JPH0733417A - Purifying method for rare gas - Google Patents
Purifying method for rare gasInfo
- Publication number
- JPH0733417A JPH0733417A JP19686593A JP19686593A JPH0733417A JP H0733417 A JPH0733417 A JP H0733417A JP 19686593 A JP19686593 A JP 19686593A JP 19686593 A JP19686593 A JP 19686593A JP H0733417 A JPH0733417 A JP H0733417A
- Authority
- JP
- Japan
- Prior art keywords
- rare gas
- getter material
- zirconium
- impurities
- calcium
- 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.)
- Pending
Links
Landscapes
- Gas Separation By Absorption (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、希ガスの精製方法に関
し、さらに詳細には不純物として少なくともハロゲン化
合物系のガスおよび窒素を含有する希ガスの精製方法に
関する。ヘリウム、ネオン、アルゴン、クリプトン、キ
セノンなどの希ガス中に含まれる不純物は、高温下でゲ
ッター金属と反応させて固定し、希ガス中から除去する
精製方法が常法となっている。この方法は吸着式精製方
法と異なり、再生用のガスを使用しないため、高価な希
ガスを無駄に消費しない特徴がある。希ガス中でヘリウ
ムやアルゴンは近年目覚しく発展しつつある半導体製造
工業で盛んに用いられており、その純度向上への要求は
益々強くなっている。また、ネオン、クリプトン、キセ
ノンは特殊なランプなどを製造するために不可欠のガス
であり、これらのガスは特に高価なこともあって、一度
使用したガスを循環して使うことが多い。この場合には
循環ガス中の不純物を除去して高純度に精製することも
必要である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying a rare gas, and more particularly to a method for purifying a rare gas containing at least a halogen compound gas and nitrogen as impurities. Impurities contained in a rare gas such as helium, neon, argon, krypton, and xenon are fixed by reacting with a getter metal at a high temperature and then removed from the rare gas. Unlike the adsorptive refining method, this method does not use a gas for regeneration, and thus has a feature that an expensive rare gas is not wasted. Helium and argon in rare gases are actively used in the semiconductor manufacturing industry, which has been developing remarkably in recent years, and the demand for improving the purity thereof is becoming stronger and stronger. Further, neon, krypton, and xenon are indispensable gases for manufacturing special lamps and the like, and since these gases are particularly expensive, the gas used once is often circulated and used. In this case, it is also necessary to remove impurities in the circulating gas and purify it to high purity.
【０００２】希ガス中に一般的に含有されている不純物
には窒素、炭化水素、一酸化炭素、二酸化炭素、酸素、
水素および水蒸気などがあり、これらのｐｐｂオーダー
まで除去して高純度に精製することが望まれている。さ
らに、最近では、これらの不純物と同時に希ガス中に含
有されるハロゲン系の不純物の除去に対する要望も半導
体製造工業を中心に拡大しつつあり、特に、エキシマレ
ーザー用のガスや半導体製造の各工程に使用される希ガ
スおよび特殊なランプの製造時に使用される高価な希ガ
スの循環システムなどにおいて高純度に高収率で精製す
る要望が強い。Impurities commonly contained in rare gases include nitrogen, hydrocarbons, carbon monoxide, carbon dioxide, oxygen,
There are hydrogen and water vapor, and it is desired to remove them to the ppb order and purify them to high purity. Furthermore, recently, the demand for removal of halogen-based impurities contained in a rare gas at the same time as these impurities has been expanding mainly in the semiconductor manufacturing industry, and in particular, gas for excimer laser and each step of semiconductor manufacturing There is a strong demand for refining to a high purity and a high yield in a rare gas circulation system used in the production of rare gases used in the above and special lamps.
【０００３】[0003]
【従来の技術】希ガスの精製には従来よりチタンまたは
ジルコニウム系のゲッター材が多用され、これらのゲッ
ター材は、希ガス中に通常含まれる窒素、炭化水素、一
酸化炭素、二酸化炭素、酸素、水素および水蒸気などの
不純物については効率よく除去することができる。しか
しながら、不純物としてハロゲン化合物が含まれる場合
には、これらの除去が困難であるため、ハロゲン化合物
除去用ゲッター技術の開発が数々研究されている。2. Description of the Related Art Titanium or zirconium-based getter materials have been frequently used for refining rare gases, and these getter materials include nitrogen, hydrocarbons, carbon monoxide, carbon dioxide and oxygen which are usually contained in rare gases. Impurities such as hydrogen, water vapor, etc. can be removed efficiently. However, when a halogen compound is contained as an impurity, it is difficult to remove them, and therefore, many studies have been conducted on the development of getter technology for removing a halogen compound.
