JP2011093716A - Method for refining rare gas - Google Patents
Method for refining rare gas Download PDFInfo
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- JP2011093716A JP2011093716A JP2009246008A JP2009246008A JP2011093716A JP 2011093716 A JP2011093716 A JP 2011093716A JP 2009246008 A JP2009246008 A JP 2009246008A JP 2009246008 A JP2009246008 A JP 2009246008A JP 2011093716 A JP2011093716 A JP 2011093716A
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000007670 refining Methods 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 114
- 239000007789 gas Substances 0.000 claims abstract description 84
- 239000012535 impurity Substances 0.000 claims abstract description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 230000009257 reactivity Effects 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 229910052756 noble gas Inorganic materials 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 229910052786 argon Inorganic materials 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、酸素、及び窒素、炭化水素、一酸化炭素、二酸化炭素、水素、水蒸気から選ばれる１種以上のガスを不純物として含む希ガスを、加熱下でゲッタ材と接触させて、該希ガスに含まれる不純物を除去する希ガスの精製方法に関する。 In the present invention, a rare gas containing oxygen and at least one gas selected from nitrogen, hydrocarbons, carbon monoxide, carbon dioxide, hydrogen, and water vapor as an impurity is brought into contact with a getter material under heating, thereby The present invention relates to a method for purifying a rare gas that removes impurities contained in the gas.
半導体製造工程においては、ヘリウム、アルゴン等の希ガスが頻繁に使用されている。ヘリウム等の希ガスは、工業的には液体空気を分留する方法により製造されているが、これらの希ガスには、二酸化炭素、酸素等が数ｐｐｍ〜数百ｐｐｍ程度含まれている。半導体分野においては、これらの希ガスは、成膜技術の進歩とともに極めて高純度であることが強く要求されているとともに、多量に使用されることから、高純度で連続して半導体製造工程に供給することが可能な希ガスの精製方法が要求されている。 In semiconductor manufacturing processes, rare gases such as helium and argon are frequently used. A rare gas such as helium is industrially produced by a method of fractionating liquid air, and these rare gases contain carbon dioxide, oxygen, etc., in the order of several ppm to several hundred ppm. In the semiconductor field, these rare gases are strongly required to have extremely high purity as the film forming technology advances, and since they are used in large quantities, they are continuously supplied to the semiconductor manufacturing process with high purity. There is a need for a method of purifying a rare gas that can be performed.
このため、従来から不純物を含む希ガス（不活性ガス）を加熱下でゲッタ材と接触させて精製する方法が研究されており、例えばゲッタ材として、（１）鉄５〜４０重量％及び残部ジルコニウムからなる合金ゲッタ材（特開平４−１６００１０）、（２）バナジウム５〜９０重量部及び残部ジルコニウムからなる合金ゲッタ材（特開平５−４８０９）、（３）バナジウム、ジルコニウム、及び鉄からなり重量組成が限定された合金ゲッタ材（特開平２−１１６６０７）等が開発されている。 For this reason, a method for purifying a rare gas (inert gas) containing impurities by heating it in contact with a getter material under heating has been studied. For example, as a getter material, (1) 5 to 40% by weight of iron and the balance Alloy getter material made of zirconium (Japanese Patent Laid-Open No. 4-160010), (2) Alloy getter material made of 5 to 90 parts by weight of vanadium and the remainder zirconium (Japanese Patent Laid-Open No. 5-4809), (3) Made of vanadium, zirconium and iron An alloy getter material (JP-A-2-116607) having a limited weight composition has been developed.
しかしながら、前述のようなゲッタ材を用いて希ガスを精製する際に、希ガスに不純物が多く含まれている場合、ゲッタ材の充填部において圧力損失が徐々に大きくなり、ゲッタ材に不純物の除去能力が残っていても圧力損失が大きくなりすぎて希ガスの精製を中止しなければならないことがあった。
従って、本発明が解決しようとする課題は、圧力損失が大きくなる原因を解明し、希ガスに不純物が多く含まれている場合であっても、圧力損失の上昇を抑制できる精製方法を提供することである。
However, when purifying a rare gas using the getter material as described above, if the rare gas contains a large amount of impurities, the pressure loss gradually increases in the filling portion of the getter material, and the getter material contains impurities. Even if the removal capability remains, the pressure loss becomes so large that the purification of the rare gas has to be stopped.
