JPH05124813A - Refining method of gaseous ammonia - Google Patents
Refining method of gaseous ammoniaInfo
- Publication number
- JPH05124813A JPH05124813A JP3289867A JP28986791A JPH05124813A JP H05124813 A JPH05124813 A JP H05124813A JP 3289867 A JP3289867 A JP 3289867A JP 28986791 A JP28986791 A JP 28986791A JP H05124813 A JPH05124813 A JP H05124813A
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- nickel
- catalyst
- oxygen
- ppm
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/024—Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はアンモニアの精製方法に
関し、さらに詳細にはアンモニア中に不純物として含ま
れる酸素を極低濃度まで除去しうるアンモニアの精製方
法に関する。アンモニアは、シリコン半導体製造プロセ
スにおいて窒化珪素膜生成のためにシランとともに使用
され、また、トリエチルガリウムなどとともに窒化ガリ
ウムなどの化合物半導体製造に使用されており、成膜技
術の進歩とともに不純物の極めて少ないものが要求され
ている。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying ammonia, and more particularly to a method for purifying ammonia capable of removing oxygen contained as an impurity in ammonia to an extremely low concentration. Ammonia is used together with silane to form a silicon nitride film in the silicon semiconductor manufacturing process, and is also used along with triethylgallium and the like to manufacture compound semiconductors such as gallium nitride. Is required.
【０００２】[0002]
【従来の技術】半導体製造時に使用されるアンモニアは
一般的には純アンモニアの他、水素ガスまたは不活性ガ
スで希釈された形態で市販されており、通常はガスの状
態で半導体製造装置に供給される。これらのアンモニア
中には不純物として酸素および水分などが含有され、通
常は原料アンモニアの蒸留などによって精製される。ま
た、水分についてはこの他に合成ゼオライトなどの脱湿
剤により除去することが可能である。市販の精製アンモ
ニア中の酸素含有量は通常は１０ｐｐｍ以下であるが、
最近のボンベ入りのアンモニアでは、その酸素含有量
０．５〜１．０ｐｐｍと比較的低いものも市販されてい
る。2. Description of the Related Art Ammonia used in semiconductor manufacturing is generally marketed in a form diluted with hydrogen gas or an inert gas in addition to pure ammonia, and is usually supplied to a semiconductor manufacturing apparatus in a gas state. To be done. Oxygen and water are contained in these ammonia as impurities, and are usually purified by distillation of raw material ammonia. In addition, water can be removed by a dehumidifying agent such as synthetic zeolite. The oxygen content in commercially available purified ammonia is usually 10 ppm or less,
Recent cylinder-filled ammonia has a relatively low oxygen content of 0.5 to 1.0 ppm and is commercially available.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、酸素含
有量が１ｐｐｍを切る程度では最近の半導体製造プロセ
スにおける要求に充分に対応することはできず、０．１
ｐｐｍ以下、さらには、０．０１ｐｐｍ以下とすること
が強く望まれている。また、最近、半導体製造時にアン
モニアと同時に使用されるシランなどは高純度に精製す
ることが可能となり、例えば不純物として含有する酸素
は０．０１ｐｐｍ以下まで除去することが可能となって
いる。このため、アンモニアについても酸素含有量の極
めて低いものが要望されつつある。また、これらアンモ
ニアはボンベの接続時や配管の切替時など半導体装置へ
の供給過程において空気など不純物の混入による汚染も
あるため、装置の直前で不純物を最終的に除去すること
が望ましい。しかしながら、このように高純度アンモニ
アに対する需要は年々増加しているが、アンモニア中に
含有される酸素を効率よく除去して高純度のアンモニア
系のガスを半導体製造プロセスなどに供給する方法につ
いての公知技術はほとんど見あたらない。However, if the oxygen content is less than 1 ppm, it is not possible to sufficiently meet the demands in the recent semiconductor manufacturing process.
