel 3 is divided into two parts 3a, 3b which are introduced into the high-temperature zone and the low-temperature zone, respectively. The staring reagent, NH4F.HF is put into the container 3a, the ground-in part 4 is connected to the pipe 2, and the support tube 2 is evacuated with the vacuum pump 8. After ascertaining the complete evacuation of the pipe 2 by a vacuum gauge 7, the electric furnace 1 is electrified and the tube 2 is cooled from outside by the cooling device 1'. NH4F.HF sublimes and is deposited to the inner wall of the vessel 3b. After a definite time, the furnace 1 is switched off, and the pump 8 is stopped to finish the sublimation. The ground connection 4 is disconnected, the vessel 3 is taken out of the pipe 2, and the sublimed NH4F.HF is peeled and recovered from the inner wall of the vessel 3b.

Description

【発明の詳細な説明】 本発明はガラス浸蝕性試薬を超高純度に精製する精製装
置に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a purification device for purifying a glass corrosive reagent to ultra-high purity.

低損失光ファイバを得るには、吸収を示す不純物、たと
えば遷移金属、水分等の含有量を極端に減少させた原料
を使用してファイバを作製しなければならないことは周
知のことである。It is well known that in order to obtain a low-loss optical fiber, the fiber must be fabricated using a raw material that has an extremely reduced content of absorbing impurities such as transition metals, water, and the like.

フッ化物ガラスファイバにおいて、含有不純物を減少さ
せるには、ガラス原料となるフッ化物、たとえばＢａＦ
　＊　ＧｄＦ　ｒ　ＺｒＦ　＋　ＩＦ８などおよび２　
８　４ フッ素化剤ＮＨ，Ｆ−ＨＦの超高純度な試薬の使用が不
可欠である。In order to reduce the impurities contained in fluoride glass fiber, fluoride as a glass raw material, such as BaF
*GdF r ZrF + IF8 etc. and 2
8 4 It is essential to use ultrapure reagents for the fluorinating agents NH, F-HF.

従来、この種試薬の精製においては、耐腐蝕性材料、た
とえばプラスデック容器を用いた湿式精製法が用いられ
てきた。この方法により精製したフッ化物ガラス原料を
用い、ガラスファイバを作製した。作製したファイバの
損失特性には遷移金属不純物による損失増のピークが生
じ、低損失値が得られなかった。したがってこの試薬で
は不純物の除来が充分にされていないことが明らかとな
った。Conventionally, in the purification of this type of reagent, a wet purification method using a corrosion-resistant material, such as a PlusDeck container, has been used. A glass fiber was produced using the fluoride glass raw material purified by this method. The loss characteristics of the fabricated fiber showed a peak of increased loss due to transition metal impurities, and low loss values could not be obtained. Therefore, it became clear that this reagent did not sufficiently remove impurities.

一方、本発明者らは、より高純度化せしめるため、減圧
中での昇華精製を試みた。この場合、減圧下でａＯＯ〜
１８００°Ｃまでの加熱が必要であるので、容器にはプ
ラスチックの使用が不可能である。さらに本精製装置で
は高純度であることが大切であるので、従来使用されて
いるニッケル合金等の金属製容器も使用できない。もち
論、腐蝕されず高温に耐える金属として白金が考えられ
るが、本減圧機能を有する精製装Ｍをすべて白金製にす
ることは、経済的なデメリットが大きすぎる。On the other hand, the present inventors attempted sublimation purification under reduced pressure in order to achieve higher purity. In this case, under reduced pressure aOO~
Since heating up to 1800°C is required, it is not possible to use plastic for the container. Furthermore, since high purity is important in this purification device, conventional metal containers such as nickel alloy cannot be used. Of course, platinum can be considered as a metal that does not corrode and can withstand high temperatures, but it would be economically disadvantageous to make all of the refining equipment M having the pressure reduction function made of platinum.