Therefore, the problem to be solved by the present invention is to elucidate the cause of the increase in pressure loss and to provide a purification method capable of suppressing an increase in pressure loss even when the rare gas contains a large amount of impurities. That is.
本発明者らは、この課題を解決すべく鋭意検討した結果、不純物として酸素が含まれる場合、ゲッタ材と酸素が反応しゲッタ材が粉化することにより、圧力損失の上昇が起こることを見出した。さらに、希ガスを、最初に不純物（酸素）に対する反応性が比較的に低く空隙率が高いゲッタ材と接触させて希ガスから主に酸素を除去した後、不純物（酸素）に対する反応性が比較的に高く空隙率が低いゲッタ材と接触させて効率よく希ガスから主に酸素以外の不純物を除去することにより、圧力損失の上昇を抑制できることを見出し、本発明の希ガスの精製方法に到達した。 As a result of intensive studies to solve this problem, the present inventors have found that when oxygen is contained as an impurity, the getter material and oxygen react to cause the getter material to be pulverized, thereby increasing the pressure loss. It was. In addition, after first removing oxygen from the rare gas by first contacting the rare gas with a getter material having a relatively low reactivity to the impurity (oxygen) and a high porosity, the reactivity to the impurity (oxygen) is compared. Found that the increase in pressure loss can be suppressed by efficiently removing mainly impurities other than oxygen from the noble gas efficiently by contacting with a getter material having a high porosity and a low porosity, and reached the noble gas purification method of the present invention. did.
すなわち本発明は、酸素、及び窒素、炭化水素、一酸化炭素、二酸化炭素、水素、水蒸気から選ばれる１種以上のガスを不純物として含む希ガスを、加熱下でゲッタ材と接触させて、該希ガスに含まれる不純物を除去する希ガスの精製方法であって、不純物を含む希ガスを、第２のゲッタ材よりも不純物に対する反応性が低く空隙率が高い第１のゲッタ材と接触させて該希ガスから酸素を除去した後、第１のゲッタ材よりも不純物に対する反応性が高く空隙率が低い第２のゲッタ材と接触させて該希ガスから酸素以外の不純物を除去することを特徴とする希ガスの精製方法である。 That is, the present invention is a method in which a rare gas containing oxygen and at least one gas selected from nitrogen, hydrocarbons, carbon monoxide, carbon dioxide, hydrogen, and water vapor as an impurity is brought into contact with a getter material under heating. A method for purifying a noble gas that removes impurities contained in a noble gas, wherein the noble gas containing impurities is brought into contact with a first getter material having a lower reactivity to impurities and a higher porosity than the second getter material. Removing oxygen from the rare gas, and then removing impurities other than oxygen from the rare gas by contacting with a second getter material having a higher reactivity to impurities and a lower porosity than the first getter material. This is a characteristic noble gas purification method.
本発明の希ガスの精製方法により、不純物として少なくとも酸素が含まれる希ガスを精製する際に、空筒線速度を比較的に大きく設定しても、圧力損失の上昇を抑制できるようになった。その結果、例えば内径の小さな精製筒を用いても、圧力損失の上昇速度が遅くなり、精製筒の小型化を図ることができるようになった。 According to the method for purifying a rare gas of the present invention, when a rare gas containing at least oxygen as an impurity is purified, an increase in pressure loss can be suppressed even if the cylinder linear velocity is set to be relatively large. . As a result, even if, for example, a purification cylinder having a small inner diameter is used, the rate of increase in pressure loss is reduced, and the purification cylinder can be downsized.