It is strongly desired that the content be ppm or less, further 0.01 ppm or less. Further, recently, silane and the like used together with ammonia during semiconductor manufacturing can be purified to high purity, and for example, oxygen contained as impurities can be removed to 0.01 ppm or less. For this reason, ammonia is also required to have an extremely low oxygen content. Further, these ammonias may be contaminated by the inclusion of impurities such as air during the supply process to the semiconductor device, such as when connecting the cylinder or switching the pipes, so it is desirable to finally remove the impurities immediately before the device. However, although the demand for high-purity ammonia has been increasing year by year, publicly known methods for efficiently removing oxygen contained in ammonia to supply a high-purity ammonia-based gas to a semiconductor manufacturing process or the like. Almost no technology is found.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、アンモニ
ア中に含有される酸素を極低濃度まで効率よく除去する
べく鋭意研究を重ねた結果、アンモニアをニッケルを主
成分とする触媒と接触させることにより、酸素濃度を
０．１ｐｐｍ以下、さらには０．０１ｐｐｍ以下まで除
去しうることを見いだし、本発明を完成した。すなわち
本発明は、粗アンモニアをニッケルを主成分とする触媒
と接触させて該粗アンモニア中に含有される酸素を除去
することを特徴とするアンモニアの精製方法である。本
発明はアンモニア単独、水素（水素ガスベース）および
窒素、アルゴンなどの不活性ガス（不活性ガスベース）
で希釈されたアンモニア（以下総称して粗アンモニアと
記す）中に含有される酸素の除去に適用される。Means for Solving the Problems As a result of intensive studies conducted by the present inventors to efficiently remove oxygen contained in ammonia to an extremely low concentration, ammonia was contacted with a catalyst containing nickel as a main component. By doing so, it was found that the oxygen concentration can be reduced to 0.1 ppm or less, further 0.01 ppm or less, and the present invention was completed. That is, the present invention is a method for purifying ammonia, which comprises contacting crude ammonia with a catalyst containing nickel as a main component to remove oxygen contained in the crude ammonia. The present invention includes ammonia alone, hydrogen (hydrogen gas base) and inert gases such as nitrogen and argon (inert gas base).
It is applied to remove oxygen contained in ammonia diluted with (hereinafter collectively referred to as crude ammonia).
【０００５】本発明において用いられる触媒は金属ニッ
ケルまたはニッケルの酸化物など還元され易いニッケル
化合物を主成分とするものである。また、ニッケル以外
の金属成分としてクロム、鉄、コバルト、銅などの金属
が少量含まれているものであってもよい。これらのニッ
ケルは単独で用いられてもよく、また、触媒担体などに
担持させた形体で用いてもよいが、ニッケルの表面とガ
スとの接触効率を高める目的などから、通常は触媒担体
などに担持させた形態で使用することが好ましい。ニッ
ケルを担体に担持させる方法としては、例えば、ニッケ
ル塩の水溶液中に珪藻土、アルミナ、シリカアルミナ、
アルミノシリケートおよびカルシウムシリケートなどの
担体粉末を分散させ、さらにアルカリを添加して担体の
粉末上にニッケル成分を沈澱させ、次いで濾過し必要に
応じて水洗して得たケーキを１２０〜１５０℃で乾燥
後、３００℃以上で焼成し、この焼成物を粉砕する、あ
るいはＮｉＣＯ3 、Ｎｉ（ＯＨ）2 、Ｎｉ（ＮＯ3 ）2
などの無機塩、ＮｉＣ2 Ｏ4、Ｎｉ（ＣＨ3 ＣＯＯ）2
などの有機塩を焼成し、粉砕した後、これに耐熱性セメ
ントを混合し、焼成するなどが挙げられる。これらは、
通常は、押出成型、打錠成型などで成型体とされ、その
まま、あるいは必要に応じて適当な大きさに破砕して使
用される。成型方法としては乾式法あるいは湿式法を用
いることができ、その際、少量の水、滑剤などを使用し
てもよい。また、ニッケル系触媒として例えば水蒸気変
成触媒、Ｃ１１−２−０３（ＮｉＯ−セメント）、Ｃ１
１−２−０６（ＮｉＯ−耐火物）、Ｃ１１−２（Ｎｉ−
カルシウムアルミネート）、Ｃ１１−９（Ｎｉ−アルミ
ナ）；水素化触媒、Ｃ４６−７（Ｎｉ−珪藻土）、Ｃ４
６−８（Ｎｉ−シリカ）、Ｃ３６（Ｎｉ−Ｃｏ−Ｃｒ−
アルミナ）；ガス化触媒、ＸＣ９９（ＮｉＯ）；水素化
変成触媒、Ｃ２０−７（Ｎｉ−Ｍｏ−アルミナ）〔以
上、東洋ＣＣＩ（株）製〕および水素化触媒、Ｎ−１１
１（Ｎｉ−珪藻土）；ガス化変成触媒、Ｎ−１７４（Ｎ
ｉＯ）；ガス化触媒、Ｎ−１８５（ＮｉＯ）〔以上、日
揮（株）製〕など種々なものがあるのでそれらから選択
したものを使用してもよい。要は、還元ニッケル、酸化
ニッケルなどが微細に分散されて、その表面積が大きく
