JP3162588B2 - Method for producing high-purity nitrogen trifluoride gas - Google Patents
Method for producing high-purity nitrogen trifluoride gasInfo
- Publication number
- JP3162588B2 JP3162588B2 JP25651494A JP25651494A JP3162588B2 JP 3162588 B2 JP3162588 B2 JP 3162588B2 JP 25651494 A JP25651494 A JP 25651494A JP 25651494 A JP25651494 A JP 25651494A JP 3162588 B2 JP3162588 B2 JP 3162588B2
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- gas
- purity
- nitrogen trifluoride
- hydrofluoric acid
- producing high
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Description
【0001】[0001]
【産業上の利用分野】本発明は、高純度の三フッ化窒素
(NF3 )の製造法に関する。更に、詳しくは、工業的
に、高純度の三フッ化窒素を安価に提供する製造方法に
関し、所定の純度のフッ酸ガス及びアンモニアガスを反
応せしめ、得られた酸性フッ化アンモニウムを電解液と
し、更には陽極及び陰極に所定の純度のニッケル電極を
用い、溶融塩電解法によって電解を行うことを特徴とす
るものである。本発明における高純度の三フッ化窒素
(NF3 )とは、純度99.99容量%(以下4Nとい
う)以上のものをいう。The present invention relates to a method for producing high purity nitrogen trifluoride (NF 3 ). More specifically, industrially, the present invention relates to a manufacturing method for providing high-purity nitrogen trifluoride at a low cost, by reacting hydrofluoric acid gas and ammonia gas of a predetermined purity, and using the obtained ammonium acid fluoride as an electrolyte. Further, the present invention is characterized in that electrolysis is performed by a molten salt electrolysis method using nickel electrodes of a predetermined purity for the anode and the cathode. The high-purity nitrogen trifluoride (NF 3 ) in the present invention refers to one having a purity of 99.99% by volume (hereinafter referred to as 4N) or more.
【0002】[0002]
【従来の技術とその問題点】三フッ化窒素は、電子材料
向け、特にCVD装置のクリーリングガスとして、また
半導体のドライエッチング剤やTFTの液晶分野での枚
葉式装置のクリーニング用として、近年注目され、その
生産量は著しく伸びている。2. Description of the Related Art Nitrogen trifluoride is used for electronic materials, in particular, as a cleaning gas for CVD equipment, and for cleaning dry etching agents for semiconductors and single-wafer devices in the liquid crystal field for TFTs. In recent years, it has attracted attention and its production has increased significantly.
【0003】これらの用途に使用されるNF3 ガスは、
近年、益々高純度のものが要求されて来ている。[0003] NF 3 gas used in these applications is
In recent years, there has been an increasing demand for higher purity.
【0004】従来より、NF3 の溶融塩電解による製造
法としては、種々の方法が提案されている。例えば、用
いる電極については、工業的には、陽極にニッケルを使
用する方法が不純物分、例えばCF4 を生成しないこと
で広く用いられている。Conventionally, various methods have been proposed as methods for producing NF 3 by molten salt electrolysis. For example, for an electrode to be used, a method using nickel for the anode is widely used industrially because it does not generate impurities, for example, CF 4 .
【0005】また、用いる溶融塩電解を行う際の原料と
しては、本出願人による方法;特開平4-56789 などによ
る方法は、従来技術と比較して、不純物分が少ない点で
好ましい方法である。しかしながら、近年、技術の進歩
に伴い、高純度のNF3 ガスのニーズがあり、更なる、
製品ガスの高純度化が必要であった。As a raw material for performing molten salt electrolysis, a method according to the present applicant; a method according to Japanese Patent Application Laid-Open No. 4-56789 or the like is a preferable method because it has less impurities compared to the prior art. . However, in recent years, with the progress of technology, there has been a need for high-purity NF 3 gas.
Higher purity of the product gas was required.
【0006】その高純度化を行う方法としては、電解し
て得られた粗ガス(以下粗ガスという。)を、キャリヤ
ーガスと共に精製装置に導き、例えば、ゼオライト、活
性アルミナ、シリカゲル等による吸着及び/または薬液
洗浄処理及び/またはプラズマ分解及び/または深冷分
離及び/またはガスの液化精留等、によってガスの精製
を行っていた。[0006] As a method of purifying the crude gas, a crude gas obtained by electrolysis (hereinafter referred to as a crude gas) is led to a purifying apparatus together with a carrier gas, and is adsorbed by, for example, zeolite, activated alumina, silica gel or the like. Gas purification has been performed by chemical cleaning treatment and / or plasma decomposition and / or cryogenic separation and / or liquefaction rectification of gas.
