JPH08245207A - Refining method of substituted hydrazine gas - Google Patents
Refining method of substituted hydrazine gasInfo
- Publication number
- JPH08245207A JPH08245207A JP7077146A JP7714695A JPH08245207A JP H08245207 A JPH08245207 A JP H08245207A JP 7077146 A JP7077146 A JP 7077146A JP 7714695 A JP7714695 A JP 7714695A JP H08245207 A JPH08245207 A JP H08245207A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- hydrazine
- substd
- substituted hydrazine
- hydrazine gas
- 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.)
- Granted
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
Description
【０００１】[0001]
【産業状の利用分野】本発明は置換ヒドラジンガスの精
製方法に関し、さらに詳細にはメチルヒドラジン、エチ
ルヒドラジンなどの置換ヒドラジンガス中に不純物とし
て含有される水分を極低濃度まで除去しうる置換ヒドラ
ジンガスの精製方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying a substituted hydrazine gas, and more specifically, a substituted hydrazine capable of removing water contained as an impurity in a substituted hydrazine gas such as methylhydrazine and ethylhydrazine to an extremely low concentration. The present invention relates to a gas refining method.
【０００２】ヒドラジンおよびその誘導体はロケットの
燃料などとして古くから知られているが、最近に至りメ
チルヒドラジン、エチルヒドラジン、ジメチルヒドラジ
ンなどヒドラジンの水素がアルキル基、アリール基など
で置き換えられたいわゆる置換ヒドラジンが、ガリウム
−窒素（ＧａＮ）のような光半導体素子、窒化チタン
（ＴｉＮ）のような絶縁膜などの原料として使用され始
め、その量が年々増加すると同時に不純物の含有量の極
めて低いものが要求されている。Hydrazine and its derivatives have long been known as rocket fuels, etc., but recently, so-called substituted hydrazine in which hydrogen of hydrazine such as methylhydrazine, ethylhydrazine and dimethylhydrazine is replaced by an alkyl group or an aryl group. However, it is used as a raw material for an optical semiconductor device such as gallium-nitrogen (GaN) and an insulating film such as titanium nitride (TiN), and the amount thereof is increasing year by year, and at the same time, an extremely low content of impurities is required. Has been done.
【０００３】これらの置換ヒドラジンは一般的には常温
で液体であり、ステンレス製ドラムなどの容器に充填さ
れて市販されているが、上記のような目的で半導体や絶
縁膜のなどの製造プロセスに供給する場合には、これら
液体の置換ヒドラジンを適当な温度に加温しながら水
素、窒素などの希釈ガスでバブリングすることによって
気化させ、置換ヒドラジンガスとして流量を制御しなが
ら装置に供給する方法などが採られてる。しかしなが
ら、一般的に市販されている置換ヒドラジン中には水
分、酸素などが不純物として含有されているため、使用
に際してはこれらを確実に除去する必要がある。These substituted hydrazines are generally liquid at room temperature and are commercially available in a container such as a stainless steel drum. However, they are used in the manufacturing process of semiconductors and insulating films for the above-mentioned purposes. When supplied, these liquid substituted hydrazines are vaporized by bubbling with a diluting gas such as hydrogen or nitrogen while heating to an appropriate temperature, and then supplied to the device as a substituted hydrazine gas while controlling the flow rate. Is taken. However, in general, commercially available substituted hydrazine contains water, oxygen and the like as impurities, and therefore, it is necessary to surely remove them before use.
【０００４】[0004]
【従来の技術】従来、ガス中に含まれる水分を除去する
方法としては、ガスを活性アルミナ、シリカゲル、ゼオ
ライトおよび塩化カルシウムなどの脱湿剤と接触させる
方法が知られているが、取扱いおよび再生が容易なこと
などから合成ゼオライトが多く用いられている。中でも
吸着力の強さから、特にモレキュラーシーブ４Ａ、５Ａ
（米、ユニオンカーバイド社）、あるいはハイシリカゼ
オライトＴＳＺ−６００ＨＯＥ（東ソー（株））など細
孔径の大きめのものが主流であり、これらの吸着剤によ
って一般的なガスについては露点が−８０℃、さらには
それ以下のような低い値になるまで水分を除去すること
が可能である。2. Description of the Related Art Conventionally, as a method of removing water contained in a gas, a method of contacting the gas with a dehumidifying agent such as activated alumina, silica gel, zeolite and calcium chloride has been known. Synthetic zeolite is often used because it is easy to do. Above all, the molecular sieves 4A and 5A are particularly strong due to their strong adsorption power.
