JPH0781901A - Method for purifying gaseous hydride or gas obtained by diluting the same - Google Patents
Method for purifying gaseous hydride or gas obtained by diluting the sameInfo
- Publication number
- JPH0781901A JPH0781901A JP5254963A JP25496393A JPH0781901A JP H0781901 A JPH0781901 A JP H0781901A JP 5254963 A JP5254963 A JP 5254963A JP 25496393 A JP25496393 A JP 25496393A JP H0781901 A JPH0781901 A JP H0781901A
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- Prior art keywords
- gas
- hydrogen sulfide
- gaseous
- iron
- oxygen
- 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.)
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- Gas Separation By Absorption (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、不純物として酸素ガス
と硫化水素ガスとを含む気状水素化物またはそれを稀釈
したガスからなる対象ガスから、酸素ガスと硫化水素ガ
スとを同時に除去することにより気状水素化物を精製す
る方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention simultaneously removes oxygen gas and hydrogen sulfide gas from a target gas consisting of a gaseous hydride containing oxygen gas and hydrogen sulfide gas as impurities or a gas obtained by diluting it. The present invention relates to a method for purifying gaseous hydride according to.
【０００２】[0002]
【従来の技術】ホスフィン、モノシラン、アルシンをは
じめとする気状水素化物は、半導体工場において用いる
ガスとして重要である。2. Description of the Related Art Gaseous hydrides such as phosphine, monosilane and arsine are important as gases used in semiconductor factories.
【０００３】これらの気状水素化物は、主としてボンベ
に詰めた状態で取り扱われるが、原材料中に含まれてい
る硫黄に起因して硫化水素が混入したり、製造工程中あ
るいは爾後の取り扱い工程において大気成分である酸素
が混入したりすることを完全には防止できない。These gaseous hydrides are mainly handled in a state of being packed in a cylinder, but hydrogen sulfide is mixed in due to the sulfur contained in the raw material, or in the handling process during or after the manufacturing process. It is not possible to completely prevent mixing of oxygen, which is an atmospheric component.
【０００４】気状水素化物に含まれる酸素や硫化水素は
反応性に富むものであり、気状水素化物を半導体工場で
用いた場合、これらの不純物が原因と見られる半導体製
品の不良が発生することがある。そこで気状水素化物を
使用するときには、これらの不純物を許容限度以下にま
で除去することが必要である。Oxygen and hydrogen sulfide contained in the gaseous hydride are highly reactive, and when the gaseous hydride is used in a semiconductor factory, defects of semiconductor products which are considered to be caused by these impurities occur. Sometimes. Therefore, when using a gaseous hydride, it is necessary to remove these impurities to below the allowable limit.
【０００５】一般のガス中に含まれる酸素は、鉄系反応
剤を用いて除去することが可能である。気状水素化物に
含まれる酸素の除去にかかるものではないが、英国特許
第５５３９９１号には、真空包装またはガス置換包装し
た乾燥製品を入れた容器の雰囲気から残存酸素を常温で
除去するために、水素ガスで処理した活性鉄粉を用いる
技術が示されている。Oxygen contained in general gas can be removed by using an iron-based reactant. Although it is not related to the removal of oxygen contained in a gaseous hydride, British Patent No. 555991 discloses a method for removing residual oxygen from the atmosphere of a container containing a dry product packaged in a vacuum package or a gas displacement package at room temperature. , A technique using activated iron powder treated with hydrogen gas is shown.
【０００６】特開平２−１８８４０８号公報には、粗水
素化物ガスをニッケルのりん化物と接触させて、該粗水
素化物ガス中に含有される酸素を除去する水素化物ガス
の精製方法が開示されている。Japanese Unexamined Patent Publication (Kokai) No. 2-188408 discloses a method for purifying a hydride gas in which a crude hydride gas is brought into contact with nickel phosphide to remove oxygen contained in the crude hydride gas. ing.
【０００７】ガス中に含まれる還元性ガスについては、
たとえば還元性ガスが硫化水素である場合、その硫化水
素を酸化鉄を用いて除去することが原理的には可能であ
る。Regarding the reducing gas contained in the gas,
For example, when the reducing gas is hydrogen sulfide, it is possible in principle to remove the hydrogen sulfide using iron oxide.
【０００８】特開平５−１７０４０５号には、ジシロキ
サンを含有するシランのような不純物含有ガスを、水素
化したゲッタ金属（たとえばＺｒ−Ｖ−Ｆｅゲッタ合
金）に接触させることにより、ジシロキサンを除去する
方法が示されている。In JP-A-5-170405, an impurity-containing gas such as silane containing disiloxane is brought into contact with a hydrogenated getter metal (for example, Zr-V-Fe getter alloy) to form disiloxane. The method of removal is shown.
【０００９】[0009]
【発明が解決しようとする課題】先に述べたように、気
状水素化物には不純物として酸素や硫化水素が含まれる
ことが多いが、不純物が酸素のみである場合は酸素除去
に適した反応剤を充填したカラムを通過させることによ
り、不純物が硫化水素のみである場合は硫化水素除去に
適した反応剤を充填したカラムを通過させることによ
り、それぞれの不純物を除去することができる。As described above, the gaseous hydride often contains oxygen and hydrogen sulfide as impurities, but when the impurities are only oxygen, a reaction suitable for oxygen removal. When the impurities are only hydrogen sulfide by passing through the column filled with the agent, the impurities can be removed by passing through the column filled with the reactant suitable for removing hydrogen sulfide.