【0007】粗ガス中の不純物分としては、キャリヤー
ガス成分及び水分(H2 O)を除いては、亜酸化窒素
(N2 O)、二酸化炭素(CO2 )、一酸化炭素(C
O)、二フッ化二窒素(N2 F2 )、二フッ化酸素(O
F2 )、六フッ化硫黄(SF6 )、四フッ化炭素(CF
4 )などを多く含んでいるため精製が必要であり、前述
の精製装置にて粗ガスの精製を実施していた。[0007] As impurities in the crude gas, nitrous oxide (N 2 O), carbon dioxide (CO 2 ), carbon monoxide (C 2 ) except for the carrier gas component and water (H 2 O).
O), dinitrogen difluoride (N 2 F 2 ), oxygen difluoride (O
F 2 ), sulfur hexafluoride (SF 6 ), carbon tetrafluoride (CF
4 ), etc., so that purification was necessary, and the purification of the crude gas was carried out by the above-mentioned purification apparatus.
【0008】これら精製装置を用いる場合は、不純物分
の含有量やバラツキによって、性能をコントロールする
必要があり、例えば吸着剤を用いた場合は、吸着速度、
吸着剤の更新、再生頻度の変更等種々の条件のパラメー
タを変化させる必要があり、その分労力を要すると共
に、得られた精製ガスについても、かなりの頻度で製品
の純度のバラツキを調査する必要がある等の品質管理が
大変であり、その分製造コストの増加を招いていた。In the case of using these refining devices, it is necessary to control the performance depending on the content and dispersion of impurities. For example, when an adsorbent is used, the adsorption speed,
It is necessary to change parameters of various conditions, such as renewal of the adsorbent and change of the regeneration frequency, which requires labor, and it is also necessary to examine the purity of the obtained purified gas with considerable frequency. However, quality control, such as the presence of a product, is difficult, which has led to an increase in manufacturing costs.
【0009】更に、4N(純度99.99%)、5N
(純度99.999%)あるいはそれ以上の高純度のN
F3 ガスを工業的に製造する場合、粗ガス中の不純物レ
ベル、即ち微量成分量が問題となってくる。粗ガスの精
製し、純度を高め、高純度化を図ることは、該精製を実
施する際、装置的にかつ経済的に限界点があり、高純度
のガスを、経済的に製造することが、実質的に、困難で
あった。Further, 4N (purity 99.99%), 5N
(Purity 99.999%) or higher
When F 3 gas is produced industrially, the level of impurities in the crude gas, that is, the amount of trace components, becomes a problem. Purifying a crude gas, increasing its purity, and achieving high purity have a limit in terms of equipment and economy when performing the purification, and it is necessary to economically produce high-purity gas. Was practically difficult.
【0010】[0010]
【発明を解決するための手段】本発明の目的は上記問題
点に鑑み、経済的に高純度のNF3 を製造する方法に関
し、用いる電極、原料を所定の成分とすることを特徴と
するものであり、粗ガス中の不純物レベルを大幅に低減
させることで、高純度のNF3 ガスを工業的かつ経済的
に製造することを見い出し、本発明を完成するに至った
ものである。The object of the present invention means to solve] In view of the above problems, relates to economically process for producing high-purity NF 3, which is characterized in that the electrode is used, raw materials and predetermined component The present inventors have found that high-purity NF 3 gas can be industrially and economically produced by greatly reducing the impurity level in the crude gas, and have completed the present invention.