(US, Union Carbide Co., Ltd.), or high silica zeolite TSZ-600HOE (Tosoh Corp.) with a larger pore size is the mainstream, and due to these adsorbents, the dew point of a general gas is -80 ° C. Furthermore, it is possible to remove water until the value becomes lower than that.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
の吸着剤は水分を効率よく除去しうる反面、精製の対象
となる置換ヒドラジンガスをも同時に相当量吸着するた
め、精製の開始時には精製筒出口ガス中の置換ヒドラジ
ン濃度が一時的に低下し、本来の濃度（精製筒入口と同
じ濃度）に回復するまでにかなりの時間を要するという
問題点がある。そして、原料ガス中の置換ヒドラジンの
濃度が低いほど回復には長時間を要し、また、吸着剤の
交換操作時などには多量に吸着された置換ヒドラジンが
脱着する虞れがあるため、これらの取扱に対する安全上
の問題点もあった。However, while these adsorbents can efficiently remove water, they also adsorb a considerable amount of the substituted hydrazine gas that is the object of purification, so at the start of purification, the gas at the outlet of the purification column There is a problem that the concentration of the substituted hydrazine therein temporarily decreases and it takes a considerable time to recover to the original concentration (the same concentration as the inlet of the purifying cylinder). And, the lower the concentration of the substituted hydrazine in the raw material gas, the longer the time required for the recovery, and the larger the amount of the substituted hydrazine adsorbed during the exchange operation of the adsorbent may be desorbed. There was also a safety issue with the handling of.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、置換ヒド
ラジンガス中に含有される水分を極低濃度まで効率よく
除去するとともに精製を始めてから短時間で出口ガス中
の置換ヒドラジンを本来の濃度に回復させるべく鋭意研
究を重ねた結果、特定の細孔径の合成ゼオライトを用い
ることにより、水分は吸着するが置換ヒドラジンガスを
吸着し難いことを見出し本発明を完成した。すなわち本
発明は、置換ヒドラジンガスを細孔径が３Å相当の合成
ゼオライト系の吸着剤と接触させて、該置換ヒドラジン
ガス中に含有される水分を除去することを特徴とする置
換ヒドラジンガスの精製方法である。The inventors of the present invention efficiently remove the water contained in the substituted hydrazine gas to an extremely low concentration and at the same time remove the substituted hydrazine in the outlet gas in a short time after starting the purification. As a result of intensive studies to restore the concentration, the inventors have found that the use of a synthetic zeolite having a specific pore size allows water to be adsorbed, but it is difficult to adsorb a substituted hydrazine gas, thereby completing the present invention. That is, the present invention provides a method for purifying a substituted hydrazine gas, which comprises contacting the substituted hydrazine gas with a synthetic zeolite-based adsorbent having a pore diameter of 3Å to remove water contained in the substituted hydrazine gas. Is.
【０００７】本発明は置換ヒドラジン単独、あるいは、
窒素、アルゴン、ヘリウム、ネオンのような不活性ガス
および水素などで希釈された置換ヒドラジン（以下総称
して置換ヒドラジンガスと記す）中に含有される水分の
除去に適用される。The present invention is a substituted hydrazine alone or
It is applied to remove water contained in a substituted hydrazine diluted with an inert gas such as nitrogen, argon, helium, or neon and hydrogen (hereinafter collectively referred to as a substituted hydrazine gas).
【０００８】本発明において、精製の対象となる置換ヒ
ドラジンとしてはヒドラジン〔Ｎ2Ｈ4 〕の水素がアル
キル基またはアリール基で置換された一般化学式〔Ｒn
Ｎ2Ｈ4-n ；式中「Ｒ」はアルキル基またはアリール
基、「n 」は１〜４の正の整数〕で示されるものある
が、主に一置換ヒドラジン（ＲＮ2 Ｈ3 ）および二置換
ヒドラジン（Ｒ2 Ｎ2 Ｈ2 ）である。In the present invention, as the substituted hydrazine to be purified, hydrazine [N 2 H 4 ] in which hydrogen is substituted with an alkyl group or an aryl group is represented by the general formula [R n
N 2 H 4−n ; in the formula, “R” is an alkyl group or an aryl group, and “ n ” is a positive integer of 1 to 4, and is mainly a monosubstituted hydrazine (RN 2 H 3 ) and It is a di-substituted hydrazine (R 2 N 2 H 2 ).