ガスとの接触効率の高い形態のものであればよい。The catalyst used in the present invention contains a nickel compound such as metallic nickel or nickel oxide, which is easily reduced, as a main component. Also, a small amount of a metal such as chromium, iron, cobalt, or copper may be contained as a metal component other than nickel. These nickels may be used alone, or may be used in the form of being supported on a catalyst carrier, but for the purpose of improving the contact efficiency between the surface of nickel and a gas, etc., they are usually used as a catalyst carrier. It is preferably used in a supported form. As a method of supporting nickel on a carrier, for example, diatomaceous earth in an aqueous solution of nickel salt, alumina, silica alumina,
A carrier powder such as aluminosilicate and calcium silicate is dispersed, and an alkali is further added to precipitate the nickel component on the powder of the carrier, which is then filtered and washed with water if necessary, and the cake obtained is dried at 120 to 150 ° C. Then, it is fired at 300 ° C. or higher, and the fired product is crushed, or NiCO 3 , Ni (OH) 2 , Ni (NO 3 ) 2
Inorganic salts such as NiC 2 O 4 , Ni (CH 3 COO) 2
Examples of the method include firing an organic salt such as the above, pulverizing it, mixing it with heat resistant cement, and firing. They are,
Usually, a molded body is formed by extrusion molding, tablet molding or the like, and is used as it is or crushed to an appropriate size as needed. As a molding method, a dry method or a wet method can be used, in which case a small amount of water, a lubricant or the like may be used. Further, as the nickel-based catalyst, for example, a steam conversion catalyst, C11-2-03 (NiO-cement), C1
1-2-06 (NiO-refractory), C11-2 (Ni-
Calcium aluminate), C11-9 (Ni-alumina); hydrogenation catalyst, C46-7 (Ni-diatomaceous earth), C4
6-8 (Ni-silica), C36 (Ni-Co-Cr-
Alumina); gasification catalyst, XC99 (NiO); hydrogenation shift catalyst, C20-7 (Ni-Mo-alumina) [above, Toyo CCI Co., Ltd.] and hydrogenation catalyst, N-11
1 (Ni-diatomaceous earth); gasification shift catalyst, N-174 (N
iO); various catalysts such as gasification catalyst, N-185 (NiO) [above, manufactured by JGC Corporation], so that one selected from them may be used. The point is that reduced nickel, nickel oxide, etc. are finely dispersed and have a large surface area and high contact efficiency with gas.
【０００６】触媒の比表面積としては通常は、ＢＥＴ法
で１０〜３００ｍ2 ／ｇの範囲のもの、好ましくは３０
〜２５０ｍ2 ／ｇの範囲のものである。また、ニッケル
の含有量は金属ニッケル換算で通常は、５〜９５ｗｔ
％、好ましくは２０〜９５ｗｔ％である。ニッケルの含
有量が５ｗｔ％よりも少なくなると脱酸素能力が低くな
り、また９５ｗｔ％よりも高くなると水素による還元の
際にシンタリングが生じて活性が低下する恐れがある。
触媒を活性化するためには通常は水素還元を行う。水素
還元に際しては、例えば３５０℃以下程度で水素−窒素
の混合ガスを空筒線速度（ＬＶ）５ｃｍ／ｓｅｃ程度で
通すことによっておこなうことができるが、発熱反応で
あるため温度が急上昇しないよう注意が必要である。The specific surface area of the catalyst is usually in the range of 10 to 300 m 2 / g by the BET method, preferably 30.
In the range of up to 250 m 2 / g. The content of nickel is usually 5 to 95 wt% in terms of metallic nickel.
%, Preferably 20 to 95 wt%. If the nickel content is less than 5 wt%, the deoxidizing ability will be low, and if it is higher than 95 wt%, sintering will occur during reduction with hydrogen and the activity may be reduced.