【００１０】しかしながら、気状水素化物には酸素ガス
および硫化水素ガスの双方が不純物として含まれること
が多いので、酸素除去に適した反応剤を充填したカラム
を用いた場合には硫化水素の除去を行うことができず、
一方硫化水素の除去に適した反応剤を充填したカラムを
用いた場合には酸素を除去を行うことができない。However, since the gaseous hydride often contains both oxygen gas and hydrogen sulfide gas as impurities, when a column packed with a reagent suitable for oxygen removal is used, hydrogen sulfide removal is performed. Can't do
On the other hand, when a column packed with a reactant suitable for removing hydrogen sulfide is used, oxygen cannot be removed.
【００１１】そこでそのような場合には、酸素除去に適
した反応剤を充填したカラムと、硫化水素除去に適した
反応剤を充填したカラムとを任意の順序で直列に結び、
そこに気状水素化物を通過させることが考えられるが、
そのようにすると、各カラムの反応剤充填部分以外の空
間が無視しえなくなって、使用に際し事前にその空間の
ガスを完全に除去することが難しくなり、また両カラム
の連結操作時に大気が侵入することを防止しえなくな
る。Therefore, in such a case, a column packed with a reagent suitable for oxygen removal and a column packed with a reagent suitable for hydrogen sulfide removal are connected in series in any order.
It is possible to pass gaseous hydride there,
In that case, the space other than the part filled with the reactant in each column cannot be ignored, and it becomes difficult to completely remove the gas in that space before use. Can't be prevented.
【００１２】本発明は、このような背景下において、酸
素ガスおよび硫化水素ガスの双方を不純物として含む気
状水素化物またはそれを稀釈したガスからなる対象ガス
から、酸素ガスと硫化水素ガスとを同時に除去すること
により、気状水素化物を精製する方法を提供することを
目的とするものである。Under such a background, the present invention extracts oxygen gas and hydrogen sulfide gas from a target gas consisting of a gaseous hydride containing both oxygen gas and hydrogen sulfide gas as impurities or a gas obtained by diluting it. It is an object of the present invention to provide a method for purifying a gaseous hydride by removing it at the same time.
【００１３】[0013]
【課題を解決するための手段】本発明の気状水素化物ま
たはそれを稀釈したガスの精製方法は、不純物として酸
素ガスおよび硫化水素ガスを含む気状水素化物またはそ
れを稀釈用ガスで稀釈した対象ガスを、鉄系反応剤を充
填したカラムを通過させることにより、前記対象ガス中
に含まれる酸素ガスおよび硫化水素ガスを同時に除去す
ることを特徴とするものである。A method for purifying a gaseous hydride or a gas obtained by diluting the gaseous hydride according to the present invention comprises a gaseous hydride containing oxygen gas and hydrogen sulfide gas as impurities or a gas for diluting the gaseous hydride. The target gas is passed through a column filled with an iron-based reactant to simultaneously remove oxygen gas and hydrogen sulfide gas contained in the target gas.
【００１４】以下本発明を詳細に説明する。The present invention will be described in detail below.
【００１５】本発明における対象ガスとしては、ホスフ
ィン、アルシン、ジボラン、モノシラン、ジシラン、セ
レン化水素、モノゲルマン、スチビンなどの気状水素化
物からなる単一成分ガス、あるいはこれらのガスを水
素、窒素、アルゴン、ヘリウムなどの稀釈用ガスで稀釈
したガス、さらにはこれらの稀釈ガス中に上記の気状水
素化物の２種以上を混合したガスがあげられる。As the target gas in the present invention, a single component gas composed of a gaseous hydride such as phosphine, arsine, diborane, monosilane, disilane, hydrogen selenide, monogermane and stibine, or these gases are hydrogen and nitrogen. Examples of the gas include a gas diluted with a diluent gas such as argon and helium, and a gas obtained by mixing two or more kinds of the above gaseous hydrides in these diluent gases.
【００１６】この対象ガスには、製造工程あるいは爾後
の取り扱い工程において、不純物として酸素ガスおよび
硫化水素ガスが含まれることが多いが、本発明はそのよ
うな不純物が含まれるガスから酸素ガスおよび硫化水素
ガスを一挙に除去しようとするものである。The target gas often contains oxygen gas and hydrogen sulfide gas as impurities in the manufacturing process or the subsequent handling process. In the present invention, however, oxygen gas and sulfide are contained in the gas containing such impurities. It is intended to remove hydrogen gas all at once.
【００１７】本発明においては、上記の対象ガスを鉄系
反応剤を充填したカラムを通過させることにより、前記
対象ガス中に含まれる酸素ガスおよび硫化水素ガスを同
時に除去する。In the present invention, the above target gas is passed through a column filled with an iron-based reactant to simultaneously remove oxygen gas and hydrogen sulfide gas contained in the target gas.