【0011】即ち、本発明における高純度NF3 の製造
方法とは、金属電極を用いて溶融塩電解法により高純度
の三フッ化窒素を製造する方法において、金属電極とし
てはニッケルを用い、電解液用の原料としては、フッ酸
ガス及びアンモニアガスを反応せしめ、酸性フッ化アン
モニウムとし、該酸性フッ化アンモニウムを電解液とす
ることを特徴とする方法で、用いる金属電極としてのニ
ッケルはニッケルの純度が、98.5wt%以上を特徴とし、
用いるフッ酸ガスとしては、純度99.8wt%以上を特徴と
し、用いるアンモニアガスとしては、純度99.5wt%を特
徴とする方法である。That is, the method for producing high-purity NF 3 in the present invention refers to a method for producing high-purity nitrogen trifluoride by a molten salt electrolysis method using a metal electrode. As a raw material for the liquid, a method characterized by reacting hydrofluoric acid gas and ammonia gas to form ammonium acid fluoride and using the ammonium acid fluoride as an electrolytic solution, wherein nickel as a metal electrode used is nickel Purity is more than 98.5wt%,
The method is characterized in that the hydrofluoric acid gas used has a purity of 99.8 wt% or more, and the ammonia gas used has a purity of 99.5 wt%.
【0012】[0012]
【発明の詳細な開示】以下、本発明を、添付する図面を
参照しながら詳細に説明する。DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
【0013】図1は本発明の実施に好適な一実施態様の
フローシートを示す図である。図1において、所定量の
フッ酸ガス(HF)及びアンモニアガス(NH3 )を、
原料調合槽に導き、反応せしめ、酸性フッ化アンモニウ
ムとし、該酸性フッ化アンモニウムを電解槽へ供給し、
溶融塩電解法によって電極の陽極側に、NF3ガスを生
成せしめる。尚、原料調製槽3は適量の窒素ガス、アル
ゴンガス、ヘリウムガス等にて外気の影響を受けない目
的でシールすることが好ましい。FIG. 1 is a view showing a flow sheet of an embodiment suitable for carrying out the present invention. In FIG. 1, predetermined amounts of hydrofluoric acid gas (HF) and ammonia gas (NH 3 )
It is led to a raw material preparation tank, reacted, and made into ammonium acid fluoride. The ammonium acid fluoride is supplied to an electrolytic cell,
NF 3 gas is generated on the anode side of the electrode by a molten salt electrolysis method. The raw material preparation tank 3 is preferably sealed with an appropriate amount of nitrogen gas, argon gas, helium gas or the like for the purpose of not being affected by outside air.
【0014】用いるフッ酸ガス(HF)としては、純度
99.8wt%以上、用いるアンモニアガス(NH3 )として
は純度99.5wt%以上、用いる電極としてのニッケル(N
i)の純度としては、純度98.5wt%以上、であることが
好ましい。フッ酸ガス純度99.8wt%以下及び/またはア
ンモニアガス99.5wt%以下及び/または電極として用い
るニッケルの純度98.5wt%以下になれは、三フッ化窒素
の純度4N以上の高純度品を得ることが、難しくなり、
好適でない。[0014] The hydrofluoric acid gas (HF) used may be
99.8 wt% or more, the purity of ammonia gas (NH 3 ) used is 99.5 wt% or more, and nickel (N
The purity of i) is preferably 98.5 wt% or more. If the purity of hydrofluoric acid gas is 99.8 wt% or less and / or the ammonia gas is 99.5 wt% or less and / or the purity of nickel used as an electrode is 98.5 wt% or less, a highly pure product with a purity of nitrogen trifluoride of 4 N or more can be obtained. Becomes difficult,
Not suitable.
【0015】フッ酸ガスとアンモニアガスとの反応は、
極めて速やかに進むため、特に充分な撹拌等も不要で、
フッ酸ガスとアンモニアガスが接触出来るものであれば
特に限定はない。また、反応条件としては、HF/NH
4 Fモル比として1.5〜2.0程度が好適である。The reaction between hydrofluoric acid gas and ammonia gas is as follows:
Because it proceeds very quickly, there is no need for sufficient stirring, etc.
There is no particular limitation as long as the hydrofluoric acid gas and the ammonia gas can contact each other. The reaction conditions are HF / NH
The 4 F molar ratio is preferably about 1.5 to 2.0.