本発明は、酸素、及び窒素、炭化水素、一酸化炭素、二酸化炭素、水素、水蒸気から選ばれる１種以上のガスを不純物として含む希ガスを、加熱下でゲッタ材と接触させて、該希ガスに含まれる不純物を除去する希ガスの精製方法に適用される。本発明に使用される精製装置としては、例えば図１のような精製筒を挙げることができる。本発明における希ガスは、ヘリウム、ネオン、アルゴン、クリプトン、キセノン等であり、不純物として前記のガスが数ｐｐｍ〜数百ｐｐｍ程度含まれる希ガスである。 In the present invention, a rare gas containing oxygen and at least one gas selected from nitrogen, hydrocarbons, carbon monoxide, carbon dioxide, hydrogen, and water vapor as an impurity is brought into contact with a getter material under heating, thereby The present invention is applied to a noble gas purification method for removing impurities contained in a gas. An example of the purification apparatus used in the present invention is a purification cylinder as shown in FIG. The rare gas in the present invention is helium, neon, argon, krypton, xenon, etc., and is a rare gas containing about several ppm to several hundred ppm of the gas as an impurity.
本発明の精製方法においては、精製筒に少なくとも２種類のゲッタ材が充填される。精製筒の上流側に充填される第１のゲッタ材としては、精製筒の下流側に充填される第２のゲッタ材と較べて、不純物（酸素）に対する反応性が低く空隙率が高いゲッタ材が用いられる。このような構成とすることにより、不純物の中でも反応性が高いガスである酸素は、第１のゲッタ材との接触により希ガスから除去され、反応性が低いその他の不純物は、第１のゲッタ材を通過し、第２のゲッタ材との接触により希ガスから除去される。 In the purification method of the present invention, the purification cylinder is filled with at least two types of getter materials. As the first getter material filled on the upstream side of the refining cylinder, the getter material having a low reactivity to impurities (oxygen) and a high porosity as compared with the second getter material filled on the downstream side of the refining cylinder. Is used. With this configuration, oxygen, which is a highly reactive gas among impurities, is removed from the rare gas by contact with the first getter material, and other impurities with low reactivity are removed from the first getter. It passes through the material and is removed from the noble gas by contact with the second getter material.
本発明の精製方法において、第１のゲッタ材としては、例えば、（１）単一の金属からなるゲッタ材、（２）鉄、コバルト、ニッケル、クロム、チタン、アルミニウム等、不純物に対する反応性が低い２種以上の金属から選ばれる合金からなるゲッタ材を挙げることができる。但し、これらは、第２のゲッタ材よりも空隙率を高く設定する必要がある。従って、本発明においては、入手が容易で廉価な単一の金属からなるゲッタ材を用いることが好ましく、さらにスポンジチタン、スポンジジルコニウム等、スポンジ状の単一の金属からなるゲッタ材を用いることがより好ましい。 In the purification method of the present invention, as the first getter material, for example, (1) a getter material made of a single metal, (2) reactivity with impurities such as iron, cobalt, nickel, chromium, titanium, aluminum, etc. Examples thereof include a getter material made of an alloy selected from two or more kinds of low metals. However, it is necessary to set the porosity higher than that of the second getter material. Therefore, in the present invention, it is preferable to use a getter material made of a single metal that is easily available and inexpensive, and further, a getter material made of a sponge-like single metal such as sponge titanium or sponge zirconium is used. More preferred.
また、第２のゲッタ材としては、例えば、ジルコニウム及びバナジウムを含む合金からなるゲッタ材、具体的には、ジルコニウム及びバナジウムのほか、鉄、コバルト、ニッケル、クロム、チタン、及びアルミニウムから選ばれる１種以上の金属を含む合金からなるゲッタ材を挙げることができる。第２のゲッタ材は、第１のゲッタ材より空隙率が小さく設定されたものであり、スポンジ状ではなく、球状、円柱状、角柱状、円筒状、角筒状、または粒状のものを使用することが好ましい。 The second getter material is, for example, a getter material made of an alloy containing zirconium and vanadium, specifically, 1 selected from iron, cobalt, nickel, chromium, titanium, and aluminum in addition to zirconium and vanadium. A getter material made of an alloy containing more than one kind of metal can be given. The second getter material has a lower porosity than the first getter material, and is not spongy, but a spherical, cylindrical, prismatic, cylindrical, rectangular tube, or granular material is used. It is preferable to do.
