JP2800838B2 - Nitrogen trifluoride production method - Google Patents
Nitrogen trifluoride production methodInfo
- Publication number
- JP2800838B2 JP2800838B2 JP1307242A JP30724289A JP2800838B2 JP 2800838 B2 JP2800838 B2 JP 2800838B2 JP 1307242 A JP1307242 A JP 1307242A JP 30724289 A JP30724289 A JP 30724289A JP 2800838 B2 JP2800838 B2 JP 2800838B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- reaction
- fluoride
- fluorine
- nitrogen trifluoride
- 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.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/083—Compounds containing nitrogen and non-metals and optionally metals containing one or more halogen atoms
- C01B21/0832—Binary compounds of nitrogen with halogens
- C01B21/0835—Nitrogen trifluoride
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Drying Of Semiconductors (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は三フッ化窒素（NF3）の製造法に関する。The present invention relates to a method for producing nitrogen trifluoride (NF 3 ).
三フッ化窒素は沸点−129℃の無色のガスであり、CVD
装置のプラズマ洗浄用ガスとして、またシリコン、ポリ
シリコン、Si3N4,WSi2,MoSi2などのドライエッチングガ
ス及びエキシマレーザー用ガスとして、またNF3はフッ
素より適度に活性が低いフッ素源として、また低い毒性
のため、従来特に、フルオロオレフィンの調製における
フッ素源としてや高エネルギー燃料の酸化剤に用いられ
る工業的に重要なガスである。Nitrogen trifluoride is a colorless gas with a boiling point of -129 ° C,
As a plasma cleaning gas for equipment, as a dry etching gas such as silicon, polysilicon, Si 3 N 4 , WSi 2 , MoSi 2 and a gas for excimer laser, and NF 3 as a fluorine source whose activity is appropriately lower than fluorine Due to its low toxicity, it is an industrially important gas conventionally used especially as a fluorine source in the preparation of fluoroolefins and as an oxidizer for high energy fuels.
従来の技術とその問題点 従来よりNF3の製造法として種々の方法が提案されて
いる。例えば米国特許第330428号には気体窒素を1000℃
を越える温度でプラズマアーク中を通過させ、また気体
フッ素を陽極に近いポスト・アーク域に導入することに
よりNF3を得る方法が開示されている。Various methods have been proposed as a conventional art method for producing NF 3 from the problems conventionally. For example, U.S. Pat.
How to obtain NF 3 discloses by passed through a plasma arc, also introducing a gas fluorine post-arc zone close to the anode at a temperature above.
また、特許公報昭62−21724には固体状の金属フッ化
物のアンモニウム錯体と元素状フッ素とを室温以上で気
固反応させてNF3を製造する方法が開示されている。A method of producing NF 3 by gas-solid reaction at room temperature or a solid ammonium complex and elemental fluorine of metal fluoride is disclosed in Japanese Patent Publication Sho 62-21724.
また、特許公報昭55−8926には気相状フッ素を融解温
度から実質的に400℃以下の温度までの温度に維持され
た液相アンモニウム酸フッ化物と反応を行わせてNF3を
製造する方法が述べられている。Also, Japanese Patent Publication No. 55-8926 discloses that NF 3 is produced by reacting gaseous fluorine with a liquid phase ammonium oxyfluoride maintained at a temperature from a melting temperature to substantially 400 ° C. or less. The method is described.
ジャーナル オブ アメリカン ケミカルソサイアテ
ィ（J.Am.Chem.Soc.）82巻、5301ページ（1960年）記載
の論文にはアンモニア対フッ素のモル比、約1:1から2:1
を用いてアンモニアの直接気相フッ素化によるNF3の合
成について開示している。反応条件の詳細について記載
はみられないがフッ素基準で約10〜25％のNF3の収率を
報告している。The Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 82 , p. 5301 (1960) contains a molar ratio of ammonia to fluorine, about 1: 1 to 2: 1.
It discloses the synthesis of NF 3 by the direct vapor phase fluorination of ammonia with. Although the details of the reaction conditions are not described, a yield of NF 3 of about 10 to 25% based on fluorine is reported.
米国特許第325474号には酸性フッ化アンモニウムの溶
融塩電解法について記載されている。U.S. Pat. No. 325,474 describes a molten salt electrolysis method of ammonium acid fluoride.