【０００４】ハロゲン化合物を除去する方法としては、
本発明者らによるカルシウムまたはマグネシウムをゲ
ッター材とし、加熱下に希ガスと接触させる方法（特開
平４−１４９０１０号公報）、カルシウムまたはマグ
ネシウムと、ニッケル、コバルト、銅などからなる合
金、あるいは、Ｚｒ−Ｎｉ−（Ｖ、Ｍｎ、Ｆｅなど）か
らなる合金をゲッター材とし、加熱下に希ガスと接触さ
せる方法（特開平４−２５９３４８号公報）などが知ら
れている。As a method for removing halogen compounds,
A method of using calcium or magnesium as a getter material by the present inventors and bringing it into contact with a rare gas under heating (JP-A-4-149010), an alloy of calcium or magnesium and nickel, cobalt, copper, or Zr. A method is known in which an alloy made of —Ni— (V, Mn, Fe, etc.) is used as a getter material and brought into contact with a rare gas under heating (Japanese Patent Laid-Open No. 4-259348).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、カルシ
ウム、マグネシウム系の合金やＺｒ−Ｎｉ系多元合金の
ような合金ゲッター材では、カルシウム、マグネシウム
単体のゲッター材よりもハロゲン化合物の除去能力が小
さいばかりでなく、高温加熱を必要とするため、合金と
の反応によって生じたハロゲン化金属などの生成物の一
部が気化してゲッター材の下流に移動し、低温部で凝縮
して流路を閉塞し、短時間で差圧が上昇するという欠点
がある。However, an alloy getter material such as a calcium-magnesium alloy or a Zr-Ni multi-component alloy has a smaller halogen compound removing ability than a getter material containing only calcium or magnesium. However, since high temperature heating is required, some of the products such as metal halides generated by the reaction with the alloy are vaporized and move to the downstream of the getter material, and are condensed in the low temperature part to block the flow path. However, there is a drawback that the differential pressure rises in a short time.
【０００６】一方、ゲッター材としてカルシウムまたは
マグネシウムの単体を用いた場合には、上記の合金のよ
うに閉塞の原因となるハロゲン化金属などは生成せず、
また、合金ゲッター材の場合に比べてハロゲン化合物と
の反応性が高く、しかも化学量論的に１００％近く反応
するためか、その除去能力は著しく大きいという利点が
ある。しかしながら、優れた除去能力のあるカルシウム
またはマグネシウムのゲッター材も希ガス中にハロゲン
化物以外の不純物が含まれる場合には、これらも同時に
除去することができるものの精製時間の経過とともにゲ
ッター材部での流路が狭まって差圧が次第に増大すると
いう問題のあることが判明した。On the other hand, when a simple substance of calcium or magnesium is used as the getter material, a metal halide that causes clogging unlike the above alloys is not produced,
Further, it has an advantage that its removing ability is remarkably large, probably because it has a higher reactivity with a halogen compound than in the case of an alloy getter material and reacts in a stoichiometrically nearly 100% manner. However, even if the getter material of calcium or magnesium having an excellent removing ability also contains impurities other than halides in the rare gas, these can be removed at the same time, but with the progress of the purification time, the getter material part It was found that there is a problem that the flow path becomes narrow and the differential pressure gradually increases.
【０００７】[0007]
【課題を解決するための手段】本発明者らは前記のカル
シウム、マグネシウムなどのゲッター材における差圧上
昇の原因について究明を続けた結果、不純物成分に特に
窒素が含まれるときに差圧が増大するという事実をつき
とめるとともに、希ガスをこれらのゲッター材による処
理をおこなう前に、あらかじめ、希ガスをジルコニウ
ム、チタン系のゲッター材と接触させることにより、課
題を解決しうることを見い出し、本発明を完成した。す
なわち本発明は、不純物として少なくともハロゲン化合
物および窒素を含む希ガスから不純物を除去し、高純度
希ガスを得る希ガスの精製方法において、希ガスをジル
コニウムまたはチタン系のゲッター材と加熱下に接触さ
せ、次いで、カルシウムまたはマグネシウムのゲッター
材と加熱下に接触させることを特徴とする希ガスの精製
方法。As a result of continuing investigation into the cause of the increase in the differential pressure in the getter materials such as calcium and magnesium described above, the present inventors have found that the differential pressure increases when the impurity component particularly contains nitrogen. In addition to finding the fact that the rare gas is treated with these getter materials, it was found that the problem can be solved by contacting the rare gas with a zirconium-titanium-based getter material in advance. Was completed. That is, in the present invention, in a method for purifying a rare gas in which impurities are removed from a rare gas containing at least a halogen compound and nitrogen as impurities to obtain a high-purity rare gas, the rare gas is contacted with a zirconium- or titanium-based getter material under heating. And then contacting with a calcium or magnesium getter material under heating, a method for purifying a noble gas.