【０００９】一置換ヒドラジンとしては、例えばメチル
ヒドラジン〔ＣＨ3 Ｎ2 Ｈ3 〕、エチルヒドラジン〔Ｃ
2 Ｈ5 Ｎ2 Ｈ3 〕、フェニルヒドラジン〔Ｃ6 Ｈ5 Ｎ2
Ｈ3〕など、また、二置換ヒドラジンとしては、例え
ば、１，２ジメチルヒドラジン〔ＣＨ3 Ｎ2 Ｈ2 Ｃ
Ｈ3 〕、１，１ジメチルヒドラジン〔（ＣＨ3 ）2 Ｎ2
Ｈ2〕、１，２ジエチルヒドラジン〔Ｃ2 Ｈ5 Ｎ2 Ｈ2
Ｃ2 Ｈ5 〕、１，１ジエチルヒドラジン〔（Ｃ2 Ｈ5 ）
2 Ｎ2 Ｈ2 〕などがある。これらのうちでも比較的沸点
が低く気化しやすく、また、入手も容易なことなどから
前記のような用途に対しては、メチルヒドラジン、エチ
ルヒドラジン、１，２ジメチルヒドラジンおよび１，１
ジメチルヒドラジンなどが一般的に多く用いられる。Examples of monosubstituted hydrazines include methylhydrazine [CH 3 N 2 H 3 ], ethylhydrazine [C
2 H 5 N 2 H 3 ], phenylhydrazine [C 6 H 5 N 2
H 3 ], and examples of the disubstituted hydrazine include 1,2 dimethylhydrazine [CH 3 N 2 H 2 C
H 3 ], 1,1-dimethyl hydrazine [(CH 3 ) 2 N 2
H 2 ], 1,2-diethylhydrazine [C 2 H 5 N 2 H 2
C 2 H 5 ], 1,1-diethylhydrazine [(C 2 H 5 ).
2 N 2 H 2 ]. Among them, methylhydrazine, ethylhydrazine, 1,2 dimethylhydrazine and 1,1 are suitable for the above-mentioned applications because they have a relatively low boiling point and are easily vaporized and easily available.
Dimethylhydrazine and the like are commonly used.
【００１０】本発明に使用される吸着剤は化学的には合
成結晶アルミノ・シリケート含水ナトリウム塩のナトリ
ウムの一部をカリウムで置換した合成ゼイライト（通
称、モレキュラーシーブ）であり、その細孔径が３Å
（オングストローム）にほぼ揃っていることが特徴であ
る。このため、ヒドラジンガスをほとんど吸着すること
なく水分のみを選択的に、かつ、低濃度まで吸着除去す
ることができる。この条件に適合する市販の合成ゼオラ
イトとしては、モレキュラーシーブ３Ａ（米、ユニオン
カーバイド社またはユニオン昭和（株））、ゼオラム３
Ａ（東ソー（株））などが挙げられる。The adsorbent used in the present invention is chemically synthetic zeylite (commonly called molecular sieve) in which a part of sodium in synthetic crystalline alumino-silicate hydrous sodium salt is replaced with potassium, and the pore size thereof is 3Å.
The feature is that they are almost the same (Angstrom). Therefore, it is possible to selectively adsorb and remove only the water to a low concentration without adsorbing the hydrazine gas. Commercially available synthetic zeolites that meet these conditions are molecular sieve 3A (US, Union Carbide Co. or Union Showa Co., Ltd.), Zeolum 3
A (Tosoh Corporation) and the like can be mentioned.