これらはいずれも元素状のフッ素を使用しており、第
一義的には爆発の危険性があり、従って、爆発防止のた
めに種々の提案がなされているが、いずれも満足しうる
ものではなく、結果的には収率の低下を招くものであ
る。All of these use elemental fluorine, and there is a danger of explosion in the first place. Therefore, various proposals have been made to prevent explosion, but none of them are satisfactory. However, as a result, the yield is reduced.
また電解法において酸性フッ化アンモニウムまたはフ
ッ化アンモニウムとフッ化水素を原料とするNH4・HF系
やこれに更にフッ化カリウムまたはフッ化カリウムを原
料として加えたKF・NH4F・HF系で溶解塩電解を行いNF3
を製造する場合、電解槽の陽極からはNF3ガスが発生
し、陰極からH2ガスが発生する。このNF3とH2は混合す
ると爆発を引き起こす。従って、その運転法に種々の工
夫をする必要がある。Also, in the electrolytic method, NH 4 · HF system using ammonium acid fluoride or ammonium fluoride and hydrogen fluoride as raw materials or KF · NH 4 F · HF system further added with potassium fluoride or potassium fluoride as raw materials NF 3
When producing, an NF 3 gas is generated from the anode of the electrolytic cell and an H 2 gas is generated from the cathode. This NF 3 and H 2 cause an explosion when mixed. Therefore, it is necessary to make various contrivances in the operation method.
発明の目的 本発明の目的は、上記従来法の欠点を排除し、爆発の
危険なく、特別な装置を必要とせず、効率よくNF3を製
造することである。OBJECT OF THE INVENTION An object of the present invention is to eliminate the drawbacks of the above-mentioned conventional methods, to produce NF 3 efficiently without danger of explosion, without requiring special equipment.
発明の内容 本発明は、アンモニアをフッ素化するにあたり、従来
の特許文献等にみられるような元素状フッ素を用いるこ
となく、三フッ化コバルト（CoF3）、二フッ化銀（Ag
F2）、三フッ化マンガン（MnF3）、及びCoF3とKFの複合
塩（KCoF4）等でフッ素化することによりNF3を製造する
方法である。反応温度は50〜450℃の範囲が好ましい。
また、アンモニアを窒素等の不活性ガスで希釈したり、
NF3で希釈してCoF3等と反応させる等、適宜選択するこ
とができる。DETAILED DESCRIPTION OF THE INVENTION In the present invention, in fluorinating ammonia, cobalt trifluoride (CoF 3 ), silver difluoride (Ag
This is a method for producing NF 3 by fluorination with F 2 ), manganese trifluoride (MnF 3 ), a complex salt of CoF 3 and KF (KCoF 4 ), or the like. The reaction temperature is preferably in the range of 50 to 450 ° C.
Also, ammonia may be diluted with an inert gas such as nitrogen,
It can be appropriately selected, for example, by diluting with NF 3 and reacting with CoF 3 or the like.
また、本発明は反応によりフッ素化能力がなくなった
金属フッ化物を元素状フッ素で再生する際、反応により
副生したフッ化アンモニウム（NH4F）や酸性フッ化アン
モニウム（NH4F・nHF）は元素状フッ素と反応させNF3を
生成することが出来る。The present invention also provides a method for regenerating metal fluoride, which has lost its fluorination ability by a reaction, with elemental fluorine, such as ammonium fluoride (NH 4 F) or ammonium ammonium fluoride (NH 4 F · nHF) by-produced by the reaction. can generate an NF 3 is reacted with elemental fluorine.
従って、本発明は本反応の副生物も無駄なく利用し連
続してNF3を生成することができる。Therefore, the present invention can continuously produce NF 3 by using the by-product of this reaction without waste.
また、本発明は元素状フッ素を利用する従来法に比べ
活性の弱い三フッ化コバルト等を使用するため反応の制
御が容易、しかも安全にNF3を高収率で得ることが出来
る利点がある。In addition, the present invention has an advantage that NF 3 can be easily obtained in a high yield with ease of control of the reaction because cobalt trifluoride or the like having a low activity is used as compared with the conventional method utilizing elemental fluorine. .
さらに、本発明を実施するに際し、アンモニアは一
括、分割仕込を適宜選択することが出来る。Further, in carrying out the present invention, the batch preparation and the division preparation of ammonia can be appropriately selected.
実施例 以下実施例により本発明をさらに詳細に説明する。Examples Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例−１ ニッケル製反応器に三フッ化コバルト（CoF3）を50kg
仕込んだ。EXAMPLE -1 nickel reactor trifluoride cobalt (CoF 3) 50 kg
I charged.