【０００８】本発明は不純物として少なくともハロゲン
化合物および窒素を含むヘリウム、ネオン、アルゴン、
クリプトン、キセノンなどの希ガスの精製に適用され
る。除去の対象となるハロゲン化合物としては、ハロゲ
ン化水素、ハロゲン化炭素、ハロゲン化炭化水素および
６Ｂ族元素のハロゲン化物、主に弗素、塩素系のハロゲ
ン化合物などであり、６Ｂ族元素としては硫黄、セレン
またはテルルなどである。例えば、ＨＣｌ，ＨＦなどの
ハロゲン化水素、ＣＦ4 、ＣＣｌ4 などのハロゲン化炭
素、ＣＨＦ3 、Ｃ2 Ｈ2 Ｆ4 、ＣＨＣｌ3 、Ｃ2 Ｈ2 Ｃ
ｌ4 などのハロゲン化炭化水素、また、６Ｂ族元素のハ
ロゲン化物ではＳＦ、ＳＦ2 、ＳＦ4、ＳＦ5 、Ｓ
Ｆ6 、ＳｅＦ、ＳｅＦ4 、ＳｅＦ6 、ＴｅＦ4 、ＴｅＦ
6 などが挙げられる。また、ハロゲン化合物および窒素
以外に除去しうる不純物としては、例えば炭化水素、一
酸化炭素、二酸化炭素、水素、酸素、水蒸気、弗素、塩
素、臭素などである。According to the present invention, helium, neon, argon containing at least a halogen compound and nitrogen as impurities,
It is applied to the purification of noble gases such as krypton and xenon. The halogen compounds to be removed include hydrogen halides, carbon halides, halogenated hydrocarbons and halides of 6B group elements, mainly fluorine and chlorine type halogen compounds, and 6B group elements include sulfur, Such as selenium or tellurium. For example, hydrogen halides such as HCl and HF, carbon halides such as CF 4 and CCl 4 , CHF 3 , C 2 H 2 F 4 , CHCl 3 and C 2 H 2 C
For halogenated hydrocarbons such as l 4 and halides of 6B group elements, SF, SF 2 , SF 4 , SF 5 , S
F 6 , SeF, SeF 4 , SeF 6 , TeF 4 , TeF
6 and so on. In addition to halogen compounds and nitrogen, impurities that can be removed are, for example, hydrocarbons, carbon monoxide, carbon dioxide, hydrogen, oxygen, water vapor, fluorine, chlorine, bromine and the like.
【０００９】本発明において、カルシウムまたはマグネ
シウムのゲッター材による処理に先立って希ガスと接触
せしめられるジルコニウムまたはチタン系のゲッター材
（以下ゲッター材Ａと記す）は少くとも窒素を効率よく
除去しうるものであり、ジルコニウム、チタンまたはジ
ルコニウムとチタン、バナジウム、鉄、ニッケル、クロ
ム、コバルトなどの合金が使用される。合金では例えば
Ｚｒ−Ｔｉ、Ｚｒ−Ｆｅ、Ｚｒ−Ｖ、Ｚｒ−Ｖ−Ｆｅ、
Ｚｒ−Ｖ−Ｎｉ、Ｚｒ−Ｖ−Ｃｒなどの二元または多元
合金が好ましい。これらの金属および合金は、粒状また
は１００メッシュ以上の微細粒で用いるか、１００メッ
シュ程度の微細粒としたものをペレット状などに成型し
た形態で使用される。また精製に先立って、あらかじめ
真空中または希ガス中で、例えば４００〜９５０℃程度
で１０〜２００分間活性化処理を施すことが好ましい。In the present invention, a zirconium- or titanium-based getter material (hereinafter referred to as getter material A) which is brought into contact with a rare gas prior to treatment with a calcium or magnesium getter material can remove nitrogen at least efficiently. And zirconium, titanium or an alloy of zirconium and titanium, vanadium, iron, nickel, chromium, cobalt or the like is used. For alloys, for example, Zr-Ti, Zr-Fe, Zr-V, Zr-V-Fe,
Binary or multi-component alloys such as Zr-V-Ni and Zr-V-Cr are preferred. These metals and alloys are used in the form of granules or fine particles of 100 mesh or more, or in the form of pellets formed by making fine particles of about 100 mesh. Further, prior to the purification, it is preferable to carry out an activation treatment in advance in vacuum or in a rare gas at, for example, about 400 to 950 ° C. for 10 to 200 minutes.