【0016】また、用いる電極、フッ酸ガス及びアンモ
ニアガスは、多種多用な不純物を含んでいる。例えば、
フッ酸ガスは、水分、二酸化硫黄や硫酸に代表される硫
黄分、ケイフッ化水素酸に代表されるケイ素分、二酸化
炭素や一酸化炭素やその他の炭素分、酸素分及びその他
微量成分がある。アンモニアガスは、水分、二酸化硫黄
や硫酸に代表される硫黄分、二酸化炭素や一酸化炭素や
その他の炭素分、酸素分及びその他微量成分がある、ニ
ッケル電極は、水分や炭素分を含め、微量金属Mn、Fe、
S 、Si、Cu、Mo、Cr、P 、Al、Ti、Na、K 、Co、W 等の
微量成分を含有している。The electrodes, hydrofluoric acid gas, and ammonia gas used contain various kinds of impurities. For example,
The hydrofluoric acid gas contains moisture, sulfur represented by sulfur dioxide and sulfuric acid, silicon represented by hydrofluoric acid, carbon dioxide, carbon monoxide, other carbon, oxygen, and other trace components. Ammonia gas has moisture, sulfur represented by sulfur dioxide and sulfuric acid, carbon dioxide, carbon monoxide and other carbon, oxygen and other trace components.Nickel electrode contains traces of moisture and carbon. Metal Mn, Fe,
It contains trace components such as S, Si, Cu, Mo, Cr, P, Al, Ti, Na, K, Co, and W.
【0017】本発明者らの研究によれば、三フッ化窒素
ガス中の主な不純物分はN2O,CO2,CO,N2F2,OF2,SF6,CF4
であり、その構成成分としては、N,O,C,F,S であり、三
弗化窒素(NF3) の構成成分を除けば、O,C,S の成分とな
る、即ち、原料中等の不純物成分のうち、特にO,C,S か
らなる構成成分をコントロールすれば良いことになる。
しかしながら、微量であるためその不純物が何であるか
の同定は非常に困難である。そこで、それに代わるもの
として本発明では電極、フッ酸ガス及びアンモニアガス
の純度を特定したものである。According to the study of the present inventors, the main impurities in nitrogen trifluoride gas are N 2 O, CO 2 , CO, N 2 F 2 , OF 2 , SF 6 and CF 4.
The components are N, O, C, F, and S. Excluding the components of nitrogen trifluoride (NF 3 ), the components become O, C, and S. It is only necessary to control the constituents composed of O, C, and S among the impurity components.
However, it is very difficult to identify what the impurities are due to the small amount. Thus, as an alternative, the present invention specifies the purity of the electrode, hydrofluoric acid gas and ammonia gas.
【0018】各不純物の含有量により、得られる三フッ
化窒素ガスの純度への影響は、異なるが、本発明者等の
研究によれば、電極として用いるニッケル、フッ酸ガス
及びアンモニアガスの純度を測定し、本発明の記載の範
囲内の純度であれば、得られた粗ガスを、従来と同様の
精製装置に導くことで、高純度の三フッ化窒素ガスを容
易に得ることが出来る。。The influence on the purity of the obtained nitrogen trifluoride gas varies depending on the content of each impurity, but according to the study of the present inventors, the purity of nickel, hydrofluoric acid gas, and ammonia gas used as electrodes is determined. Is measured, and if the purity is within the range described in the present invention, the obtained crude gas is led to a purification device similar to the conventional one, whereby a high-purity nitrogen trifluoride gas can be easily obtained. . .
【0019】尚、本発明における純度とは、ニッケルは
ニッケル(Ni)としての純度を示し、フッ酸ガス及び
アンモニアガス中の不純物のうち水分を除いた状態での
それぞれフッ酸(HF)及びアンモニア(NH3 )の純
度をいう。但し、両者のガス中の水分は、精製工程にて
他の不純物とは異なり容易に、取り除くことが出来るた
め高純度の三フッ化窒素ガスを得る際に大きな問題とは
ならないが、用いる材質等の点から、本発明者等の研究
によれば、H2 Oとして、0.01容量%以下が好まし
い。In the present invention, the term "purity" refers to the purity of nickel as nickel (Ni), and each of the impurities in the hydrofluoric acid gas and the ammonia gas, excluding water, is a hydrofluoric acid (HF) and an ammonia gas. It refers to the purity of (NH 3 ). However, unlike the other impurities in the refining process, the water in both gases can be easily removed and does not pose a major problem in obtaining high-purity nitrogen trifluoride gas. In view of the above, according to the study by the present inventors, H 2 O is preferably 0.01% by volume or less.
【0020】生成した粗ガスであるNF3 ガスは精製装
置へ導き微量の不純物を除去せしめ高純度の三フッ化窒
素ガスを得る。The generated NF 3 gas, which is a crude gas, is led to a purification device to remove a trace amount of impurities to obtain a high-purity nitrogen trifluoride gas.