【００１８】ここで鉄系反応剤用の鉄系材料としては、
鉄、四酸化三鉄、酸化第二鉄、水酸化鉄等やこれらの混
合物、あるいはこれらをゼオライト、アルミナ、活性炭
等に担持させたものが用いられる。鉄系材料は、予め適
当な粒度の粉粒状にしておくことが望ましい。Here, as the iron-based material for the iron-based reactant,
Iron, triiron tetroxide, ferric oxide, iron hydroxide and the like, or a mixture thereof, or those obtained by supporting these on zeolite, alumina, activated carbon or the like are used. It is desirable that the iron-based material be in the form of powder having an appropriate particle size in advance.
【００１９】上記の鉄系材料は、水素ガス中で不完全に
還元して鉄系反応剤となす。このときの還元反応の温度
は２１０〜４００℃、殊に２２０〜３６０℃とすること
が望ましく、還元温度が低すぎるときは還元性が不足し
て酸素ガスの除去量が減少し、一方還元温度が高すぎる
ときは還元過多となって硫化水素の除去量が減少する。
従って、対象ガス中に含まれる酸素ガスおよび硫化水素
ガスの濃度比を考慮して、上記温度範囲の中から最適の
温度条件を採用すればよい。還元時間、水素ガスの流速
や流量については、還元の程度を考慮して適宜に設定す
る。The above iron-based material is incompletely reduced in hydrogen gas to form an iron-based reactant. The temperature of the reduction reaction at this time is preferably 210 to 400 ° C., particularly 220 to 360 ° C. When the reduction temperature is too low, the reducibility is insufficient and the amount of oxygen gas removed decreases, while the reduction temperature When is too high, the amount of hydrogen sulfide removed decreases due to excessive reduction.
Therefore, in consideration of the concentration ratio of oxygen gas and hydrogen sulfide gas contained in the target gas, the optimum temperature condition may be adopted from the above temperature range. The reduction time, the flow rate and flow rate of hydrogen gas are appropriately set in consideration of the degree of reduction.
【００２０】鉄系材料の還元処理は、通常はこれをカラ
ム内に充填した状態で加熱下に水素ガスを通過させる方
法が好適に採用される。還元処理後は、このカラムを封
止し、気状水素化物またはそれを稀釈したガスを充填し
たボンベと使用個所への配管との間に接続すればよい。For the reduction treatment of the iron-based material, usually, a method of passing hydrogen gas under heating while the column is filled with the material is suitably adopted. After the reduction treatment, this column may be sealed and connected between a cylinder filled with a gaseous hydride or a gas obtained by diluting the gaseous hydride and a pipe to a place of use.
【００２１】なお事情が許せば、一旦大容量のカラム中
で鉄系材料の還元処理を行ってから、得られた鉄系反応
剤を取り出して小カラムに充填することもできる。この
場合は、異なる還元温度で処理したものあるいは異なる
組成の鉄系材料を還元処理したものを２種以上混合して
小カラムに充填することもできる。If circumstances allow, the iron-based material may be once subjected to reduction treatment in a large capacity column, and then the obtained iron-based reactant may be taken out and packed in a small column. In this case, it is also possible to mix two or more kinds of materials that have been treated at different reduction temperatures or those that have been subjected to reduction treatment of iron-based materials of different compositions and fill the small column.
【００２２】対象ガスをカラムに通す方法としては、対
象ガスが鉄系反応剤と接触すればいかなる方法でも構わ
ないが、たとえば、配管の入口と出口に目皿のようなも
のを設け、両目皿間の空間に粉粒状の鉄系反応剤を配し
た状態で対象ガスを通す方法が採用される。The target gas may be passed through the column by any method so long as the target gas comes into contact with the iron-based reactant. For example, a pipe plate is provided at the inlet and the outlet of the pipe, and both plate plates are provided. A method of passing the target gas in a state in which a powdery granular iron-based reactive agent is placed in the space between the two is adopted.
【００２３】[0023]
【作用】本発明によれば、不純物として酸素ガスおよび
硫化水素ガスを含む気状水素化物またはそれを稀釈用ガ
スで稀釈した対象ガスを、鉄系反応剤を充填したカラム
を通過させるだけで、酸素ガスと硫化水素ガスとを同時
に除去することができる。この場合、鉄系反応剤は母ガ
スである気状水素化物とは反応しない。According to the present invention, a gaseous hydride containing oxygen gas and hydrogen sulfide gas as impurities or a target gas obtained by diluting it with a diluent gas is passed through a column filled with an iron-based reactant, Oxygen gas and hydrogen sulfide gas can be removed at the same time. In this case, the iron-based reactant does not react with the gaseous hydride that is the mother gas.
【００２４】[0024]
【実施例】次に実施例をあげて本発明をさらに説明す
る。なおいずれの検討例および実施例においても、カラ
ムとしてはＳＵＳ３１６Ｌ製のカラムを用いた。EXAMPLES The present invention will be further described with reference to examples. In addition, a column made of SUS316L was used as a column in any of the examination examples and examples.
【００２５】検討例１〜２ まず、窒素ガス中に含まれる酸素ガスおよびヘリウムガ
ス中に含まれる硫化水素ガスの除去量と、鉄系反応剤を
得るための鉄系材料の還元処理温度との関係を見るため
に、次のような予備実験を行った。Study Examples 1 and 2 First, the removal amount of oxygen gas contained in nitrogen gas and hydrogen sulfide gas contained in helium gas and the reduction treatment temperature of the iron-based material for obtaining the iron-based reactant are To see the relationship, we conducted the following preliminary experiment.