【００１０】また、カルシウムまたはマグネシウム系の
ゲッター材（以下ゲッター材Ｂと記す）としては、カル
シウムの単体またはマグネシウムの単体が好ましいが、
両者を混合したものであってもよい。通常は市販のカル
シウム、マグネシウムを使用することができ、粒状また
は１００メッシュ以上の微細粒で用いるか、１００メッ
シュ程度の微細粒としたものをペレット状に成型した形
態などで使用される。ゲッター材Ｂについても精製に先
立って、あらかじめ真空中または希ガス中において、例
えば４００〜８００℃程度で１０〜２００分間活性化処
理を施すことが好ましい。The calcium or magnesium-based getter material (hereinafter referred to as getter material B) is preferably calcium alone or magnesium alone.
It may be a mixture of both. Usually, commercially available calcium and magnesium can be used, and they are used in the form of granules or fine particles of 100 mesh or more, or formed into pellets by making fine particles of about 100 mesh. Prior to purification, the getter material B is also preferably subjected to an activation treatment in advance in vacuum or in a rare gas at, for example, about 400 to 800 ° C. for 10 to 200 minutes.
【００１１】希ガスの精製に際しては、ゲッター材Ａが
精製筒の入口側に、ゲッター材Ｂが出口側に充填され、
精製筒を所定の温度に加熱しながら原料希ガスが流され
る。接触温度は希ガス中に含まれる不純物の種類、濃
度、ゲッター材の種類などによって異なり一概に特定は
できないが、ゲッター材Ａでは、通常は３００〜９００
℃、好ましくは４００〜８５０℃である。接触温度が９
００℃を超えると不純物としてハロゲン化合物が含まれ
ているとゲッター材Ａの金属との反応による生成物が気
化し、下流で詰まりを生ずる恐れがあり、３００℃より
も低くなると不純物の除去能力が低下する恐れがある。In refining the rare gas, the getter material A is filled in the inlet side of the refining cylinder, and the getter material B is filled in the outlet side.
The raw material rare gas is caused to flow while heating the refining cylinder to a predetermined temperature. The contact temperature varies depending on the type and concentration of impurities contained in the rare gas, the type of getter material, etc., and cannot be specified unconditionally, but in the getter material A, it is usually 300 to 900.
C., preferably 400 to 850.degree. Contact temperature is 9
If the temperature exceeds 00 ° C and the halogen compound is contained as an impurity, the product of the reaction of the getter material A with the metal may be vaporized to cause clogging in the downstream, and if the temperature is lower than 300 ° C, the ability to remove impurities may be reduced. It may decrease.
【００１２】また、ゲッター材Ｂでは、例えば、カルシ
ウムを用いる場合には通常は１５０〜８００℃、好まし
くは４００〜８００℃、マグネシウムを用いる場合には
通常は１５０〜６２０℃、好ましくは３５０〜６２０℃
の範囲で選択される。接触温度が１５０℃よりも低いと
含有される不純物の種類などによっては除去能力が低下
する。本発明において、ゲッター材ＡおよびＢは、通常
は前記のように同じ精製筒に充填されるが、ハロゲン化
合物の不純物の種類などによってはゲッター材をそれぞ
れ別の精製筒に充填し、ゲッター材Ａが上流側、ゲッタ
ー材Ｂが下流側となるように連結し、それぞれを所望の
温度に設定して精製をおこなってもよい。In the getter material B, for example, when calcium is used, it is usually 150 to 800 ° C., preferably 400 to 800 ° C. When magnesium is used, it is usually 150 to 620 ° C., preferably 350 to 620. ℃
The range is selected. When the contact temperature is lower than 150 ° C., the removing ability is lowered depending on the kind of impurities contained. In the present invention, the getter materials A and B are usually packed in the same purification column as described above, but the getter materials may be filled in different purification columns depending on the type of impurities of the halogen compound. May be connected on the upstream side, and the getter material B may be connected on the downstream side, and each may be set to a desired temperature for purification.