【0021】図2は、本発明における、図1における電
解槽の詳細を示す図である。図2において、反応せしめ
た酸性フッ化アンモニウムを電解槽本体1に導き、電解
液2とする。電解液の供給は、連続式あるいは回分式い
ずれでもかまわないが、連続的に一定量の三フッ化窒素
を得ようとした場合、連続式が好ましい。電解槽本体1
は、陽極室3と陰極室5に隔板7にて、仕切られてい
る。陽極室3には、所定の純度のニッケル陽極4があ
り、陰極室5には陽極4と同じ純度の陰極6が取り付け
られている。尚、電解槽本体1は、陽極及び陰極が複数
個からなるものでも特に問題はなく、工業的には、生産
効率等から複数個の構成が一般的である。FIG. 2 is a diagram showing details of the electrolytic cell in FIG. 1 according to the present invention. In FIG. 2, the reacted ammonium ammonium fluoride is led to the electrolytic cell main body 1 to be used as an electrolytic solution 2. The supply of the electrolytic solution may be either a continuous type or a batch type. However, when it is desired to continuously obtain a fixed amount of nitrogen trifluoride, the continuous type is preferable. Electrolytic cell body 1
Is partitioned by the partition plate 7 into the anode chamber 3 and the cathode chamber 5. The anode chamber 3 has a nickel anode 4 having a predetermined purity, and the cathode chamber 5 has a cathode 6 having the same purity as the anode 4. It should be noted that there is no particular problem even if the electrolytic cell main body 1 has a plurality of anodes and cathodes, and a plurality of structures are generally used industrially from the viewpoint of production efficiency and the like.
【0022】電解の条件としては、三フッ化窒素の溶融
塩電解法として温度110〜140℃程度に保持し、電
解槽本体1にある電極4及び6に直流の電流を通電して
溶融塩電解を行う。The electrolysis conditions are as follows: a molten salt electrolysis method of nitrogen trifluoride is carried out at a temperature of about 110 to 140 ° C., and a direct current is applied to the electrodes 4 and 6 in the electrolytic cell main body 1 so that I do.
【0023】電解時の電圧は5〜10V、電流密度は1
〜15A/dm2 程度で実施される。The voltage during electrolysis is 5 to 10 V, and the current density is 1
Approximately 15 A / dm 2 .
【0024】この溶融塩電解によって、陽極からは、N
F3 ガスが、また陰極からはH2 ガスが発生する。尚、
電解槽1には発生したNF3 ガスとH2 ガスの混合を避
けるために陽極4と陰極6の間に隔板7が設けてある。By this molten salt electrolysis, N
F 3 gas is generated, and H 2 gas is generated from the cathode. still,
In the electrolytic cell 1, a partition plate 7 is provided between the anode 4 and the cathode 6 in order to avoid mixing of the generated NF 3 gas and H 2 gas.
【0025】電極から発生したNF3 ガス及びH2 ガス
は混合しないようにそれぞれ個別の導管8及び9にて取
り出される。導管8にて取り出された粗NF3 ガスは精
製装置へ導かれる。また、陰極6から発生したH2 ガス
は、除外装置(図示していない)等を経て、大気中に放
出される。The NF 3 gas and the H 2 gas generated from the electrodes are taken out through separate conduits 8 and 9 so as not to mix. The crude NF 3 gas taken out through the conduit 8 is led to a purification device. Further, the H 2 gas generated from the cathode 6 is discharged into the atmosphere via an elimination device (not shown) or the like.
【0026】精製装置(方法)としては、例えば、従来
より一般的に使用されている薬液洗浄によるガス洗浄装
置、吸着剤を用いた吸着塔及び精留塔等からなる精製装
置で良い。The purifying apparatus (method) may be, for example, a purifying apparatus comprising a gas cleaning apparatus for cleaning with a chemical solution, an adsorption tower using an adsorbent, a rectifying tower, and the like which have been generally used.