Hydrogen reduction is usually performed to activate the catalyst. The hydrogen reduction can be performed by passing a hydrogen-nitrogen mixed gas at a hollow cylinder linear velocity (LV) of about 5 cm / sec at about 350 ° C. or less, but be careful not to raise the temperature suddenly because it is an exothermic reaction. is necessary.
【０００７】アンモニアの精製は、通常は、還元処理し
たニッケルを主成分とする触媒が充填された精製筒に粗
アンモニアを通すことによって行われ、粗アンモニアが
ニッケル触媒と接触することによって粗アンモニア中に
不純物として含有される酸素が除去される。本発明に適
用される粗アンモニア中の酸素濃度は通常は１００ｐｐ
ｍ以下である。酸素濃度がこれよりも高くなると発熱量
が増加するため条件によっては除熱手段が必要となる。
精製筒に充填されるニッケル触媒の充填長は、実用上通
常は５０〜１５００ｍｍとされる。充填長が５０ｍｍよ
りも短くなると酸素除去率が低下する恐れがあり、ま
た、１５００ｍｍよりも長くなると圧力損失が大きくな
り過ぎる恐れが生ずる。精製時の粗アンモニアの空筒線
速度（ＬＶ）は供給されるアンモニア中の酸素濃度およ
び操作条件などによって異なり一概に特定できないが、
通常は１００ｃｍ／ｓｅｃ以下、好ましくは３０ｃｍ／
ｓｅｃ以下である。アンモニアとニッケル触媒の接触温
度は精製筒の入口に供給されるガスの温度で、２００℃
以下、好ましくは１００℃以下であり、通常は常温でよ
く、特に加熱や冷却を必要としない。触媒との接触時の
圧力にも特に制限はなく常圧、減圧、加圧のいずれでも
処理が可能であるが、通常は２０ｋｇ／ｃｍ2 ａｂｓ以
下、好ましくは０．１〜１０ｋｇ／ｃｍ2 ａｂｓであ
る。また、アンモニア中に少量の水分が含有されていて
も脱酸素能力には特に悪影響を及ぼすことはなく、さら
に触媒に担体などを用いている場合には、その種類によ
っては水分も同時に除去される。本発明においてニッケ
ル触媒による酸素除去工程に、必要に応じて合成ゼオラ
イトなどの脱湿剤による水分除去工程を適宜組み合わせ
ることも可能であり、これによって水分も完全に除去さ
れ、極めて高純度のアンモニアを得ることができる。Purification of ammonia is usually carried out by passing crude ammonia through a purifying column filled with a reduced nickel-based catalyst, and by contacting the crude ammonia with the nickel catalyst, Oxygen contained as an impurity is removed. The oxygen concentration in the crude ammonia applied to the present invention is usually 100 pp.
m or less. If the oxygen concentration is higher than this, the amount of heat generated increases, so heat removal means is required depending on the conditions.
In practice, the filling length of the nickel catalyst filled in the purification column is usually 50 to 1500 mm. If the filling length is shorter than 50 mm, the oxygen removal rate may be reduced, and if it is longer than 1500 mm, the pressure loss may be too large. The empty cylinder linear velocity (LV) of crude ammonia at the time of purification varies depending on the oxygen concentration in the supplied ammonia and the operating conditions, and cannot be specified unconditionally.
Usually 100 cm / sec or less, preferably 30 cm /
It is less than or equal to sec. The contact temperature between the ammonia and the nickel catalyst is the temperature of the gas supplied to the inlet of the purification column, which is 200 ° C.
Hereafter, the temperature is preferably 100 ° C. or lower, usually room temperature, and heating or cooling is not particularly required. The pressure at the time of contact with the catalyst is not particularly limited, and the treatment can be carried out under any of normal pressure, reduced pressure and increased pressure, but it is usually 20 kg / cm 2 abs or less, preferably 0.1-10 kg / cm 2 abs. Is. In addition, even if a small amount of water is contained in ammonia, it does not particularly affect the deoxidizing ability, and when a carrier is used as the catalyst, the water is also removed at the same time depending on the type. .. In the present invention, the oxygen removal step using a nickel catalyst can be appropriately combined with a water removal step using a dehumidifying agent such as synthetic zeolite, if necessary, whereby water is also completely removed and extremely high-purity ammonia is obtained. Obtainable.