【００１３】次に本発明を図面により例示して、さらに
具体的に説明する。図１は本発明に使用される希ガスの
精製装置のフローシートである。図１において、ガスの
入口１および出口２を有し、下部にゲッター材Ｂが充填
され、その上流にはゲッター材Ａが充填され、且つ、加
熱用ヒーター３が配置された精製筒４の入口１には、原
料希ガスの供給管５、出口２側には冷却器６が接続され
ている。また、冷却器６の下流には精製ガスの抜出し管
７が接続されて希ガスの精製装置となっている。Next, the present invention will be described in more detail with reference to the drawings. FIG. 1 is a flow sheet of a rare gas refining apparatus used in the present invention. In FIG. 1, an inlet 1 and an outlet 2 for gas, a lower portion is filled with a getter material B, an upstream thereof is filled with a getter material A, and an inlet of a purification cylinder 4 in which a heater 3 for heating is arranged. 1, a raw material rare gas supply pipe 5 is connected, and a cooler 6 is connected to the outlet 2 side. A refined gas extraction pipe 7 is connected downstream of the cooler 6 to form a rare gas refiner.
【００１４】希ガスの精製に際しては、加熱用ヒーター
３で精製筒４を所定の温度に加熱した状態で、原料希ガ
スが供給管７から入口を経て精製筒４内に供給される。
精製筒４に入った希ガスは、先ずゲッター材Ａと接触す
ることにより、希ガス中に含まれる窒素がゲッター材Ａ
と反応して確実に除去される。同時にハロゲン化合物以
外の不純物である炭化水素、一酸化炭素、二酸化炭素、
水素、酸素などの一部または大部分も除去される。窒素
が除去されたガスは、ゲッター材Ｂと反応してハロゲン
化合物およびゲッター材Ａで除去されなかった他の不純
物が確実に除去され、出口２を経て冷却器６に入り、こ
こで所定の温度にまで冷却され、精製ガスの吹き出し管
７を経由して目的の用途に供される。When refining the rare gas, the raw material rare gas is supplied from the supply pipe 7 into the refining cylinder 4 through the inlet while the refining cylinder 4 is heated to a predetermined temperature by the heater 3 for heating.
The rare gas that has entered the refining cylinder 4 first comes into contact with the getter material A, so that the nitrogen contained in the rare gas is contained in the getter material A.
Reacts with and is reliably removed. At the same time, hydrocarbons, carbon monoxide, carbon dioxide, which are impurities other than halogen compounds,
Some or most of hydrogen, oxygen, etc. are also removed. The nitrogen-removed gas reacts with the getter material B to surely remove halogen compounds and other impurities not removed by the getter material A, and then enters the cooler 6 through the outlet 2 where a predetermined temperature is reached. It is cooled down to 1, and supplied to the intended use via the purified gas blowing pipe 7.
【００１５】[0015]
実施例１ 図１で示したと同じ構成の装置で、外径１７．３ｍｍ、
内径１４ｍｍのステンレス管製の精製筒に、ハロゲン化
合物除去用のゲッター材Ｂとして市販の粒状カルシウム
（純度９９％）をふるい分けた４〜１０メッシュのもの
を５００ｍｍ、その上流に窒素除去用のゲッター材Ａと
して市販のフェロジルコ合金（鉄２０〜２５重量％、残
部ジルコニウム）で６〜１４メッシュのものを１００ｍ
ｍ充填した。Example 1 An apparatus having the same configuration as shown in FIG. 1 and having an outer diameter of 17.3 mm,
500 mm of 4 to 10 mesh, which is obtained by sieving commercially available granular calcium (purity 99%) as a getter material B for removing halogen compounds into a refining cylinder made of a stainless steel tube with an inner diameter of 14 mm, and a getter material for removing nitrogen upstream thereof. A commercially available ferro zirco alloy (iron 20 to 25% by weight, balance zirconium) having a mesh of 6 to 14 is 100 m.
m filled.