【0027】尚、電解に際して、電解反応をマイルドに
進行させるためと、陽極室3及び陰極室5の圧力を出来
るだけ均一に維持する目的で窒素ガス、アルゴンガス、
ヘリウムガスなどのガスをキャリアーガスとしてそれぞ
れ適量、陽極室3及び陰極室5へ導管10及び11を通
して導く。At the time of electrolysis, nitrogen gas, argon gas, and the like are used in order to make the electrolysis reaction proceed mildly and to maintain the pressure in the anode chamber 3 and the cathode chamber 5 as uniform as possible.
An appropriate amount of a gas such as helium gas is introduced as a carrier gas to the anode chamber 3 and the cathode chamber 5 through the conduits 10 and 11, respectively.
【0028】このキャリアーガスの純度としては、NF
3 の純度に影響を与えない純度が好ましく、本発明者等
の研究では、純度4N以上が好ましく、6N以上が好適
である。該キャリアーガスとしては、工業的には、安価
でかつ高純度品を容易に入手可能な、窒素ガスの使用
が、好ましい。The carrier gas has a purity of NF
The purity which does not affect the purity of 3 is preferable, and in the study of the present inventors, the purity is preferably 4N or more, and more preferably 6N or more. As the carrier gas, it is preferable to use nitrogen gas, which is industrially inexpensive and easily obtains a high-purity product.
【0029】[0029]
【実施例】以下実施例により本発明をより具体的に説明
する。The present invention will be described more specifically with reference to the following examples.
【0030】実施例1 図1、図2に示すフローシート及び電解槽を用いて溶融
塩電解法によりNF3の製造をおこなった。Example 1 NF 3 was produced by a molten salt electrolysis method using the flow sheet and the electrolytic cell shown in FIGS.
【0031】まず、純度99.90 〜99.95wt %のフッ酸ガ
ス2.00kg/hr と純度99.6〜99.7wt%のアンモニアガス0.
71kg/hr とをSS-400にPFA をライニングした500lの反応
器にて、純度99.9999 %のN2ガスのシール下で反応さ
せ、HF/NH4 Fのモル比が1.7モルの酸性フッ化
アンモニウムを得た。First, 2.00 kg / hr of hydrofluoric acid gas having a purity of 99.90 to 99.95 wt% and ammonia gas having a purity of 99.6 to 99.7 wt%.
And 71 kg / hr at reactor 500l lined with PFA in SS-400, is reacted with a seal of a purity of 99.9999% of the N 2 gas, the molar ratio of HF / NH 4 F is 1.7 mole acid fluoride Ammonium chloride was obtained.
【0032】次に、SUS-304 にPSA をライニングした容
量450lの電解槽(電極が3セットあり)に酸性フッ化ア
ンモニウムを連続的に供給しながら、120℃の温度に
調整した。つぎに、陽極室に窒素ガスを0.11/minの
流量で導入しながら陽極から陰極に5アンペア(A)の
電流を流して電解を行った。このとき、陽極及び陰極は
純度99.0wt%のニッケル製とした。電解は連続3、000時
間実施した。Next, the temperature was adjusted to 120 ° C. while continuously supplying ammonium acid fluoride to a 450-liter electrolytic bath (three sets of electrodes) in which PSA was lined with SUS-304. Next, while introducing nitrogen gas into the anode chamber at a flow rate of 0.11 / min, a current of 5 amperes (A) was passed from the anode to the cathode to perform electrolysis. At this time, the anode and the cathode were made of nickel having a purity of 99.0 wt%. The electrolysis was carried out continuously for 3,000 hours.
【0033】陽極室からの発生した粗ガスを水、亜硫酸
ソーダ及び水酸化カリウムの薬液洗浄によるガス洗浄装
置、天然ゼオライトを充填した吸着塔及び精留塔とから
なる精製装置に送り、該装置出口ガスメーターによりガ
ス量を測定した。また出口ガス純度分析は、オンライン
のガスクロマトグラフィー用いて分析した。その結果、
ガス量10〜11l/minあり、得られたNF3 ガス
の純度は表1の通りであった。The crude gas generated from the anode chamber is sent to a purifying device comprising a gas washing device for washing water, sodium sulfite and potassium hydroxide with a chemical solution, an adsorption tower filled with natural zeolite and a rectification column, and the outlet of the device The gas amount was measured with a gas meter. Outlet gas purity analysis was performed using online gas chromatography. as a result,
The gas amount was 10 to 11 l / min, and the purity of the obtained NF 3 gas was as shown in Table 1.