【００２６】検討例１（窒素ガス中の酸素ガスの除去） 還元処理温度を下記のように変更して鉄系材料の還元処
理を行い、鉄系反応剤となした。 (1) 鉄系材料の一例としてのＦｅ2 Ｏ3 0.2ｇを外径6.
35mm×長さ２５mmのカラムに充填し、水素ガスを１１０
ml/minの流速で流しながら、２００℃で３時間加熱して
還元処理を行った。還元処理後は常温にまで放冷した。 (2) 還元処理条件を温度３００℃×３時間としたほか
は、上記(1) の操作を繰り返した。 (3) 還元処理条件を温度４００℃×３時間としたほか
は、上記(1) の操作を繰り返した。Study Example 1 (Removal of Oxygen Gas in Nitrogen Gas) The reduction treatment temperature was changed as follows to reduce the iron-based material to obtain an iron-based reactant. (1) Fe 2 O 3 0.2 g as an example of iron-based material has an outer diameter of 6.
Fill a column of 35 mm x 25 mm in length and fill it with hydrogen gas at 110
The reduction treatment was performed by heating at 200 ° C. for 3 hours while flowing at a flow rate of ml / min. After the reduction treatment, it was left to cool to room temperature. (2) The operation of (1) above was repeated except that the reduction treatment conditions were a temperature of 300 ° C. for 3 hours. (3) The operation of (1) above was repeated except that the reduction treatment condition was a temperature of 400 ° C. for 3 hours.
【００２７】次に、上記(1), (2), (3) のカラムに、２
５ppm の酸素ガスを添加した窒素ガスを 1.2リットル/m
inの流速で通したところ、(1) においては初めから出口
ガス中に酸素ガスが検出され、(2）においては８３分間
にわたって出口ガス中の酸素ガス濃度が0.01ppm 以下と
なり、(3) においては８５分間にわたって出口ガス中の
酸素ガス濃度が0.01ppm 以下となった。Next, in the columns of (1), (2) and (3) above, 2
Nitrogen gas with 5ppm oxygen gas added 1.2 liters / m
Oxygen gas was detected in the outlet gas from the beginning in (1) when passing through at a flow rate of in, and in (2) the oxygen gas concentration in the outlet gas was 0.01 ppm or less over 83 minutes, and in (3) Over 85 minutes, the oxygen gas concentration in the outlet gas became 0.01 ppm or less.
【００２８】検討例２（ヘリウムガス中の硫化水素ガス
の除去） 還元処理温度を種々変更して、鉄系材料の還元処理を行
った。 (1) 鉄系材料の一例としてのＦｅ2 Ｏ3 0.1ｇを外径6.
35mm×長さ２５mmのカラムに充填し、水素ガスを１１０
ml/minの流速で流しながら、２００℃で３時間加熱して
還元処理を行った。還元処理後は常温にまで放冷した。 (2) 還元処理条件を温度３００℃×３時間としたほか
は、上記(1) の操作を繰り返した。 (3) 還元処理条件を温度４００℃×３時間としたほか
は、上記(1) の操作を繰り返した。Study Example 2 (Removal of Hydrogen Sulfide Gas in Helium Gas) The reduction treatment temperature was variously changed to perform reduction treatment of the iron-based material. (1) Fe 2 O 3 0.1 g as an example of an iron-based material has an outer diameter of 6.
Fill a column of 35 mm x 25 mm in length and fill it with hydrogen gas at 110
The reduction treatment was performed by heating at 200 ° C. for 3 hours while flowing at a flow rate of ml / min. After the reduction treatment, it was left to cool to room temperature. (2) The operation of (1) above was repeated except that the reduction treatment conditions were a temperature of 300 ° C. for 3 hours. (3) The operation of (1) above was repeated except that the reduction treatment condition was a temperature of 400 ° C. for 3 hours.
【００２９】次に、上記(1), (2), (3) のカラムに、 1
0.65ppm の硫化水素ガスを添加したヘリウムガスを１６
０ml/minの流速で通したところ、(1) においては９００
分間にわたって出口ガス中の硫化水素ガス濃度が 0.2pp
m 以下となり、(2) においては２６５分間にわたって出
口ガス中の硫化水素ガス濃度が0.2ppm以下となり、(3)
においては１６０分間にわたって出口ガス中の硫化水素
ガス濃度が0.2ppm以下となった。Next, in the columns of (1), (2) and (3) above, 1
16 helium gas added with 0.65 ppm hydrogen sulfide gas
When it was passed at a flow rate of 0 ml / min, it was 900 in (1).
The concentration of hydrogen sulfide gas in the outlet gas is 0.2pp
m or less, and in (2), the hydrogen sulfide gas concentration in the outlet gas becomes 0.2 ppm or less over 265 minutes, (3)
In, the hydrogen sulfide gas concentration in the outlet gas became 0.2 ppm or less for 160 minutes.