【００１６】引続き、ヘリウム気流中７２０℃で３時間
活性化処理をおこなった後、精製筒の温度を７００℃に
調節して精製をおこなった。不純物として、ハロゲン化
合物中で最も除去が困難な四フッ化炭素（ＣＦ4 ）を１
００ｐｐｍ、六フッ化硫黄（ＳＦ6 ）を３０ｐｐｍ、お
よび差圧増加の原因となっていた窒素を５０ｐｐｍの濃
度になるようにマスフローコントローラを用いてヘリウ
ムガスに添加し、０．８９ＮＬ／ｍｉｎ、圧力４ｋｇｆ
／ｃｍ2 で供給して連続的に精製をおこないながら精製
筒の出口ガスをＴＣＤガスクロマトグラフにより分析し
た。その結果、精製開始から３００時間経過後に四フッ
化炭素の破過を認めたが、この間に、その他の不純物の
破過は認められず、また精製筒出口ガス配管の閉塞も発
生しなかった。また、精製筒の入口と出口の間の差圧
は、精製開始時で０．２ｋｇｆ／ｃｍ2 、四フッ化炭素
の破過時で０．３ｋｇｆ／ｃｍ2 であった。Subsequently, after performing activation treatment at 720 ° C. for 3 hours in a helium gas stream, the temperature of the purification column was adjusted to 700 ° C. for purification. Carbon tetrafluoride (CF 4 ), which is the most difficult to remove among halogen compounds, is used as an impurity.
Add 00 ppm, sulfur hexafluoride (SF 6 ) to 30 ppm, and nitrogen, which was the cause of the increase in differential pressure, to helium gas using a mass flow controller to a concentration of 50 ppm, and add 0.89 NL / min pressure. 4 kgf
The gas at the outlet of the purifying column was analyzed by TCD gas chromatograph while continuously purifying by supplying the gas at a rate of / cm 2 . As a result, breakthrough of carbon tetrafluoride was recognized after 300 hours had passed from the start of purification, but during this period, breakthrough of other impurities was not recognized, and clogging of the purification cylinder outlet gas pipe did not occur. Further, the pressure difference between the inlet and the outlet of the purification column is, 0.2 kgf / cm 2 at the time of purification starting was 0.3 kgf / cm 2 at the time of breakthrough of carbon tetrafluoride.
【００１７】実施例２ カルシウムの代わりに市販の削り状マグネシウム（純度
９７％以上）をハロゲン化物除去のゲッター材Ｂとし、
活性化を６００℃で３時間、精製温度を５００℃とした
他は実施例１と同様にして精製をおこない、精製筒出口
ガスの分析をおこなった。その結果、ガスを流し始めて
から１３０時間後に四フッ化炭素の破過を認めたが、こ
の間に、その他の不純物の破過を認められず、また、精
製筒出口ガス配管の閉塞も発生しなかった。また、精製
筒の入口と出口の間の差圧は、精製開始時で０．２ｋｇ
ｆ／ｃｍ2 、四フッ化炭素の破過時で０．３ｋｇｆ／ｃ
ｍ2 であった。Example 2 Instead of calcium, commercially available shaving magnesium (purity of 97% or more) was used as a getter material B for removing halides.
Purification was performed in the same manner as in Example 1 except that activation was carried out at 600 ° C. for 3 hours and the purification temperature was 500 ° C., and the gas at the outlet of the purification cylinder was analyzed. As a result, breakthrough of carbon tetrafluoride was observed 130 hours after starting to flow the gas, but during this period, breakthrough of other impurities was not observed and clogging of the gas pipe at the outlet of the refining cylinder did not occur. It was Also, the differential pressure between the inlet and outlet of the refining cylinder is 0.2 kg at the start of refining.
f / cm 2 , 0.3 kgf / c when breakthrough of carbon tetrafluoride
It was m 2 .
【００１８】比較例１ 窒素除去用ゲッター材Ａを充填しなかった他は実施例１
と同様にしてヘリウムガスの精製をおこなった。その結
果、精製開始から３００時間経過後に四フッ化炭素の破
過を認めたが、この間に、その他の不純物の破過は認め
られず、また精製筒出口ガス配管の閉塞も発生しなかっ
た。しかしながら、精製筒の入口と出口の間の差圧は精
製開始時で０．２ｋｇｆ／ｃｍ2 であったものが、四フ
ッ化炭素の破過時には１．３ｋｇｆ／ｃｍ2 まで上昇し
た。Comparative Example 1 Example 1 except that the getter material A for nitrogen removal was not filled.