【０００８】[0008]
実施例１ （ニッケルの還元処理）市販のニッケル触媒（日揮
（株）製、Ｎ−１１１）を用いた。このものの組成はＮ
ｉ＋ＮｉＯの形であり、Ｎｉとして４５〜４７ｗｔ％、
Ｃｒ２〜３ｗｔ％、Ｃｕ２〜３ｗｔ％、珪藻土２７〜２
９ｗｔ％および黒鉛４〜５ｗｔ％、比表面積が１５０ｍ
2 ／ｇであり、直径５ｍｍ、高さ４．５ｍｍの成型体で
ある。このニッケル触媒を８〜１０ｍｅｓｈに破砕した
もの６３ｍｌを内径１６．４ｍｍ、長さ４００ｍｍのス
テンレス製の精製筒に充填長３００ｍｍ（充填密度：
１．０ｇ／ｍｌ）に充填した。これに水素を常圧で温度
１５０℃、流量５９５ｍｌ／ｍｉｎ（ＬＶ＝３．６ｃｍ
／ｓｅｃ）で３時間還元処理を行った後、常温に冷却し
た。 （アンモニアの精製）引き続き、この精製筒にアンモニ
ア１０ｖｏｌ％および不純物として０．５３ｐｐｍの酸
素を含有する水素ベースの粗アンモニアを、常温（２０
℃）において６３３ｍｌ／ｍｉｎ（ＬＶ＝５ｃｍ／ｓｅ
ｃ）の速度で流して黄燐発光式酸素分析計（測定下限濃
度０．０１ｐｐｍ）を用いて出口ガス中の酸素濃度を測
定した結果、酸素は検出されず０．０１ｐｐｍ以下であ
った。また、ガスを流し始めてから１００分後において
も出口ガス中の酸素濃度は、０．０１ｐｐｍ以下であっ
た。、Example 1 (Reduction treatment of nickel) A commercially available nickel catalyst (N-111, manufactured by JGC Corporation) was used. The composition of this product is N
i + NiO form, 45-47 wt% as Ni,
Cr 2-3 wt%, Cu 2-3 wt%, diatomaceous earth 27-2
9 wt% and graphite 4-5 wt%, specific surface area 150 m
2 / g, which is a molded body having a diameter of 5 mm and a height of 4.5 mm. 63 ml of this nickel catalyst crushed to 8 to 10 mesh was filled in a stainless steel purification cylinder having an inner diameter of 16.4 mm and a length of 400 mm with a filling length of 300 mm (filling density:
1.0 g / ml). Hydrogen was added to this at atmospheric pressure at a temperature of 150 ° C. and a flow rate of 595 ml / min (LV = 3.6 cm).
/ Sec) for 3 hours and then cooled to room temperature. (Ammonia purification) Subsequently, hydrogen-based crude ammonia containing 10 vol% ammonia and 0.53 ppm oxygen as an impurity was charged to this purification cylinder at room temperature (20
633 ml / min (LV = 5 cm / se)
As a result of measuring the oxygen concentration in the outlet gas using a yellow phosphorus luminescence type oxygen analyzer (lower limit concentration of 0.01 ppm), oxygen was not detected and was 0.01 ppm or less. In addition, the oxygen concentration in the outlet gas was 0.01 ppm or less even 100 minutes after the gas started to flow. ,
【０００９】実施例２ （ニッケル触媒の調製）３Ｌの水にＡｌ（ＮＯ3 ）3 ９
Ｈ2 Ｏ、４５４ｇを溶解し、氷浴で５〜１０℃に冷却し
た。激しくかき混ぜながら、これにＮａＯＨ、２００ｇ
を１Ｌの水に溶解して５〜１０℃に冷却した溶液を２時
間かけて滴下し、アルミン酸ナトリウムとした。次に、
Ｎｉ（ＮＯ3 ）2 ・６Ｈ2 Ｏ、１０１ｇを６００ｍｌの
水に溶解し、これに４５ｍｌの濃硝酸を加えて５〜１０
℃に冷却したものを、アルミン酸ナトリウム溶液に激し
くかき混ぜながら１時間かけて加えた。生じた沈澱を濾
過し、得られた沈澱を２Ｌの水中で１５分間かき混ぜて
洗う操作を６回繰り返して中性とした。得られた沈澱物
を細分して空気浴中で１０５℃で１６時間乾燥してから
粉砕し、これをふるい分けて１２〜２４ｍｅｓｈのもの
を集めた。このものは２９．５ｗｔ％の酸化ニッケル
（ＮｉＯ）を含有していた。 （ニッケルの還元処理）このものを、実施例１で使用し
たと同じ精製筒に６３ｍｌ充填し（充填密度：０．７７
ｇ／ｍｌ）、これに水素を常圧で温度３５０℃、流量１
６５ｃｃ／ｍｉｎ（ＬＶ＝１ｃｍ／ｓｅｃ）で１６時間