【００３０】〈検討例１および２のまとめ〉検討例１お
よび２の結果を次の表１にまとめて示す。また、そのと
きの還元温度と不純物除去量との関係を図１に示す。な
お、鉄系反応剤の単位重量当りの不純物の除去量は、次
の関係式に基いて求めた。 Ｍ＝[(C1-C2)・10-6・ｖ・ｔ] ／（22.4・103 ・ｗ） Ｍ: 鉄系反応剤の単位重量当りの不純物除去量(mol/g) C1: 供給ガス中の不純物の濃度(ppm) C2: 出口ガス中の不純物の濃度(ppm) ｖ: 流速(ml/min) ｔ: C2濃度維持時間(min) ｗ: 鉄系反応剤重量（還元処理前の鉄系材料重量）(g)<Summary of Study Examples 1 and 2> The results of Study Examples 1 and 2 are summarized in Table 1 below. Further, FIG. 1 shows the relationship between the reduction temperature and the amount of impurities removed at that time. The amount of impurities removed per unit weight of the iron-based reactant was calculated based on the following relational expression. M = [(C 1 -C 2 ) ・ 10 -6・ v ・ t] /(22.4 ・ 10 3・ w) M: Impurity removal amount (mol / g) C 1 : per unit weight of iron-based reactant Concentration of impurities in supply gas (ppm) C 2 : Concentration of impurities in outlet gas (ppm) v: Flow rate (ml / min) t: C 2 concentration maintenance time (min) w: Weight of iron-based reactant (reduction Iron-based material weight before treatment) (g)
【００３１】[0031]
【表１】 還 元 温 度 200℃ 300℃ 400℃ O2ガス除去量 (mol/g) 0.00000 0.00056 0.00057 H2S ガス除去量 (mol/g) 0.00067 0.00020 0.00012 [Table 1] Return temperature 200 ℃ 300 ℃ 400 ℃ O 2 gas removal rate (mol / g) 0.00000 0.00056 0.00057 H 2 S gas removal rate (mol / g) 0.00067 0.00020 0.00012
【００３２】表１および図１から、２００℃での還元処
理では硫化水素は除去できるものの、酸素は全く除去で
きないこと、３００℃での還元処理では酸素は除去でき
るが、硫化水素の除去量は相当程度減少すること、４０
０℃での還元処理では酸素は除去できるが、硫化水素の
除去量はさらに減少することがわかる。従って、対象ガ
ス中の酸素と硫化水素の濃度比を考慮して、最適の温度
で還元処理したものを鉄系反応剤として用いればよいこ
とがわかる。From Table 1 and FIG. 1, hydrogen sulfide can be removed by the reduction treatment at 200 ° C., but oxygen cannot be removed at all. Oxygen can be removed by the reduction treatment at 300 ° C., but the amount of hydrogen sulfide removed is A considerable reduction, 40
It can be seen that the reduction treatment at 0 ° C. can remove oxygen, but further reduces the amount of hydrogen sulfide removed. Therefore, it is understood that it is sufficient to use, as the iron-based reactant, the one that has undergone the reduction treatment at the optimum temperature in consideration of the concentration ratio of oxygen and hydrogen sulfide in the target gas.
【００３３】検討例３〜５ 気状水素化物の種類を種々変更して、対象ガス（気状水
素化物またはこれを稀釈用ガスで稀釈したガス）中に含
まれる酸素ガスの除去性を調べる予備実験を行った。Examination Examples 3 to 5 Preliminary examination for examining the removability of oxygen gas contained in a target gas (vapor hydride or gas obtained by diluting this with a diluent gas) by changing various kinds of vapor hydride. An experiment was conducted.
【００３４】検討例３（ホスフィン中の酸素ガスの除
去） Ｆｅ2 Ｏ3 0.1ｇを外径6.35mm×長さ２５mmのカラムに
充填し、水素ガスを１１０ml/minの流速で流しながら、
３００℃で３時間加熱して還元処理を行った。還元処理
後は常温にまで放冷した。Study Example 3 (Removal of oxygen gas in phosphine) 0.1 g of Fe 2 O 3 was packed in a column having an outer diameter of 6.35 mm and a length of 25 mm, and hydrogen gas was flown at a flow rate of 110 ml / min.
A reduction treatment was performed by heating at 300 ° C. for 3 hours. After the reduction treatment, it was left to cool to room temperature.
【００３５】次に上記のカラムに、２５ppm の酸素ガス
を添加したホスフィン１０％を含むヘリウムガスを 1.2
リットル/minの流速で通したところ、出口ガス中の酸素
ガス濃度は0.01ppm 以下となった。Next, helium gas containing 10% of phosphine added with 25 ppm of oxygen gas was added to the above column in an amount of 1.2.
When passing through at a flow rate of liter / min, the oxygen gas concentration in the outlet gas became 0.01 ppm or less.
【００３６】検討例４（アルシン中の酸素ガスの除去） Ｆｅ2 Ｏ3 0.3ｇを外径6.35mm×長さ２５mmのカラムに
充填し、水素ガスを１１０ml/minの流速で流しながら、
３００℃で３時間加熱して還元処理を行った。還元処理
後は常温にまで放冷した。Study Example 4 (Removal of oxygen gas in arsine) 0.3 g of Fe 2 O 3 was packed in a column having an outer diameter of 6.35 mm and a length of 25 mm, and hydrogen gas was flown at a flow rate of 110 ml / min.