The helium gas was purified in the same manner as in. As a result, breakthrough of carbon tetrafluoride was recognized after 300 hours had passed from the start of purification, but during this period, breakthrough of other impurities was not recognized, and clogging of the purification cylinder outlet gas pipe did not occur. However, those pressure difference between the inlet and the outlet of the purification column was 0.2 kgf / cm 2 at the time of refining the start, at the time of breakthrough of carbon tetrafluoride was increased to 1.3 kgf / cm 2.
【００１９】比較例２ 窒素除去用のゲッター材Ａを充填しなかった他は実施例
２と同様にしてヘリウムガスの精製をおこなった。その
結果、精製開始から１２０時間経過後に四フッ化炭素の
破過を認めたが、この間に、その他の不純物の破過は認
められず、また精製筒出口ガス配管の閉塞も発生しなか
った。しかしながら、精製筒の入口と出口の間の差圧は
精製開始時で０．２ｋｇｆ／ｃｍ2 であったものが、四
フッ化炭素の破過時には１．１ｋｇｆ／ｃｍ2 まで上昇
した。Comparative Example 2 Helium gas was purified in the same manner as in Example 2 except that the getter material A for nitrogen removal was not filled. As a result, breakthrough of carbon tetrafluoride was observed 120 hours after the start of purification, but during this period, breakthrough of other impurities was not observed and clogging of the gas pipe at the outlet of the refining cylinder did not occur. However, those pressure difference between the inlet and the outlet of the purification column was 0.2 kgf / cm 2 at the time of refining the start, at the time of breakthrough of carbon tetrafluoride was increased to 1.1 kgf / cm 2.
【００２０】[0020]
【発明の効果】本発明によって、カルシウム、マグネシ
ウムのゲッター材を単独で用いた場合に問題になってい
た精製筒の差圧の増大を確実に防止できるようになっ
た。従って、不純物としてハロゲン化合物および窒素な
どを含む希ガスをハロゲン化合物の除去能力の大きいカ
ルシウム、マグネシウムのゲッター材を用いて効率よく
長時間連続的に、しかも、高純度に精製することが可能
となった。According to the present invention, it is possible to reliably prevent the increase in the differential pressure in the refining cylinder, which has been a problem when the calcium and magnesium getter materials are used alone. Therefore, it is possible to efficiently purify a rare gas containing a halogen compound and nitrogen as impurities by using a getter material of calcium and magnesium, which has a large ability to remove a halogen compound, continuously for a long time with high purity. It was
【００２１】[0021]
【図１】希ガスの精製装置のフローシートFIG. 1 Flow sheet of rare gas refining equipment
１ 入口 ２ 出口 ３ 加熱用ヒーター ４ 精製筒 ５ 供給管 ６ 冷却器 ７ 抜出し管 Ａ、Ｂ ゲッター材 1 inlet 2 outlet 3 heater for heating 4 refining cylinder 5 supply pipe 6 cooler 7 extraction pipe A, B getter material
Claims (6)
よび窒素を含む希ガスから不純物を除去し、高純度希ガ
スを得る希ガスの精製方法において、希ガスをジルコニ
ウムまたはチタン系のゲッター材と加熱下に接触させ、
次いで、カルシウムまたはマグネシウムのゲッター材と
加熱下に接触させることを特徴とする希ガスの精製方
法。1. A method for purifying a rare gas, which comprises removing impurities from a rare gas containing at least a halogen compound and nitrogen as impurities to obtain a high-purity rare gas, wherein the rare gas is brought into contact with a zirconium- or titanium-based getter material under heating. Let
Next, a method for purifying a rare gas, which comprises contacting with a getter material of calcium or magnesium under heating.
ン化炭素、ハロゲン化炭化水素および６Ｂ族元素のハロ
ゲン化物の１種または２種以上である請求項１に記載の
精製方法。2. The purification method according to claim 1, wherein the halogen compound is one kind or two or more kinds of a hydrogen halide, a carbon halide, a halogenated hydrocarbon and a halide of a Group 6B element.
がジルコニウム、チタン、または、ジルコニウムとチタ
ン、バナジウム、鉄、ニッケル、クロム、コバルトの少
なくとも１種からなる二元または多元合金である請求項
１に記載の精製方法。3. The zirconium- or titanium-based getter material is zirconium, titanium, or a binary or multi-element alloy composed of zirconium and at least one of titanium, vanadium, iron, nickel, chromium, and cobalt. Purification method.