容器として超高純度の得られる石英ガラスを用・いてフ
ッ化物ガラス試薬の精製を施したところ、昇華が可能で
あり、精製法として有効であることが判明した。When a fluoride glass reagent was purified using ultra-high purity quartz glass as a container, it was found that sublimation was possible and that this was an effective purification method.

しかしながら、フッ化物ガラス試薬は腐蝕性が強く、原
料試薬を設置する部分の石英ガラスを腐蝕（浸蝕）し、
数回の使用で穴があき、使用不可能となった。これは石
英ガラスからの汚染が極めて大きいことを意味する。さ
らに昇華揮発した試薬が付着する部分の低温部で、付着
した試薬が石英ガラス管内壁に焼結し、剥離せず回収が
困難になるという不都合な点があった。However, fluoride glass reagents are highly corrosive and corrode (erode) the quartz glass where the raw material reagents are placed.
After using it a few times, it developed a hole and became unusable. This means that contamination from quartz glass is extremely large. Furthermore, in the low-temperature region where the sublimated and volatilized reagent adheres, the adhered reagent is sintered on the inner wall of the quartz glass tube, making it difficult to recover without being peeled off.

本発明はこれらの欠点を解決するため、石英ガラス製の
サポート管内に耐腐蝕性材料によって作製した内側容器
を配置し、またこの容器が縦割り可能な構造とし、昇華
精製試薬の回収を可能にしたことを特徴とする薬品の精
製装置を提供することを目的とする。以下図面により本
発明の実施例について説明する。In order to solve these drawbacks, the present invention arranges an inner container made of a corrosion-resistant material inside a support tube made of quartz glass, and also has a structure in which this container can be divided vertically, making it possible to recover the sublimation purification reagent. An object of the present invention is to provide a chemical purification device characterized by the following features. Embodiments of the present invention will be described below with reference to the drawings.

実施例１ 第１図は本発明の一実施例の構成を示す概略図であって
、１は加熱用電気炉、１１．は冷却装置、２は石英ガラ
ス管からなるサポート管、３は白金製円筒からなる内側
容器、４はすり合わせ、５はコネクタ、６は排気用管、
７は真空計、８は真空ポンプである。Embodiment 1 FIG. 1 is a schematic diagram showing the configuration of an embodiment of the present invention, in which 1 is an electric furnace for heating, 11. is a cooling device, 2 is a support tube made of a quartz glass tube, 3 is an inner container made of a platinum cylinder, 4 is a joint, 5 is a connector, 6 is an exhaust pipe,
7 is a vacuum gauge, and 8 is a vacuum pump.

第２図は内側容器８の実施例で、高温部に入る部分と低
温部に入る部分が分割できる例な示す。FIG. 2 shows an embodiment of the inner container 8, which can be divided into a portion that enters the high temperature section and a section that enters the low temperature section.

８ａは高温部内側容器、８ｂは低温部内側容器、９は分
割防止用リングである。低温部内側容器３ｂは、第２１
ｍ（Ｃ）に示すように、四つに分割された部分からなり
、第２１ｆｆｌ（ａ）、（ｂ）に示すように、分割防止
リング９で止められている。8a is a high temperature section inner container, 8b is a low temperature section inner container, and 9 is a division prevention ring. The low temperature section inner container 3b is the 21st
As shown in m(C), it consists of four divided parts, and as shown in 21st ffl(a) and (b), it is stopped by a division prevention ring 9.

本装置によりＮＥＩ、Ｆ−）ＩＦの昇華精製を行うには
、すり合わせ４をはずし、高温部内側容器３ａ内に出発
試薬のＮＨ，Ｆ−１（Ｆを入れる。To perform sublimation purification of NEI,F-)IF using this apparatus, remove the grinder 4 and place the starting reagents NH,F-1(F) into the high temperature section inner container 3a.