【0034】[0034]
【表1】 [Table 1]
【0035】実施例2 実施例1と同一の装置にて、フッ酸ガスの純度を99.90
〜99.95wt%、アンモニアガスの純度を99.6〜99.7wt%、
電極の純度を99.0wt%とした以外は実施例1と同じ条件
とした。得られたNF3 の純度を分析したところ、表2
に示す結果が得られた。尚、電解は2、000時間行っ
た。Example 2 The same apparatus as in Example 1 was used to adjust the purity of hydrofluoric acid gas to 99.90.
~ 99.95wt%, purity of ammonia gas 99.6 ~ 99.7wt%,
The same conditions as in Example 1 were used except that the purity of the electrode was 99.0 wt%. The purity of the obtained NF 3 was analyzed.
The result shown in FIG. The electrolysis was performed for 2,000 hours.
【0036】[0036]
【表2】 [Table 2]
【0037】比較例1 実施例1と同一の装置にて電極の純度を98.3wt%とした
以外は、実施例1と同じ条件にて実施した。得られたN
F3 の純度を分析したところ、表3に示す結果となり、
純度4Nを下回った。尚、得られた製品純度が低いため
電解は1、000時間で停止した。Comparative Example 1 An experiment was carried out under the same conditions as in Example 1 except that the purity of the electrode was 98.3 wt% in the same apparatus as in Example 1. N obtained
When the purity of F 3 was analyzed, the results shown in Table 3 were obtained.
Purity was below 4N. The electrolysis was stopped after 1,000 hours due to the low purity of the obtained product.
【0038】[0038]
【表3】 [Table 3]
【0039】比較例2 実施例1と同一の装置にてフッ酸ガスの純度を97.5〜9
8.0wt%とした以外は、実施例1と同じ条件にて実施
した。得られたNF3 の純度を分析したところ、表4に
示す結果となり、純度4Nを下回った。尚、得られた製
品純度が低いため電解は600時間で停止した。Comparative Example 2 Using the same apparatus as in Example 1, the purity of hydrofluoric acid gas was 97.5-9.
The test was performed under the same conditions as in Example 1 except that the content was 8.0 wt%. When the purity of the obtained NF 3 was analyzed, the results shown in Table 4 were obtained, and the purity was lower than 4N. In addition, electrolysis was stopped after 600 hours because the obtained product purity was low.
【0040】[0040]
【表4】 [Table 4]
【0041】比較例3 実施例1と同一の装置にてアンモニアガスの純度を97.0
〜98.5wt%とした以外は、実施例1と同じ条件にて実施
した。得られたNF3 の純度を分析したところ、表5に
示す結果となり、純度4Nを下回った。尚、得られた製
品純度が低いため電解は700時間で停止した。Comparative Example 3 Using the same apparatus as in Example 1, the purity of ammonia gas was adjusted to 97.0
The procedure was performed under the same conditions as in Example 1 except that the content was set to 998.5 wt%. When the purity of the obtained NF 3 was analyzed, the result shown in Table 5 was obtained, which was lower than 4N. In addition, electrolysis was stopped in 700 hours because the obtained product purity was low.
【0042】[0042]
【表5】 [Table 5]
【0043】[0043]
【発明の効果】以上、詳細に説明したように本発明は、
工業的に、高純度の三フッ化窒素ガス(NF3 )を安価
に製造する方法において、所定の純度のフッ酸ガス及び
アンモニアガスを反応せしめ、得られた酸性フッ化アン
モニウムを電解液とし、更には陽極及び陰極に所定の純
度のニッケル電極を用い、溶融塩電解法によって電解を
行うという極めて簡単な方法である。As described above, the present invention provides:
Industrially, in a method of producing high-purity nitrogen trifluoride gas (NF 3 ) at low cost, a hydrofluoric acid gas and an ammonia gas having a predetermined purity are reacted, and the obtained ammonium ammonium fluoride is used as an electrolytic solution. Further, it is a very simple method of performing electrolysis by a molten salt electrolysis method using nickel electrodes of a predetermined purity for the anode and the cathode.
【0044】電極及び用いる原料の純度を特定すること
で、従来達成することか困難であった高純度のNF3 の
製造も本発明の方法によって容易に実施することが可能
となり、その意義は大きい。By specifying the purity of the electrode and the raw material to be used, it is possible to easily produce NF 3 of high purity, which was difficult to achieve conventionally, by the method of the present invention. .