本発明の精製方法を実施する際には、通常は図１に示すような上流側に第１のゲッタ材の充填部２、下流側に第２のゲッタ材の充填部３が備えられた精製筒１が用いられるが、各々の充填部を別々に１個ずつ備えた２個の精製筒を用いることもできる。尚、図１のヒータ４は、第１のゲッタ材と第２のゲッタ材を別々に温度コントロールできるように２個設定されているが、１個のヒータで両方のゲッタ材を温度コントロールするように設定してもよい。各々の充填部に第１のゲッタ材と第２のゲッタ材が充填され、ヒータを所定の温度まで上昇させた後、不純物が含まれる希ガスが希ガス導入ライン５から供給され、精製された希ガスが精製希ガス抜出しライン６から得られる。
When carrying out the refining method of the present invention, usually a refining unit provided with a first getter material filling part 2 on the upstream side and a second getter material filling part 3 on the downstream side as shown in FIG. Although the cylinder 1 is used, it is also possible to use two purification cylinders each having one filling portion. The two heaters 4 in FIG. 1 are set so that the temperature of the first getter material and the second getter material can be controlled separately, but the temperature of both getter materials is controlled by one heater. May be set. Each filling portion is filled with the first getter material and the second getter material, and after raising the heater to a predetermined temperature, a rare gas containing impurities is supplied from the rare gas introduction line 5 and purified. A rare gas is obtained from the purified rare
本発明の精製方法により、酸素、及び窒素、炭化水素、一酸化炭素、二酸化炭素、水素、水蒸気から選ばれる１種以上のガスを含む希ガスが、加熱下で第１のゲッタ材と接触すると、主に希ガス中の酸素がゲッタ材と反応し希ガスから除去されるとともに、ゲッタ材が粉化する。しかし、前述のように第１のゲッタ材は空隙率が大きいので、圧力損失の上昇を抑制することができる。次に、希ガスが第２のゲッタ材と接触すると、主に希ガス中の酸素以外の不純物がゲッタ材と反応し希ガスから除去される。酸素以外の不純物がゲッタ材と反応してもゲッタ材は粉化しないので、空隙率が小さくても圧力損失の上昇は起こらない。 When the rare gas containing oxygen and at least one gas selected from nitrogen, hydrocarbon, carbon monoxide, carbon dioxide, hydrogen, and water vapor is brought into contact with the first getter material under heating by the purification method of the present invention. Primarily, oxygen in the rare gas reacts with the getter material and is removed from the rare gas, and the getter material is pulverized. However, since the first getter material has a high porosity as described above, an increase in pressure loss can be suppressed. Next, when the rare gas comes into contact with the second getter material, impurities other than oxygen in the rare gas mainly react with the getter material and are removed from the rare gas. Even if impurities other than oxygen react with the getter material, the getter material is not pulverized. Therefore, even if the porosity is small, the pressure loss does not increase.
尚、本発明の精製方法においては、希ガス精製の際に、第１のゲッタ材の温度を第２のゲッタ材の温度よりも実質的に低くすることにより、第１のゲッタ材の不純物に対する反応性をさらに低下させて、本発明の効果をより向上させることができる。その場合、第１のゲッタ材の温度は、第２のゲッタ材の温度よりも５〜２００℃低くなることが好ましい。具体的には、第１のゲッタ材と希ガスの接触温度は、通常は３００〜７００℃である。 In the refining method of the present invention, the temperature of the first getter material is substantially lower than the temperature of the second getter material during the purification of the rare gas, thereby preventing the impurities of the first getter material. The reactivity can be further reduced, and the effects of the present invention can be further improved. In that case, the temperature of the first getter material is preferably 5 to 200 ° C. lower than the temperature of the second getter material. Specifically, the contact temperature between the first getter material and the rare gas is usually 300 to 700 ° C.