次にすり合わせ４の部分をサポート管２に接続した後、
真空ポンプ８によって管内を排気し減圧する。このとき
の真空度は真空計７で読み取れる。Next, after connecting the joint 4 part to the support pipe 2,
The inside of the tube is evacuated and depressurized by the vacuum pump 8. The degree of vacuum at this time can be read with a vacuum gauge 7.

管内が充分に排気されたら電気炉１の温度を２００°Ｃ
に上げ、さらに冷却装置１′でサポート管２の外・側か
ら冷却した。ＮＨ，Ｆ−ｆ（Ｆは２００℃で昇華して、
下流側低ｉ？ｉｉ１部の低温部内側容器３ｂの内壁に付
着する。２００°Ｃで約５時間保った後、電気炉１の電
源を切り真空ポンプ８を止めることにより、出発試薬は
約８〜９割昇華し、昇華精製は終了する。Once the inside of the tube is sufficiently exhausted, increase the temperature of electric furnace 1 to 200°C.
The support tube 2 was further cooled from the outside/side using a cooling device 1'. NH, F-f (F sublimes at 200℃,
Downstream low i? ii1 part adheres to the inner wall of the low temperature section inner container 3b. After maintaining the temperature at 200° C. for about 5 hours, the power to the electric furnace 1 is turned off and the vacuum pump 8 is stopped, whereby the starting reagent is sublimed by about 80 to 90%, and the sublimation purification is completed.

精製されたＮＨ，Ｆ−ＨＦの取り出しは、すり合わせ４
の部分をはずし、内側容器８をサポート管２から取り出
す。゛内壁に昇華したＮＨ，Ｆ−ＨＦが付着した低温部
内側容器３ｂは、分割防止リング９を取りはずすことに
より四つに分割でき、ＮＨ，Ｆ−）（Ｆは容易に剥離し
回収される。ここで内側容器８は電気炉１の内に入る部
分、すなわち出発試薬のＮＨ４Ｆ−ＨＦを入れる高温部
内側容器３ａは白金でできており、低温部内側容器８ｂ
は白金でもよいし、テフロン等の耐腐食性の材料でもよ
い。Removal of purified NH, F-HF is done by grinding 4.
Remove the inner container 8 from the support tube 2. ``The low-temperature section inner container 3b with sublimated NH, F-HF attached to the inner wall can be divided into four parts by removing the division prevention ring 9, and NH, F-) (F is easily peeled off and recovered. Here, the inner container 8 is a part that enters the electric furnace 1, that is, the high temperature inner container 3a containing the starting reagent NH4F-HF is made of platinum, and the low temperature inner container 8b.
may be platinum or a corrosion-resistant material such as Teflon.

実施例２ ＺｒＦ、の昇華精製は試薬を入れ、管内を排気するまで
は実施例１と同じ方法によった。その後電気炉］の温度
を９００°Ｃに上げ、さらに冷却装置１／でサポート管
２の外側から冷却した０ＺｒＦ、は９００°Ｃで昇華し
て、低温部内側容器８ｂの内壁に付着した。９００°Ｃ
で５分間保つことにより出発ＺｒＦ４を約９割昇華させ
た後、電気炉ｌの電源を切った。精製したＺｒＦ、の回
収は実施例１と同じ方法によった。Example 2 Sublimation purification of ZrF was carried out in the same manner as in Example 1, except for adding the reagent and evacuating the inside of the tube. Thereafter, the temperature of the electric furnace was raised to 900°C, and the 0ZrF cooled from the outside of the support tube 2 by the cooling device 1/ was sublimed at 900°C and adhered to the inner wall of the low temperature section inner container 8b. 900°C
After sublimating the starting ZrF4 by about 90% by keeping the temperature at 5 minutes, the power to the electric furnace 1 was turned off. The purified ZrF was recovered by the same method as in Example 1.

同様にしてＡｌＦ２も精ｌ！！！を行った。In the same way, AlF2 is also the best! ! ! I did it.