A reduction treatment was performed by heating at 300 ° C. for 3 hours. After the reduction treatment, it was left to cool to room temperature.
【００３７】次に上記のカラムに、２５ppm の酸素ガス
を添加したアルシン１０％を含むヘリウムガスを 1.2リ
ットル/minの流速で通したところ、出口ガス中の酸素ガ
ス濃度は0.01ppm 以下となった。Next, when helium gas containing 10% arsine added with 25 ppm oxygen gas was passed through the column at a flow rate of 1.2 liter / min, the oxygen gas concentration in the outlet gas became 0.01 ppm or less. .
【００３８】検討例５（モノシラン中の酸素ガスの除
去） Ｆｅ2 Ｏ3 0.3ｇを外径6.35mm×長さ２５mmのカラムに
充填し、水素ガスを１１０ml/minの流速で流しながら、
３００℃で３時間加熱して還元処理を行った。還元処理
後は常温にまで放冷した。Study Example 5 (Removal of Oxygen Gas in Monosilane) 0.3 g of Fe 2 O 3 was packed in a column having an outer diameter of 6.35 mm and a length of 25 mm, while flowing hydrogen gas at a flow rate of 110 ml / min.
A reduction treatment was performed by heating at 300 ° C. for 3 hours. After the reduction treatment, it was left to cool to room temperature.
【００３９】次に上記のカラムに、２５ppm の酸素ガス
を添加したモノシランガスを 1.2リットル/minの流速で
通したところ、出口ガス中の酸素ガス濃度は0.01ppm 以
下となった。Next, when monosilane gas added with 25 ppm of oxygen gas was passed through the above column at a flow rate of 1.2 liter / min, the oxygen gas concentration in the outlet gas became 0.01 ppm or less.
【００４０】〈検討例３および５のまとめ〉検討例３〜
５から、酸素ガスを含む種々の気状水素化物またはこれ
を稀釈用ガスで稀釈したガスを用いた場合、酸素ガスは
有効に除去されることがわかる。<Summary of Examination Examples 3 and 5> Examination Examples 3 to
From FIG. 5, it can be seen that oxygen gas is effectively removed when various gaseous hydrides containing oxygen gas or a gas obtained by diluting it with a diluent gas is used.
【００４１】検討例６〜８ 母ガス（気状水素化物）そのものが鉄系反応剤と反応す
るかどうかを調べる予備実験を行った。Examination Examples 6 to 8 Preliminary experiments were conducted to examine whether the mother gas (gaseous hydride) itself reacts with the iron-based reactant.
【００４２】検討例６（母ガスとの反応の有無） Ｆｅ2 Ｏ3 1.0ｇを外径12.7mm×長さ１００mmのカラム
に充填し、水素ガスを１１０ml/minの流速で流しなが
ら、３００℃で３時間加熱して還元処理を行った。還元
処理後は常温にまで放冷した。Examination Example 6 (Presence or absence of reaction with mother gas) A column having an outer diameter of 12.7 mm and a length of 100 mm was packed with 1.0 g of Fe 2 O 3 and 300 ° C. while flowing hydrogen gas at a flow rate of 110 ml / min. And reduced for 3 hours. After the reduction treatment, it was left to cool to room temperature.
【００４３】次に上記のカラムに、ホスフィン１０％を
含むヘリウムガスを４５ml/minの流速で通して出口ガス
中のホスフィンの濃度を測定したが、ホスフィン濃度は
１０％で安定しており、鉄系反応剤の発熱なども見られ
なかった。Next, helium gas containing 10% phosphine was passed through the above column at a flow rate of 45 ml / min to measure the concentration of phosphine in the outlet gas. The phosphine concentration was stable at 10%, No exotherm of the system reactant was observed.
【００４４】検討例７（母ガスとの反応の有無） Ｆｅ2 Ｏ3 0.3ｇを外径6.35mm×長さ１００mmのカラム
に充填し、水素ガスを１１０ml/minの流速で流しなが
ら、３００℃で３時間加熱して還元処理を行った。還元
処理後は常温にまで放冷した。Examination Example 7 (presence or absence of reaction with mother gas) 0.3 g of Fe 2 O 3 was packed in a column having an outer diameter of 6.35 mm and a length of 100 mm, and hydrogen gas was flowed at a flow rate of 110 ml / min to 300 ° C. And reduced for 3 hours. After the reduction treatment, it was left to cool to room temperature.
【００４５】次に上記のカラムにアルシン１０％を含む
ヘリウムガスを４５ml/minの流速で通して出口ガス中の
アルシンの濃度を測定したが、アルシン濃度は１０％で
安定しており、鉄系反応剤の発熱なども見られなかっ
た。Next, helium gas containing 10% arsine was passed through the column at a flow rate of 45 ml / min to measure the concentration of arsine in the outlet gas. The arsine concentration was stable at 10%. No exotherm of the reaction agent was observed.
【００４６】検討例８（母ガスとの反応の有無） Ｆｅ2 Ｏ3 0.3ｇを外径6.35mm×長さ１００mmのカラム
に充填し、水素ガスを１１０ml/minの流速で流しなが
ら、３００℃で３時間加熱して還元処理を行った。還元
処理後は常温にまで放冷した。Study Example 8 (Presence or absence of reaction with mother gas) 0.3 g of Fe 2 O 3 was packed in a column having an outer diameter of 6.35 mm and a length of 100 mm, and hydrogen gas was caused to flow at a flow rate of 110 ml / min to 300 ° C. And reduced for 3 hours. After the reduction treatment, it was left to cool to room temperature.