【００１１】置換ヒドラジンガスの発生およびユースポ
イントへの供給方法としては、例えば、液体の置換ヒ
ドラジンをボトルなどの容器に入れ、恒温槽に浸して適
当な温度に加温し、気化させたガスをそのまま、また
は、気化ガスを水素、窒素などで希釈し、マスフローコ
ントローラーなどで流量を制御しながら供給する方法、
あるいは、置換ヒドラジンをバブラーに入れ、所定の
温度に保ちながら水素、窒素、アルゴンなどによりバブ
リングしながら気化させ、置換ヒドラジンガスとして流
量を制御しながら供給する方法などがある。置換ヒドラ
ジンを半導体製造工程などに供給する場合にはのバブ
リングにより不活性ガスや水素などで希釈する方法が一
般的に用いられる。As a method of generating the substituted hydrazine gas and supplying it to the point of use, for example, a liquid substituted hydrazine is placed in a container such as a bottle, immersed in a constant temperature bath, heated to an appropriate temperature, and vaporized gas is used. As is, or by diluting the vaporized gas with hydrogen, nitrogen, etc. and supplying it while controlling the flow rate with a mass flow controller etc.,
Alternatively, there is a method in which a substituted hydrazine is placed in a bubbler, vaporized while bubbling with hydrogen, nitrogen, argon, etc. while maintaining a predetermined temperature, and is supplied as a substituted hydrazine gas while controlling the flow rate. When supplying substituted hydrazine to a semiconductor manufacturing process or the like, a method of diluting with an inert gas or hydrogen by bubbling is generally used.
【００１２】置換ヒドラジンガスの精製は、通常は、吸
着剤が充填された精製筒に置換ヒドラジンガスを流すこ
とによっておこなわれ、ガス中に不純物として含有され
る水分が合成ゼオライト系の吸着剤によって除去され
る。精製筒に充填される吸着剤の充填長は、実用上通常
は５０〜１５００ｍｍである。充填長が５０ｍｍよりも
短くなると水分除去率が低下する虞れがあり、一方１５
００ｍｍよりも長くなると圧力損失が大きくなる虞れが
ある。Purification of the substituted hydrazine gas is usually carried out by flowing the substituted hydrazine gas through a purification column filled with an adsorbent, and water contained as an impurity in the gas is removed by a synthetic zeolite adsorbent. To be done. The packing length of the adsorbent packed in the purification column is usually 50 to 1500 mm in practical use. If the filling length is shorter than 50 mm, the water removal rate may decrease.
If it is longer than 00 mm, the pressure loss may increase.
【００１３】精製時の置換ヒドラジンガスの空筒線速度
は（ＬＶ）は供給される置換ヒドラジンガス中に含まれ
る水分の濃度および操作条件などによって異なり一概に
特定はできないが、通常は１０ｃｍ／ｓｅｃ以下、好ま
しくは３ｃｍ／ｓｅｃ以下とされる。置換ヒドラジンガ
スと吸着剤の接触温度は通常は常温でよく、特に加熱や
冷却は必要としない。また、精製時の圧力は２０Ｋｇ／
ｃｍ2 ａｂｓ以下、好ましくは０．１〜１０Ｋｇ／ｃｍ
2 ａｂｓ程度で操作される。The hollow linear velocity (LV) of the substituted hydrazine gas during purification varies depending on the concentration of water contained in the supplied substituted hydrazine gas and operating conditions, and cannot be specified unconditionally, but is usually 10 cm / sec. The following is preferably 3 cm / sec or less. The contact temperature between the substituted hydrazine gas and the adsorbent is usually room temperature, and heating or cooling is not particularly required. The pressure during purification is 20 kg /
cm 2 abs or less, preferably 0.1 to 10 kg / cm
It is operated at about 2 abs.
【００１４】本発明において、合成ゼオライトによる水
分除去工程に、必要に応じてニッケル、銅など金属系の
脱酸素触媒を用いた酸素除去工程を適宜組み合わせるこ
とも可能であり、これによって水分と同時に酸素も完全
に除去され、極めて高純度の精製置換ヒドラジンガスを
得ることができる。In the present invention, it is possible to appropriately combine an oxygen removing step using a metal-based deoxidizing catalyst such as nickel or copper with a water removing step using a synthetic zeolite. Is completely removed, and an extremely high-purity purified substituted hydrazine gas can be obtained.