また、本発明の精製方法において、希ガス精製の際の圧力には特に制限はなく、通常は１ＫＰａのような減圧下ないし２ＭＰａ（絶対圧力）のような加圧下で処理可能であるが、通常は常圧ないし１ＭＰａ（絶対圧力）の加圧下で行なわれる。
また、第１のゲッタ材と希ガスの接触時間が、第２のゲッタ材と希ガスの接触時間よりも短く設定することが好ましい。第１のゲッタ材の充填長は、通常は３０〜３００ｍｍ、第２のゲッタ材の充填長は、通常は１００〜１０００ｍｍである。精製の際の希ガスの空筒線速度は、通常は２００ｃｍ／ｓｅｃ以下、好ましくは１００ｃｍ／ｓｅｃ以下である。
In the purification method of the present invention, there is no particular limitation on the pressure during the purification of the rare gas, and the treatment can be usually performed under a reduced pressure such as 1 KPa to a pressurized pressure such as 2 MPa (absolute pressure). Is performed under normal pressure to 1 MPa (absolute pressure).
Further, the contact time between the first getter material and the rare gas is preferably set shorter than the contact time between the second getter material and the rare gas. The filling length of the first getter material is usually 30 to 300 mm, and the filling length of the second getter material is usually 100 to 1000 mm. The empty tube linear velocity of the rare gas during the purification is usually 200 cm / sec or less, preferably 100 cm / sec or less.
次に、本発明を実施例により具体的に説明するが、本発明がこれらにより限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these.
［実施例１］
（精製装置の製作）
第１のゲッタ材として市販のスポンジチタンからなるゲッタ材を用い、第２のゲッタ材として、ジルコニウム７０重量％、バナジウム３０重量％となるように金属を混合し、高周波誘導加熱炉によりアルゴン減圧雰囲気下で溶解して合金塊を製作し、粒径１．７〜４ｍｍに粉砕したゲッタ材を調製した。内径３２ｍｍのステンレス鋼（ＳＵＳ３１６Ｌ）製の図１に示すような構成の精製筒の上流側に、第１のゲッタ材を充填長が５０ｍｍとなるように、下流側に第２のゲッタ材を充填長が４５０ｍｍとなるように充填し、精製筒の内部をアルゴンガスで置換した。
[Example 1]
(Production of purification equipment)
A commercially available getter material made of sponge titanium is used as the first getter material, a metal is mixed so that the second getter material is 70 wt% zirconium and 30 wt% vanadium, and an argon reduced pressure atmosphere is generated by a high frequency induction heating furnace. An alloy lump was manufactured by melting below, and a getter material crushed to a particle size of 1.7 to 4 mm was prepared. The first getter material is filled upstream of a refined cylinder made of stainless steel (SUS316L) having an inner diameter of 32 mm as shown in FIG. 1, and the second getter material is filled downstream so that the filling length is 50 mm. The length was filled to 450 mm, and the inside of the purification cylinder was replaced with argon gas.
（アルゴンの精製試験）
予めアルゴン気流中６００℃でゲッタ材の活性化処理を行なった。次に、ヒータによりゲッタ材を所定の温度に加熱した後、不純物として、酸素２．６ｐｐｍ、窒素５２ｐｐｍ、メタン２．６ｐｐｍ、一酸化炭素２．６ｐｐｍ、二酸化炭素２．６ｐｐｍ、水素２．６ｐｐｍ、水蒸気６５ｐｐｍを含むアルゴンを、希ガス導入ラインから０．４ＭＰａの加圧下１８Ｌ／ｍｉｎの流量で供給した。この間、精製希ガス抜出しラインから排出するガスの一部をサンプリングし、不純物が検出されないことをガスクロマトグラフにより確認するとともに、精製筒の圧力損失を測定した。その結果（時間の経過による圧力損失の増加状況）を図２に示す。尚、アルゴンの精製中、第１のゲッタ材の温度は４８０℃、第２のゲッタ材の温度は５００℃であった。
(Argon purification test)
The getter material was activated in advance at 600 ° C. in an argon stream. Next, after the getter material is heated to a predetermined temperature by a heater, oxygen 2.6 ppm, nitrogen 52 ppm, methane 2.6 ppm, carbon monoxide 2.6 ppm, carbon dioxide 2.6 ppm, hydrogen 2.6 ppm, Argon containing 65 ppm of water vapor was supplied from a rare gas introduction line at a flow rate of 18 L / min under a pressure of 0.4 MPa. During this time, a part of the gas discharged from the purified rare gas extraction line was sampled, and it was confirmed by gas chromatography that no impurities were detected, and the pressure loss of the purification cylinder was measured. The results (increase in pressure loss over time) are shown in FIG. During the purification of argon, the temperature of the first getter material was 480 ° C., and the temperature of the second getter material was 500 ° C.