【００４７】次に上記のカラムに、モノシラン１０％を
含むヘリウムガスを４５ml/minの流速で通して出口ガス
中のモノシランの濃度を測定したが、アルシン濃度は１
０％で安定しており、鉄系反応剤の発熱なども見られな
かった。Next, helium gas containing 10% of monosilane was passed through the above column at a flow rate of 45 ml / min to measure the concentration of monosilane in the outlet gas.
It was stable at 0%, and no heat generation of the iron-based reactant was observed.
【００４８】〈検討例６および８のまとめ〉検討例６〜
８から、母ガス（気状水素化物）そのものは鉄系反応剤
と反応しないことがわかる。<Summary of Study Examples 6 and 8> Study Example 6-
It can be seen from 8 that the mother gas (vapor hydride) itself does not react with the iron-based reactant.
【００４９】実施例１〜３ 実施例１ 〈気状水素化物中の酸素ガスおよび硫化水素ガスの除
去〉Ｆｅ2 Ｏ3 0.3ｇを外径6.35mm×長さ２５mmのカラ
ムに充填し、水素ガスを１１０ml/minの流速で流しなが
ら、３００℃で３時間加熱して還元処理を行った。還元
処理後は常温にまで放冷した。Examples 1 to 3 Example 1 <Removal of Oxygen Gas and Hydrogen Sulfide Gas in Gaseous Hydride> 0.3 g of Fe 2 O 3 was packed in a column having an outer diameter of 6.35 mm and a length of 25 mm, and hydrogen gas was charged. Was heated at 300 ° C. for 3 hours while flowing at a flow rate of 110 ml / min for reduction treatment. After the reduction treatment, it was left to cool to room temperature.
【００５０】次に上記のカラムに、２０ppm の酸素ガス
と3.2ppmの硫化水素ガスとを添加したホスフィン５％を
含むヘリウムガスを 1.0リットル/minの流速で通したと
ころ、出口ガス中の酸素ガス濃度は0.01ppm 以下、硫化
水素ガス濃度は0.2ppm以下となった。Next, helium gas containing 5% of phosphine added with 20 ppm of oxygen gas and 3.2 ppm of hydrogen sulfide gas was passed through the above column at a flow rate of 1.0 liter / min. The concentration was 0.01 ppm or less, and the hydrogen sulfide gas concentration was 0.2 ppm or less.
【００５１】実施例２ 〈気状水素化物中の酸素ガスおよび硫化水素ガスの除
去〉Ｆｅ2 Ｏ3 0.3ｇを外径6.35mm×長さ２５mmのカラ
ムに充填し、水素ガスを１１０ml/minの流速で流しなが
ら、３００℃で３時間加熱して還元処理を行った。還元
処理後は常温にまで放冷した。Example 2 <Removal of Oxygen Gas and Hydrogen Sulfide Gas in Gaseous Hydride> 0.3 g of Fe 2 O 3 was packed in a column having an outer diameter of 6.35 mm and a length of 25 mm, and hydrogen gas at 110 ml / min. The reduction treatment was performed by heating at 300 ° C. for 3 hours while flowing at a flow rate. After the reduction treatment, it was left to cool to room temperature.
【００５２】次に上記のカラムに、２０ppm の酸素ガス
と3.2ppmの硫化水素ガスとを添加したアルシン５％を含
むヘリウムガスを 1.0リットル/minの流速で通したとこ
ろ、出口ガス中の酸素ガス濃度は0.01ppm 以下、硫化水
素ガス濃度は0.2ppm以下となった。Next, helium gas containing 5% arsine added with 20 ppm oxygen gas and 3.2 ppm hydrogen sulfide gas was passed through the above column at a flow rate of 1.0 liter / min. The concentration was 0.01 ppm or less, and the hydrogen sulfide gas concentration was 0.2 ppm or less.
【００５３】実施例３ 〈気状水素化物中の酸素ガスおよび硫化水素ガスの除
去〉Ｆｅ2 Ｏ3 0.3ｇを外径6.35mm×長さ２５mmのカラ
ムに充填し、水素ガスを１１０ml/minの流速で流しなが
ら、３００℃で３時間加熱して還元処理を行った。還元
処理後は常温にまで放冷した。Example 3 <Removal of Oxygen Gas and Hydrogen Sulfide Gas in Gaseous Hydride> 0.3 g of Fe 2 O 3 was packed in a column having an outer diameter of 6.35 mm and a length of 25 mm, and hydrogen gas at 110 ml / min. The reduction treatment was performed by heating at 300 ° C. for 3 hours while flowing at a flow rate. After the reduction treatment, it was left to cool to room temperature.