【００１５】[0015]
実施例１〜４ 吸着剤として市販のモレキュラーシーブ３Ａ〔ユニオン
昭和（株）製、（１／１６ｉｎ．φ）ペレット品、細孔
径約３Å〕を使用した。この吸着剤４２．２ｍｌを内径
１６．４ｍｍ、長さ４００ｍｍのＳＵＳ３１６製の吸着
筒に２００ｍｍ（充填密度０．７０ｇ／ｍｌ）充填し、
これに、乾燥窒素ガスを温度２５０℃、流量６３３ｍｌ
／ｍｉｎ（ＬＶ＝５ｃｍ／ｓｅｃ）で３時間流して活性
化処理をおこない、吸着されている水分を除去した後、
常温に冷却した．Examples 1 to 4 Commercially available molecular sieve 3A [manufactured by Union Showa Co., Ltd. ((1/16 in.φ) pellet product, pore size about 3Å] was used as an adsorbent. 42.2 ml of this adsorbent was filled in an adsorption cylinder made of SUS316 having an inner diameter of 16.4 mm and a length of 400 mm for 200 mm (filling density 0.70 g / ml),
Dry nitrogen gas at a temperature of 250 ° C and a flow rate of 633 ml.
/ Min (LV = 5 cm / sec) for 3 hours for activation to remove adsorbed water,
It was cooled to room temperature.
【００１６】この精製筒に不純物として水分を含有する
種々の置換ヒドラジンガスを室温下（２０〜２５℃) に
窒素でバブリングし、２．０ｖｏｌ％になるように希釈
しながら、全流量６３３ｍｌ／ｍｉｎ（ＬＶ＝５．０ｃ
ｍ／ｓｅｃ）で流して出口ガス中の置換ヒドラジンガス
の濃度を測定したところ、いずれも２０分以内で本来の
濃度（入口と同じ２．０ｖｏｌ％）に達した。同時に出
口精製ガスの露点を静電容量式露点計で測定したとこ
ろ、露点はいずれも−８５℃以下であり、この状態で３
０分間精製を続けたが露点は変化しなかった。それぞれ
の結果を表１に示す。A variety of substituted hydrazine gas containing water as an impurity was bubbled through the purifying column with nitrogen at room temperature (20 to 25 ° C.), and the total flow rate was 633 ml / min while diluting to 2.0 vol%. (LV = 5.0c
m / sec) and the concentration of the substituted hydrazine gas in the outlet gas was measured. As a result, all reached the original concentration (2.0 vol% same as the inlet) within 20 minutes. At the same time, when the dew point of the outlet purified gas was measured by a capacitance type dew point meter, the dew points were all -85 ° C or lower.
Purification was continued for 0 minutes, but the dew point did not change. The respective results are shown in Table 1.
【００１７】[0017]
【表１】 表 １ 実施例 ガスの種類 露 点（℃） 所定濃度到達 番 号 入 口 出 口 時間（ｍｉｎ） １ ＣＨ3 Ｎ2 Ｈ3 −２８ −８６ ＜１８ ２ Ｃ2 Ｈ5 Ｎ2 Ｈ3 −２８ −８６ ＜１８ ３ ＣＨ3 Ｎ2 Ｈ2 ＣＨ3 −２７ −８５ ＜２０ ４ （ＣＨ3 ）2 Ｎ2 Ｈ2 −２６ −８５ ＜２０[Table 1] Table 1 Examples Gas type Dew point (° C) Predetermined concentration reached Number Inlet Outlet time (min) 1 CH 3 N 2 H 3 -28-86 <182 C 2 H 5 N 2 H 3 −28 −86 <18 3 CH 3 N 2 H 2 CH 3 −27 −85 <20 4 (CH 3 ) 2 N 2 H 2 −26 −85 <20
【００１８】比較例１〜４ モレキュラーシーブ５Ａ〔ユニオン昭和（株）製、（１
／１６ｉｎ．φ）ペレット品、細孔径約５Å〕４２．２
ｍｌを実施例におけると同じ精製筒に２００ｍｍ充填
（充填密度０．７０ｇ／ｍｌ）し、乾燥窒素ガスを３５
０℃で３時間流して活性化処理をおこなった後、常温に
冷却した。この精製筒に実施例１で用いたと同じ窒素ベ
ースの種々の置換ヒドラジンガス（２ｖｏｌ％）を６３
３ｍｌ／ｍｉｎ（ＬＶ＝５．０ｃｍ／ｓｅｃ）で流して
出口ガス中の置換ヒドラジンが本来の濃度（２ｖｏｌ
％）に達するまでの時間を測定したところ１〜３時間を
要した。結果を第２表に示す。Comparative Examples 1 to 4 Molecular Sieve 5A (manufactured by Union Showa Co., Ltd., (1
/ 16 in. φ) Pellets, pore size approx. 5Å] 42.2
The same purification cylinder as in Example was filled with 200 ml (packing density 0.70 g / ml), and dry nitrogen gas was supplied to 35 ml.