流して還元処理をおこなった後、常温に冷却した。 （アンモニアの精製）引き続いて、アンモニアの精製を
おこなった。実施例１で使用した約０．５３ｐｐｍの酸
素を含む１０ｖｏｌ％のアンモニア（水素ベース）を、
常温（２０℃）において精製筒に６３３ｍｌ／ｍｉｎ
（ＬＶ＝５ｃｍ／ｓｅｃ）の速度で流して出口ガス中の
酸素濃度を測定した結果、０．０１ｐｐｍ以下であっ
た。精製を始めてから１００分後においても出口ガスの
酸素濃度は０．０１ｐｐｍ以下であった。Example 2 (Preparation of nickel catalyst) Al (NO 3 ) 3 9 in 3 L of water
H 2 O (454 g) was dissolved and cooled to 5 to 10 ° C. in an ice bath. Add 200g of NaOH to this while stirring vigorously.
Was dissolved in 1 L of water and cooled to 5 to 10 ° C, and the solution was added dropwise over 2 hours to obtain sodium aluminate. next,
Ni (NO 3) 2 · 6H 2 O, the 101g was dissolved in water of 600 ml, this was added concentrated nitric acid 45 ml 5 to 10
What was cooled to 0 ° C was added to the sodium aluminate solution over 1 hour with vigorous stirring. The resulting precipitate was filtered, and the precipitate thus obtained was stirred in 2 L of water for 15 minutes and washed to obtain neutrality by repeating 6 times. The resulting precipitate was subdivided, dried in an air bath at 105 ° C. for 16 hours, then ground, and sieved to collect 12 to 24 mesh. This contained 29.5 wt% nickel oxide (NiO). (Reduction treatment of nickel) 63 ml of this was packed in the same purification cylinder as used in Example 1 (packing density: 0.77).
g / ml), and hydrogen at atmospheric pressure at a temperature of 350 ° C. and a flow rate of 1
The mixture was allowed to flow for 16 hours at 65 cc / min (LV = 1 cm / sec) to carry out the reduction treatment, and then cooled to room temperature. (Purification of Ammonia) Subsequently, purification of ammonia was performed. 10 vol% ammonia (hydrogen basis) containing about 0.53 ppm oxygen used in Example 1,
633ml / min in the purifying cylinder at room temperature (20 ℃)
As a result of measuring the oxygen concentration in the outlet gas by flowing at a velocity of (LV = 5 cm / sec), it was 0.01 ppm or less. Even after 100 minutes from the start of purification, the oxygen concentration of the outlet gas was 0.01 ppm or less.
【００１０】比較例 活性炭（椰子殻炭）を８〜２４ｍｅｓｈに破砕したもの
４８ｇを実施例１に置けると同じ精製筒に３００ｍｍ
（充填密度０．５７ｇ／ｍｌ）充填し、ヘリウム気流中
２７０〜２９０℃で時間加熱処理した後、室温に冷却し
た。この精製筒に実施例１で用いたと同じ約０．５３ｐ
ｐｍの酸素を含む１０ｖｏｌ％のアンモニア（水素ベー
ス）を精製筒に６３３ｍｌ／ｍｉｎ（ＬＶ＝５ｃｍ／ｓ
ｅｃ）で流して出口ガス中の酸素濃度を測定した結果、
０．５３ｐｐｍであり、この状態で２時間流し続けたが
酸素濃度の変化は見られなかった。Comparative Example 48 g of activated carbon (coconut shell charcoal) crushed into 8 to 24 mesh was placed in Example 1 in the same purifying cylinder of 300 mm.