【００５４】次に上記のカラムに、２０ppm の酸素ガス
と3.2ppmの硫化水素ガスとを添加したモノシラン５％を
含むヘリウムガスを 1.0リットル/minの流速で通したと
ころ、出口ガス中の酸素ガス濃度は0.01ppm 以下、硫化
水素ガス濃度は0.2ppm以下となった。Next, helium gas containing 5% of monosilane added with 20 ppm of oxygen gas and 3.2 ppm of hydrogen sulfide gas was passed through the above column at a flow rate of 1.0 liter / min. The concentration was 0.01 ppm or less, and the hydrogen sulfide gas concentration was 0.2 ppm or less.
【００５５】[0055]
【発明の効果】作用の項でも述べたように、本発明の方
法によれば、不純物として酸素ガスおよび硫化水素ガス
を含む気状水素化物またはそれを稀釈用ガスで稀釈した
対象ガスを、鉄系反応剤を充填したカラムを通過させる
だけで、酸素ガスと硫化水素ガスとを同時に除去するこ
とができる。As described in the section of the operation, according to the method of the present invention, a gaseous hydride containing oxygen gas and hydrogen sulfide gas as impurities or a target gas obtained by diluting it with a diluent gas is used. The oxygen gas and the hydrogen sulfide gas can be simultaneously removed only by passing through the column filled with the system reactant.
【００５６】このように、対象ガスを充填したボンベの
吐出口に鉄系反応剤を充填したカラムを接続するだけ
で、高純度の対象ガスを使用個所に供給することが可能
となるので、微量の不純物が問題となっている半導体製
造分野等に貢献することができる。As described above, by simply connecting the column filled with the iron-based reactant to the discharge port of the cylinder filled with the target gas, it becomes possible to supply the high-purity target gas to the use place, so It is possible to contribute to the semiconductor manufacturing field and the like, in which the above impurities are a problem.
【図１】検討例１〜２における還元温度と不純物除去量
との関係を示したグラフである。FIG. 1 is a graph showing the relationship between the reduction temperature and the amount of removed impurities in Study Examples 1 and 2.
Claims (2)
を含む気状水素化物またはそれを稀釈用ガスで稀釈した
対象ガスを、鉄系反応剤を充填したカラムを通過させる
ことにより、前記対象ガス中に含まれる酸素ガスおよび
硫化水素ガスを同時に除去することを特徴とする気状水
素化物またはそれを稀釈したガスの精製方法。1. A gaseous hydride containing oxygen gas and hydrogen sulfide gas as impurities or a target gas obtained by diluting it with a diluting gas is passed through a column filled with an iron-based reactant to obtain a gas in the target gas. A method for purifying a gaseous hydride or a gas obtained by diluting the gaseous hydride, which comprises simultaneously removing oxygen gas and hydrogen sulfide gas contained in.
度２１０〜４００℃にて還元処理したものである請求項
１記載の精製方法。2. The refining method according to claim 1, wherein the iron-based reactant is obtained by subjecting an iron-based material to reduction treatment in hydrogen gas at a temperature of 210 to 400 ° C.
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|---|---|---|---|
| JP5254963A JP2778905B2 (en) | 1993-09-16 | 1993-09-16 | Method for purifying gaseous hydride or gas diluted therefrom |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5254963A JP2778905B2 (en) | 1993-09-16 | 1993-09-16 | Method for purifying gaseous hydride or gas diluted therefrom |
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| Publication Number | Publication Date |
|---|---|
| JPH0781901A true JPH0781901A (en) | 1995-03-28 |
| JP2778905B2 JP2778905B2 (en) | 1998-07-23 |
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|---|---|---|---|
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Cited By (3)
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| WO2000020330A1 (en) * | 1998-10-02 | 2000-04-13 | Aeronex, Inc. | Method and apparatus for purification of hydride gas streams |
| WO2017047731A1 (en) * | 2015-09-17 | 2017-03-23 | 積水化学工業株式会社 | Gas treatment method and apparatus |
| WO2017047730A1 (en) * | 2015-09-17 | 2017-03-23 | 積水化学工業株式会社 | Gas treatment method |
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| JPS5228472A (en) * | 1975-08-29 | 1977-03-03 | Hitachi Ltd | Process for removal of hydrogen sulfides contained in reducing gas use d in iron making apparatus |
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| WO2000020330A1 (en) * | 1998-10-02 | 2000-04-13 | Aeronex, Inc. | Method and apparatus for purification of hydride gas streams |
| US6241955B1 (en) | 1998-10-02 | 2001-06-05 | Aeronex, Inc. | Method and apparatus for purification of hydride gas streams |
| JP2002526369A (en) * | 1998-10-02 | 2002-08-20 | エアロネクス インコーポレイテッド | Method and apparatus for purifying hydride gas streams |
| WO2017047731A1 (en) * | 2015-09-17 | 2017-03-23 | 積水化学工業株式会社 | Gas treatment method and apparatus |
| WO2017047730A1 (en) * | 2015-09-17 | 2017-03-23 | 積水化学工業株式会社 | Gas treatment method |
| JPWO2017047731A1 (en) * | 2015-09-17 | 2018-07-05 | 積水化学工業株式会社 | Gas processing method and apparatus |
| JPWO2017047730A1 (en) * | 2015-09-17 | 2018-07-05 | 積水化学工業株式会社 | Gas processing method |
| US10786782B2 (en) | 2015-09-17 | 2020-09-29 | Sekisui Chemical Co., Ltd. | Gas treatment method |
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