After activating by flowing at 0 ° C. for 3 hours, it was cooled to room temperature. 63% of the same nitrogen-based substituted hydrazine gas (2 vol%) as used in Example 1 was added to the purification column.
Flowing at 3 ml / min (LV = 5.0 cm / sec), the substituted hydrazine in the outlet gas has the original concentration (2 vol).
%), It took 1 to 3 hours. The results are shown in Table 2.
【００１９】比較例５〜８ ハイシリカゼオライト〔東ソー（株）製、ＴＳＺ−６０
０ＨＯＥ（１．８ｍｍφ）ペレット品〕４２．２ｍｌを
実施例と同様の精製筒に２００ｍｍ充填（充填密度０．
７３ｇ／ｍｌ、細孔径５Å）し、乾燥窒素ガスを３５０
℃で３時間流して活性化させた後室温に冷却した。この
精製筒に不純物として水分を含有する２ｖｏｌ％の種々
の置換ヒドラジンガス（窒素ベース）６３３ｍｌ／ｍｉ
ｎ（ＬＶ＝５．０ｃｍ／ｓｅｃ）流して出口精製ガス中
の置換ヒドラジンが本来の濃度に達するまでの時間と露
点を測定した。 結果を表２に示す。Comparative Examples 5-8 High Silica Zeolite [TSZ-60, manufactured by Tosoh Corporation]
0HOE (1.8 mmφ) pellet product] 42.2 ml was packed in a purifying cylinder similar to that of the embodiment for 200 mm (packing density:
73 g / ml, pore size 5Å) and dry nitrogen gas at 350
After flowing for 3 hours at ℃ to activate, it was cooled to room temperature. 2 vol% of various substituted hydrazine gas (nitrogen base) 633 ml / mi containing water as an impurity in this purification column
After flowing n (LV = 5.0 cm / sec), the time and the dew point until the substituted hydrazine in the outlet purified gas reaches the original concentration were measured. Table 2 shows the results.
【００２０】[0020]
【表２】 表 ２ 比較例 ガスの種類 露 点（℃） 所定濃度到達 番 号 入 口 出 口 時間（ｍｉｎ） １ ＣＨ3 Ｎ2 Ｈ3 −２８ −８６ ＞１８０ ２ Ｃ2 Ｈ5 Ｎ2 Ｈ3 −２８ −８６ ＞１８０ ３ ＣＨ3 Ｎ2 Ｈ2 ＣＨ3 −２７ −８５ １００ ４ （ＣＨ3 ）2 Ｎ2 Ｈ2 −２６ −８５ １２０ ５ ＣＨ3 Ｎ2 Ｈ3 −２８ −８６ ８０ ６ Ｃ2 Ｈ5 Ｎ2 Ｈ3 −２８ −８６ ６０ ７ （ＣＨ3 ）2 Ｎ2 Ｈ2 −２６ −８５ ５０[Table 2] Table 2 Comparative example Gas type Dew point (° C) Predetermined concentration reached Number Inlet Outlet time (min) 1 CH 3 N 2 H 3 -28 -86> 180 2 C 2 H 5 N 2 H 3 -28 -86> 180 3 CH 3 N 2 H 2 CH 3 -27 -85 100 4 (CH 3) 2 N 2 H 2 -26 -85 120 5 CH 3 N 2 H 3 -28 -86 80 6 C 2 H 5 N 2 H 3 −28 −86 607 (CH 3 ) 2 N 2 H 2 −26 −85 50
【００２１】[0021]
【発明の効果】本発明は、吸着剤に細孔径が３Å相当の
合成ゼオライトを使用するものであり、置換ヒドラジン
ガスはほとんど吸着されることがなく、精製筒出口の精
製置換ヒドラジンは短時間で所定の濃度に達し、しか
も、水分を効率よく除去することができる。INDUSTRIAL APPLICABILITY According to the present invention, a synthetic zeolite having a pore size of 3Å is used as an adsorbent, the substituted hydrazine gas is hardly adsorbed, and the purified substituted hydrazine at the outlet of the purifying cylinder is in a short time. A predetermined concentration is reached, and water can be efficiently removed.