【0045】また、本発明に開示した、所定の電極への
変更及び所定の原料へ変更することによって従来の設備
を何等変更することなく、本発明の効果を容易に受ける
ことが出来る等、本発明の工業的かつ経済的効果は極め
て、大なるものがある。Further, the effects of the present invention can be easily obtained without changing the conventional equipment by changing to the predetermined electrode and changing to the predetermined raw material disclosed in the present invention. The industrial and economic effects of the invention are extremely large.
【図1】本発明を実施するに適したフローシートの1例
を示す図FIG. 1 is a diagram showing an example of a flow sheet suitable for carrying out the present invention.
【図2】本発明を実施するに適した電解槽の1例を示す
図FIG. 2 shows an example of an electrolytic cell suitable for carrying out the present invention.
1 電解槽本体 2 電解液 3 陽極室 4 陽極 5 陰極室 6 陰極 7 隔板 8 導管 9 導管 10 キャリアーガス用導管 11 キャリアーガス用導管 DESCRIPTION OF SYMBOLS 1 Electrolyzer main body 2 Electrolyte 3 Anode chamber 4 Anode 5 Cathode chamber 6 Cathode 7 Separator 8 Conduit 9 Conduit 10 Carrier gas conduit 11 Carrier gas conduit
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C25B 1/00 - 15/08 C01B 21/083 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 7 , DB name) C25B 1/00-15/08 C01B 21/083
Claims (1)
ンモニウムを電解液とし溶融塩電解法により高純度の三
フッ化窒素を製造する方法において、該ニッケル電極が
純度98.5重量%以上であり、該酸性フッ化アンモニウム
が純度99.8重量%以上のフッ酸ガスと純度99.5重量%以
上のアンモニアガスとを反応させて得られることを特徴
とする高純度三フッ化窒素ガスの製造方法。1. A method for producing high-purity nitrogen trifluoride by molten salt electrolysis using ammonium acid fluoride as an electrolytic solution using a nickel electrode, wherein the nickel electrode has a purity of 98.5% by weight or more, A method for producing high-purity nitrogen trifluoride gas, characterized in that ammonium fluoride is obtained by reacting hydrofluoric acid gas having a purity of 99.8% by weight or more with ammonia gas having a purity of 99.5% by weight or more.
Priority Applications (1)
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JP25651494A JP3162588B2 (en) | 1994-10-21 | 1994-10-21 | Method for producing high-purity nitrogen trifluoride gas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25651494A JP3162588B2 (en) | 1994-10-21 | 1994-10-21 | Method for producing high-purity nitrogen trifluoride gas |
Publications (2)
Publication Number | Publication Date |
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JPH08120475A JPH08120475A (en) | 1996-05-14 |
JP3162588B2 true JP3162588B2 (en) | 2001-05-08 |
Family
ID=17293688
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JP25651494A Expired - Lifetime JP3162588B2 (en) | 1994-10-21 | 1994-10-21 | Method for producing high-purity nitrogen trifluoride gas |
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US7413722B2 (en) | 2005-08-04 | 2008-08-19 | Foosung Co., Ltd. | Method and apparatus for manufacturing nitrogen trifluoride |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US7413722B2 (en) | 2005-08-04 | 2008-08-19 | Foosung Co., Ltd. | Method and apparatus for manufacturing nitrogen trifluoride |
US11419675B2 (en) | 2010-06-16 | 2022-08-23 | St. Jude Medical, Llc | Ablation catheter having flexible tip with multiple flexible electrode segments |
US11457974B2 (en) | 2010-06-16 | 2022-10-04 | St. Jude Medical, Atrial Fibrillation Division, Inc. | Catheter having flexible tip with multiple flexible segments |
US8998845B2 (en) | 2012-06-04 | 2015-04-07 | St. Jude Medical, Atrial Fibrillation Division, Inc. | Deflection mechanism for an elongate medical device |
US8998844B2 (en) | 2012-06-04 | 2015-04-07 | St. Jude Medical, Atrial Fibrillation Division, Inc. | Handle extension for an elongate medical device |
KR102632513B1 (en) | 2021-06-10 | 2024-02-05 | 주식회사 로엔서지컬 | Multi-lumen tube apparatus of micro flexible surgical instrument |
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