実施例３ ＢａＦ２は実施例１．２とは逆に不純物を揮発（昇華）
する方法によった。出発試薬のＢａＦ　、を白金製ボ・
−ト内に入れ、サポート管２に入れ電気炉ｌの中央部に
挿入した。このとき実施例１，２で用いた低温部内側容
器は入れる必要がない。Example 3 BaF2 volatilizes impurities (sublimation) contrary to Example 1.2
It depends on how you do it. The starting reagent, BaF, was added to a platinum bottle.
- into the support tube 2 and inserted into the center of the electric furnace 1. At this time, there is no need to insert the low temperature section inner container used in Examples 1 and 2.

次に管内を真空に排気し、電気炉ｌの温度を１１００℃
に上げ、出発試薬中の遷移金属を揮発させた。１１００
°Ｃで５時間保った後、電気炉の温度を下げ、白金製ボ
ートを取り出し、ボート内のＢａＦ２を回収した。Next, the inside of the tube was evacuated to a vacuum, and the temperature of the electric furnace was set to 1100℃.
to volatilize the transition metal in the starting reagent. 1100
After being kept at °C for 5 hours, the temperature of the electric furnace was lowered, the platinum boat was taken out, and BaF2 inside the boat was recovered.

同様にして　ＧｄＦ３も精製した。GdF3 was also purified in the same manner.

第３図は実ｊ、Ｉｌｉ例１．２．８の方法を用いて精製
したフッ化物ガラス原料（７）　ＢａＦ　、　、ＧｄＦ
３．　ＺｒＦ、　ｔＡｌＦ３とフッ素化剤のＮＨ，Ｆ−
ＨＦをｔｉ量秤量し作製したフッ化物ガラスロッドを線
引きした光７アイパの損失特性の代表例を実線で示す。Figure 3 shows the fluoride glass raw material (7) BaF, , GdF purified using the method of Example 1.2.8.
3. ZrF, tAlF3 and fluorinating agent NH,F-
The solid line shows a representative example of the loss characteristics of the Hikari 7 Eyeper, which was drawn from a fluoride glass rod prepared by weighing the ti amount of HF.

比較のために、湿式精製法によって精製した市販品の特
級純度をもつ各ガラス原料とＮＨ４Ｆ−ＨＦで作製した
光ファイバの損失特性を破線で示す。For comparison, the loss characteristics of optical fibers made from commercially available special grade purity glass raw materials purified by the wet refining method and NH4F-HF are shown by broken lines.

湿式精製原料からなる破線の損失特性で０．８〜０．９
μｍと１．４〜１．７μｍに現われているピークはＦｅ
不純物によるもの、１〜１．８μｍはＮ１不純物による
ものであり、０．７〜１．７μｍ域における損失値は１
０００ｄＢ／Ｋｍ以上となっている。The loss characteristic of the broken line consisting of wet refining raw materials is 0.8 to 0.9.
The peaks appearing at μm and 1.4 to 1.7 μm are Fe
The loss value in the 0.7 to 1.7 μm region is due to impurities, and the loss value in the 0.7 to 1.7 μm range is 1.
000dB/Km or more.

一方、本精製法の昇華精製を施した実線の損失特性には
、不純物によるピークは見られない。また損失値も１．
７μｍで２０ｄＢ／Ｋｍを下まわり、減圧精精効果が明
確に現われている。On the other hand, no peaks due to impurities are observed in the solid line loss characteristics obtained by sublimation purification using the present purification method. Also, the loss value is 1.
At 7 μm, it was less than 20 dB/Km, clearly showing the effect of reduced pressure.

以上説明したように、本発明の耐腐蝕性材料による内側
容器を使用した減圧精製装置を用いて精製した、各種フ
ッ化物ガラス原料によって作製されたフッ化物ガラスフ
アイバの損失特性には、遷移金属不純物によって生じる
吸収ピークは見当らず、はぼ完全に不純物が除去されて
いることがわかる。As explained above, the loss characteristics of fluoride glass fibers produced from various fluoride glass raw materials refined using a vacuum purification apparatus using an inner container made of the corrosion-resistant material of the present invention include transition metal impurities. No absorption peak was observed, indicating that impurities were almost completely removed.