Claims (5)
の合成ゼオライト系の吸着剤と接触させて、該置換ヒド
ラジンガス中に含有される水分を除去することを特徴と
する置換ヒドラジンガスの精製方法。1. A method for purifying a substituted hydrazine gas, which comprises contacting the substituted hydrazine gas with a synthetic zeolite-based adsorbent having a pore diameter of 3Å to remove water contained in the substituted hydrazine gas. .
で示される一置換ヒドラジンおよび一般化学式Ｒ2 Ｎ2
Ｈ2 で示される二置換ヒドラジン〔各式中Ｒはアルキル
基またはアリール基を示す〕から選ばれる一種または二
種以上である請求項１に記載の精製方法。2. The substituted hydrazine has the general chemical formula RN 2 H 3
A monosubstituted hydrazine represented by the general formula and R 2 N 2
The purification method according to claim 1, wherein the purification method is one or more selected from disubstituted hydrazines represented by H 2 (wherein R represents an alkyl group or an aryl group).
ルヒドラジン、フェニルヒドラジン、１，２ジメチルヒ
ドラジン、１，１ジメチルヒドラジン、１，２ジエチル
ヒドラジンまたは１，１ジエチルヒドラジンである請求
項２に記載の精製方法。3. The method according to claim 2, wherein the substituted hydrazine is methylhydrazine, ethylhydrazine, phenylhydrazine, 1,2-dimethylhydrazine, 1,1-dimethylhydrazine, 1,2-diethylhydrazine or 1,1-diethylhydrazine. .
素、アルゴン、ヘリウムまたは水素で希釈したガスであ
る請求項１に記載の精製方法。4. The purification method according to claim 1, wherein the substituted hydrazine gas is a gas obtained by diluting the substituted hydrazine with nitrogen, argon, helium or hydrogen.
等品である請求項１に記載の精製方法。5. The purification method according to claim 1, wherein the adsorbent is a molecular sieve 3A or an equivalent product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07714695A JP3634890B2 (en) | 1995-03-09 | 1995-03-09 | Method for purifying substituted hydrazine gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07714695A JP3634890B2 (en) | 1995-03-09 | 1995-03-09 | Method for purifying substituted hydrazine gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08245207A true JPH08245207A (en) | 1996-09-24 |
| JP3634890B2 JP3634890B2 (en) | 2005-03-30 |
Family
ID=13625664
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07714695A Expired - Fee Related JP3634890B2 (en) | 1995-03-09 | 1995-03-09 | Method for purifying substituted hydrazine gas |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151190A (en) * | 2014-08-07 | 2014-11-19 | 山东汇海医药化工有限公司 | Method for recycle of methylhydrazine from methylthiosemicarbazide synthesis mother liquor |
| JP2018062479A (en) * | 2016-10-12 | 2018-04-19 | 大陽日酸株式会社 | Purification method of monomethylhydrazine gas |
| JP2020500104A (en) * | 2016-11-08 | 2020-01-09 | マセソン トライ−ガス， インコーポレイテッド | How to remove moisture from hydrazine |
-
1995
- 1995-03-09 JP JP07714695A patent/JP3634890B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151190A (en) * | 2014-08-07 | 2014-11-19 | 山东汇海医药化工有限公司 | Method for recycle of methylhydrazine from methylthiosemicarbazide synthesis mother liquor |
| JP2018062479A (en) * | 2016-10-12 | 2018-04-19 | 大陽日酸株式会社 | Purification method of monomethylhydrazine gas |
| JP2020500104A (en) * | 2016-11-08 | 2020-01-09 | マセソン トライ−ガス， インコーポレイテッド | How to remove moisture from hydrazine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3634890B2 (en) | 2005-03-30 |
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