ッター材との接触温度が３００〜９００℃、カルシウム
またはマグネシウムのゲッター材との接触温度が１５０
〜８００℃である請求項１に記載の精製方法。4. The contact temperature between the rare gas and the getter material of zirconium or titanium is 300 to 900 ° C., and the contact temperature between the getter material of calcium or magnesium is 150.
The purification method according to claim 1, wherein the purification temperature is from about 800 ° C.
が、炭化水素、一酸化炭素、二酸化炭素、酸素、水素、
水蒸気、弗素、塩素または臭素の１種または２種以上で
ある請求項１に記載の精製方法。5. Impurities other than halogen compounds and nitrogen are hydrocarbons, carbon monoxide, carbon dioxide, oxygen, hydrogen,
The purification method according to claim 1, which is one or more of steam, fluorine, chlorine, or bromine.
塩素であり、６Ｂ族元素が硫黄、セレンまたはテルルで
ある請求項２に記載の精製方法。6. The purification method according to claim 2, wherein the halogen in the halogen compound is fluorine or chlorine, and the Group 6B element is sulfur, selenium or tellurium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19686593A JPH0733417A (en) | 1993-07-14 | 1993-07-14 | Purifying method for rare gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19686593A JPH0733417A (en) | 1993-07-14 | 1993-07-14 | Purifying method for rare gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0733417A true JPH0733417A (en) | 1995-02-03 |
Family
ID=16364942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19686593A Pending JPH0733417A (en) | 1993-07-14 | 1993-07-14 | Purifying method for rare gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0733417A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299746B1 (en) | 1997-12-23 | 2001-10-09 | Saes Getters, S.P.A. | Getter system for purifying the confinement volume in process chambers |
| JP2004307261A (en) * | 2003-04-07 | 2004-11-04 | Central Glass Co Ltd | Method for refining xenon difluoride |
| JP2011093716A (en) * | 2009-10-27 | 2011-05-12 | Japan Pionics Co Ltd | Method for refining rare gas |
| JP2015071534A (en) * | 2013-10-03 | 2015-04-16 | エア プロダクツ アンド ケミカルズ インコーポレイテッドＡｉｒ Ｐｒｏｄｕｃｔｓ Ａｎｄ Ｃｈｅｍｉｃａｌｓ Ｉｎｃｏｒｐｏｒａｔｅｄ | System and method for xenon recovery |
| EP3176578A1 (en) | 2015-12-01 | 2017-06-07 | Japan Agency for Marine-Earth Science and Technology | Preprocessing apparatus and method for gas analysis |
| JP2017106903A (en) * | 2015-12-01 | 2017-06-15 | 国立研究開発法人海洋研究開発機構 | Pretreatment device for gas analysis and pretreatment method for gas analysis |
-
1993
- 1993-07-14 JP JP19686593A patent/JPH0733417A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299746B1 (en) | 1997-12-23 | 2001-10-09 | Saes Getters, S.P.A. | Getter system for purifying the confinement volume in process chambers |
| JP2004307261A (en) * | 2003-04-07 | 2004-11-04 | Central Glass Co Ltd | Method for refining xenon difluoride |
| JP2011093716A (en) * | 2009-10-27 | 2011-05-12 | Japan Pionics Co Ltd | Method for refining rare gas |
| JP2015071534A (en) * | 2013-10-03 | 2015-04-16 | エア プロダクツ アンド ケミカルズ インコーポレイテッドＡｉｒ Ｐｒｏｄｕｃｔｓ Ａｎｄ Ｃｈｅｍｉｃａｌｓ Ｉｎｃｏｒｐｏｒａｔｅｄ | System and method for xenon recovery |
| CN104550198A (en) * | 2013-10-03 | 2015-04-29 | 气体产品与化学公司 | System and method for xenon recovery |
| US10892132B2 (en) | 2013-10-03 | 2021-01-12 | Versum Materials Us, Llc | System and method for xenon recovery |
| EP3176578A1 (en) | 2015-12-01 | 2017-06-07 | Japan Agency for Marine-Earth Science and Technology | Preprocessing apparatus and method for gas analysis |
| JP2017106903A (en) * | 2015-12-01 | 2017-06-15 | 国立研究開発法人海洋研究開発機構 | Pretreatment device for gas analysis and pretreatment method for gas analysis |
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