また、前述のアルゴンの精製試験において、第１のゲッタ材により不純物である酸素が充分に除去されていることを確認するために、第１のゲッタ材のみを充填したほかは前述と同様の精製装置を製作し、前述のアルゴンの精製試験と同様の試験を行なった。アルゴンの精製の際に第１のゲッタ材から排出されるガスを分析した結果、酸素は第１のゲッタ材により９９％以上除去されていることがわかった。尚、酸素以外の不純物については、一酸化炭素、二酸化炭素、水素、及び水蒸気は少量除去されたが、窒素及びメタンはほとんど除去されなかった。 In the above-described argon purification test, the same purification as described above was performed except that only the first getter material was filled in order to confirm that oxygen as an impurity was sufficiently removed by the first getter material. An apparatus was manufactured and a test similar to the above-described argon purification test was performed. As a result of analyzing the gas discharged from the first getter material during the purification of argon, it was found that 99% or more of oxygen was removed by the first getter material. For impurities other than oxygen, a small amount of carbon monoxide, carbon dioxide, hydrogen, and water vapor was removed, but nitrogen and methane were hardly removed.
［実施例２］
実施例１の精製装置の製作において、第１のゲッタ材として市販のスポンジジルコニウムからなるゲッタ材を用いたほかは実施例１と同様にして精製装置を製作した。この精製装置を用いたほかは実施例１と同様にしてアルゴンの精製試験を行なった。その結果、時間の経過による圧力損失の増加状況は、ほぼ実施例１と同様であり、２００００時間経過しても圧力損失の増加は１０ＫＰａ未満であった。尚、この間、精製希ガス抜出しラインから排出するガスから、不純物は検出されなかった。
[Example 2]
In the production of the purification apparatus of Example 1, a purification apparatus was produced in the same manner as in Example 1 except that a commercially available getter material made of sponge zirconium was used as the first getter material. An argon purification test was conducted in the same manner as in Example 1 except that this purification apparatus was used. As a result, the increase in pressure loss over time was almost the same as in Example 1, and the increase in pressure loss was less than 10 KPa even after 20000 hours. During this time, no impurities were detected from the gas discharged from the purified rare gas extraction line.
［実施例３］
実施例１の精製装置の製作において、第１のゲッタ材として市販の球状チタンからなるゲッタ材を用いたほかは実施例１と同様にして精製装置を製作した。第１のゲッタ材の充填層の空隙率は、第２のゲッタ材の空隙率より約１．２倍大きかった。この精製装置を用いたほかは実施例１と同様にしてアルゴンの精製試験を行なった。その結果、時間の経過による圧力損失の増加状況は、実施例１より少し大きかったが、２００００時間経過しても圧力損失の増加は５０ＫＰａ未満であった。尚、この間、精製希ガス抜出しラインから排出するガスから、不純物は検出されなかった。
[Example 3]
In the production of the purification apparatus of Example 1, a purification apparatus was produced in the same manner as in Example 1 except that a commercially available getter material made of spherical titanium was used as the first getter material. The porosity of the packed layer of the first getter material was about 1.2 times larger than the porosity of the second getter material. An argon purification test was conducted in the same manner as in Example 1 except that this purification apparatus was used. As a result, the increase in pressure loss over time was slightly larger than that in Example 1, but the increase in pressure loss was less than 50 KPa even after 20000 hours. During this time, no impurities were detected from the gas discharged from the purified rare gas extraction line.