さらに、本発明による薬品の精製装置に使用した石英管
からなるサポート管はＩＯ向の繰り返し使用にもかかわ
らず、はとんど腐蝕されず、長期間の反復使用及可能な
利点がある。また耐腐蝕性内側容器が縦割りできるから
、付着した精製物が簡単に剥離できるので、回収、作業
も簡便である。Further, the support tube made of quartz tube used in the drug refining device according to the present invention hardly corrodes even though it is repeatedly used for IO, and has the advantage that it can be used repeatedly for a long period of time. Furthermore, since the corrosion-resistant inner container can be divided vertically, the adhered purified product can be easily peeled off, making recovery and work easier.

なお本発明の実施例で耐腐蝕性、材料による内側容器に
は白金を使用したが、白金に限らず、耐腐蝕性があり、
また耐熱性があれば、金、テフロン等でも可能である。In the examples of the present invention, platinum was used for the inner container made of corrosion-resistant material, but platinum is not limited to platinum.
Gold, Teflon, etc. can also be used as long as they have heat resistance.

さらに本発明の実施例では、最も高純度を要求する光フ
アイバ用原料に対して示したが、池の用途の高純度試薬
の精製に有効であることは言うまでもない。Further, in the embodiments of the present invention, the raw materials for optical fibers which require the highest purity are shown, but it goes without saying that the present invention is effective in purifying high-purity reagents for use in ponds.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明を実施するための装置の一例の構成を示
す概略図、 第２図（ａ）、（ｂ）、（０１は内側容器のそれぞれ正
面図、側面図、分割した状態を示す図、第３図は不発明
の実施例で精製した原料および未精製原料を用いて作製
した光７アイパの損失特性を示す図である。 ］・・・加熱用電気炉、１／・・・冷却装置、２・・・
石英ガラス管からなるサポート管、３・・・内側容器、
３ａ・・・１０高濡部内側容器、３ｂ・・・低温部内側
容器、４・・・すり合わせ、５・・・コネクタ、６・・
・排気用管、７・・・真空計、８・・・真空ポンプ、９
・・・分割防止リング。 第 （ （ｂ） ２図FIG. 1 is a schematic diagram showing the configuration of an example of a device for carrying out the present invention. Figures 3 and 3 are diagrams showing the loss characteristics of Hikari 7 Eyepa manufactured using refined raw materials and unrefined raw materials in the uninvented embodiments. ]...Electric furnace for heating, 1/... Cooling device, 2...
Support tube made of quartz glass tube, 3...inner container,
3a...10 high wet part inner container, 3b...low temperature part inner container, 4...grinding, 5...connector, 6...
・Exhaust pipe, 7... Vacuum gauge, 8... Vacuum pump, 9
...Split prevention ring. ((b) Figure 2

Claims (1)

【特許請求の範囲】 １　排気系に接続され内部が排気できる一方を閉じた石
英ガラス管からなるサポート管と、その内部に設置され
た耐腐食性材料からなる内側容器と、この内側容器を含
むサポート管の長手方向に温度分布を与えるため・の加
熱装置および冷却装置とからなることを特徴とする薬品
の精製装置。 区　耐腐食性材料からなる内側容器が縦割り可能な構造
を有することを特徴とする特許請求の範囲第１項記載の
薬品の精製装置。[Scope of Claims] 1. Includes a support tube made of a quartz glass tube with one end closed and connected to an exhaust system so that the inside can be exhausted, an inner container made of a corrosion-resistant material installed inside the support tube, and this inner container. A chemical purification device comprising a heating device and a cooling device for providing temperature distribution in the longitudinal direction of a support tube. 2. The chemical refining device according to claim 1, wherein the inner container made of a corrosion-resistant material has a structure that can be vertically divided.