(Filling density 0.57 g / ml) was filled, and after heat treatment in a helium gas stream at 270 to 290 ° C. for an hour, it was cooled to room temperature. About 0.53 p, which is the same as that used in Example 1, in this purification cylinder
10 vol% ammonia (hydrogen base) containing pm oxygen was put into the purifying cylinder at 633 ml / min (LV = 5 cm / s).
As a result of measuring the oxygen concentration in the outlet gas by flowing in step ec),
It was 0.53 ppm, and in this state, the oxygen concentration was not changed although the flow was continued for 2 hours.
【００１１】[0011]
【発明の効果】本発明によって、従来除去が困難であっ
たアンモニア中の酸素を０．１ｐｐｍ以下、さらには
０．０１ｐｐｍ以下のような極低濃度まで除去すること
ができ、超高純度のアンモニアを得ることが可能となっ
た。EFFECTS OF THE INVENTION According to the present invention, it is possible to remove oxygen in ammonia, which has been difficult to remove in the past, to an extremely low concentration of 0.1 ppm or less, further 0.01 ppm or less, and to obtain ultra-high purity ammonia. It became possible to obtain.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安田 雅子 神奈川県平塚市田村5181番地 日本パイオ ニクス株式会社平塚工場内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masako Yasuda 5181 Tamura, Hiratsuka-shi, Kanagawa Japan Pionics Co., Ltd. Hiratsuka factory
Claims (3)
媒と接触させて、該粗アンモニアに含有される酸素を除
去することを特徴とするアンモニアの精製方法。1. A method for purifying ammonia, which comprises contacting crude ammonia with a catalyst containing nickel as a main component to remove oxygen contained in the crude ammonia.
ケルを含有し、かつ比表面積がＢＥＴ法で１０〜３００
ｍ2 ／ｇである請求項１に記載のアンモニアの精製方
法。2. The catalyst contains nickel in an amount of 5 to 95 wt% in terms of metal, and has a specific surface area of 10 to 300 by the BET method.
The method for purifying ammonia according to claim 1, wherein the method is m 2 / g.
以下である請求項１に記載のアンモニアの精製方法。3. The contact temperature between ammonia and the catalyst is 200 ° C.
The method for purifying ammonia according to claim 1, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28986791A JP3359928B2 (en) | 1991-11-06 | 1991-11-06 | Ammonia purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28986791A JP3359928B2 (en) | 1991-11-06 | 1991-11-06 | Ammonia purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05124813A true JPH05124813A (en) | 1993-05-21 |
| JP3359928B2 JP3359928B2 (en) | 2002-12-24 |
Family
ID=17748791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28986791A Expired - Fee Related JP3359928B2 (en) | 1991-11-06 | 1991-11-06 | Ammonia purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3359928B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002037624A (en) * | 2000-07-28 | 2002-02-06 | Japan Pionics Co Ltd | Method for purifying ammonia |
| JP2002037623A (en) * | 2000-07-28 | 2002-02-06 | Japan Pionics Co Ltd | Method for purifying ammonia |
| JP2008132475A (en) * | 2006-10-27 | 2008-06-12 | Japan Pionics Co Ltd | Gas treatment method |
| JP2014047089A (en) * | 2012-08-30 | 2014-03-17 | Japan Pionics Co Ltd | Apparatus for feeding purified ammonia |
| JP2015519192A (en) * | 2012-04-24 | 2015-07-09 | サエス・ゲッターズ・エッセ・ピ・ア | Renewable room temperature purification apparatus and method for nitrous oxide |
-
1991
- 1991-11-06 JP JP28986791A patent/JP3359928B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002037624A (en) * | 2000-07-28 | 2002-02-06 | Japan Pionics Co Ltd | Method for purifying ammonia |
| JP2002037623A (en) * | 2000-07-28 | 2002-02-06 | Japan Pionics Co Ltd | Method for purifying ammonia |
| JP2008132475A (en) * | 2006-10-27 | 2008-06-12 | Japan Pionics Co Ltd | Gas treatment method |
| JP2015519192A (en) * | 2012-04-24 | 2015-07-09 | サエス・ゲッターズ・エッセ・ピ・ア | Renewable room temperature purification apparatus and method for nitrous oxide |
| JP2014047089A (en) * | 2012-08-30 | 2014-03-17 | Japan Pionics Co Ltd | Apparatus for feeding purified ammonia |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3359928B2 (en) | 2002-12-24 |
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