［実施例４］
実施例１の精製装置の製作において、第２のゲッタ材として、ジルコニウム７０重量％、バナジウム２５重量％、鉄５重量％の合金からなるゲッタ材を調製し用いたほかは実施例１と同様にして精製装置を製作した。この精製装置を用いたほかは実施例１と同様にしてアルゴンの精製試験を行なった。その結果、時間の経過による圧力損失の増加状況は、ほぼ実施例１と同様であり、２００００時間経過しても圧力損失の増加は１０ＫＰａ未満であった。尚、この間、精製希ガス抜出しラインから排出するガスから、不純物は検出されなかった。
[Example 4]
In the manufacture of the refining apparatus of Example 1, the same as in Example 1 except that a getter material made of an alloy of 70 wt% zirconium, 25 wt% vanadium and 5 wt% iron was prepared and used as the second getter material. A refining device was manufactured. An argon purification test was conducted in the same manner as in Example 1 except that this purification apparatus was used. As a result, the increase in pressure loss over time was almost the same as in Example 1, and the increase in pressure loss was less than 10 KPa even after 20000 hours. During this time, no impurities were detected from the gas discharged from the purified rare gas extraction line.
［実施例５］
実施例１の精製装置の製作において、第２のゲッタ材として、ジルコニウム７０重量％、バナジウム２５重量％、チタン５重量％の合金からなるゲッタ材を調製し用いたほかは実施例１と同様にして精製装置を製作した。この精製装置を用いたほかは実施例１と同様にしてアルゴンの精製試験を行なった。その結果、時間の経過による圧力損失の増加状況は、ほぼ実施例１と同様であり、２００００時間経過しても圧力損失の増加は１０ＫＰａ未満であった。尚、この間、精製希ガス抜出しラインから排出するガスから、不純物は検出されなかった。
[Example 5]
In the manufacture of the refining apparatus of Example 1, a getter material made of an alloy of 70% by weight of zirconium, 25% by weight of vanadium and 5% by weight of titanium was prepared and used as the second getter material. A refining device was manufactured. An argon purification test was conducted in the same manner as in Example 1 except that this purification apparatus was used. As a result, the increase in pressure loss over time was almost the same as in Example 1, and the increase in pressure loss was less than 10 KPa even after 20000 hours. During this time, no impurities were detected from the gas discharged from the purified rare gas extraction line.
［比較例１］
実施例１の精製装置の製作において、第１のゲッタ材を用いなかったほかは実施例１と同様にして精製装置を製作した。この精製装置を用いたほかは実施例１と同様にしてアルゴンの精製試験を行なった。その結果、図２に示すように、７０００時間経過した後、圧力損失は急激に増加することが確認された。尚、ゲッタ材には不純物の除去能力が残っていたが、圧力損失増加のためアルゴンの精製を中止した。
[Comparative Example 1]
In the production of the purification apparatus of Example 1, a purification apparatus was produced in the same manner as in Example 1 except that the first getter material was not used. An argon purification test was conducted in the same manner as in Example 1 except that this purification apparatus was used. As a result, as shown in FIG. 2, it was confirmed that the pressure loss increased rapidly after 7000 hours. Although the getter material still had the ability to remove impurities, the purification of argon was stopped due to an increase in pressure loss.
以上のように、本発明の実施例の希ガスの精製方法は、不純物として酸素が含まれる希ガスを精製する際に、空筒線速度を比較的に大きく設定しても、圧力損失の上昇を抑制できることが確認された。 As described above, the method for purifying a rare gas according to the embodiment of the present invention increases the pressure loss even when the cylinder linear velocity is set relatively large when purifying a rare gas containing oxygen as an impurity. It was confirmed that it can be suppressed.
１ 精製筒
２ 第１のゲッタ材の充填部
３ 第２のゲッタ材の充填部
４ ヒータ
５ 希ガス導入ライン
６ 精製希ガス抜出しライン
DESCRIPTION OF SYMBOLS 1 Purifying cylinder 2 Filling part of 1st getter material 3 Filling part of 2nd getter material 4 Heater 5 Noble
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