この反応器を80℃（CoF3層温度）に調節し、アンモニ
アガスを10／分の割合で送入した。反応ガスを10％水
酸化カリウム水溶液が循環しているアルカリ洗浄塔で洗
浄後、ガスメータで計量し、ガスクロマトグラフィーに
よって組成を分析した。The reactor was adjusted to 80 ° C. (CoF 3 layer temperature) and ammonia gas was fed in at a rate of 10 / min. After the reaction gas was washed with an alkaline washing tower in which a 10% aqueous potassium hydroxide solution was circulated, the reaction gas was weighed with a gas meter, and the composition was analyzed by gas chromatography.
その結果、平均ガス組成は次の通りであった。（ガス
クロマトグラフィー面積パーセント、以下同じ） O2 0.2％ N2 79.3％ NF3 19.8％ その他 0.7％ 実施例−２ 実施例−１と同じ反応器で反応温度を160℃（CoF3層
温度）に調節し、アンモニアと窒素の混合ガス（1:1）
を10／分の割合で送入した。反応ガスは10％水酸化カ
リウム水溶液が循環するアルカリ洗浄塔で洗浄後、ガス
メーターで計量し、ガスクロマトグラフィーによって組
成を分析した。As a result, the average gas composition was as follows. (Gas chromatography area percent, the same applies hereinafter) O 2 0.2% N 2 79.3% NF 3 19.8% Other 0.7% Example-2 The reaction temperature was set to 160 ° C (CoF three- layer temperature) in the same reactor as in Example-1. Adjust the ammonia and nitrogen mixture gas (1: 1)
At a rate of 10 / min. The reaction gas was washed with an alkaline washing tower in which a 10% aqueous solution of potassium hydroxide circulates, then weighed with a gas meter, and analyzed for composition by gas chromatography.
その結果、平均ガス組成は次の通りであった。 As a result, the average gas composition was as follows.
O2 0.1％ N2 90.6％ NF3 8.5％ その他 0.8％ 実施例−３ 実施例−１と同じ反応器でCoF3の代わりにCoF3とKFの
複合塩（1:1）を入れ、反応器を300℃（CoF3−KF層温
度）に調節し、アンモニアガスを10／分の割合で送入
した。反応ガスを10％水酸化カリウム水溶液が循環して
いるアルカリ洗浄塔で洗浄後、ガスメーターで計量し、
ガスクロマトグラフィーによって平均組成を分析した。 O 2 0.1% N 2 90.6% NF 3 8.5% Others 0.8% Example -3 CoF 3 and KF composite salt in place of Example -1 and CoF 3 in the same reactor (1: 1) were charged, the reactor Was adjusted to 300 ° C. (CoF 3 −KF layer temperature), and ammonia gas was fed at a rate of 10 / min. After washing the reaction gas with an alkaline washing tower in which a 10% aqueous potassium hydroxide solution is circulated, weigh it with a gas meter,
The average composition was analyzed by gas chromatography.
O2 0.1％ N2 65.3％ NF3 34.2％ その他 0.4％ 実施例−４ 実施例−1,2,3それぞれ反応終了後、元素状フッ素を
５／分で送入した。反応生成ガスは10％水酸化カリウ
ム水溶液が循環するアルカリ洗浄塔で洗浄後、ガスメー
ターで計量し、ガスクロマトグラフィーによって組成を
分析した。平均組成は以下の通りであった。O 2 0.1% N 2 65.3% NF 3 34.2% Others 0.4% Example-4 After completion of the reaction in each of Examples 1, 2, and 3, elemental fluorine was fed in at 5 / min. The reaction product gas was washed with an alkaline washing tower in which a 10% aqueous solution of potassium hydroxide circulates, then weighed with a gas meter, and analyzed for composition by gas chromatography. The average composition was as follows.
O2 3.6％ N2 35.3％ NF3 56.7％ その他 4.4％ 実施例−５ 実施例１で使用した反応器に更にガス送入口を２ヶ所
取り付け、反応器を120℃に調節し、３ヶ所よりNH3を各
々５／分の流速で計15／分送入した。反応ガスを実
施例１〜４と同様に後処理し、ガス組成をガラスクロマ
トグラフィーで分析したところ平均ガス組成は次の通り
であった。O 2 3.6% N 2 35.3% NF 3 56.7% Other 4.4% Example-5 Two more gas inlets were installed in the reactor used in Example 1, the reactor was adjusted to 120 ° C, and NH was introduced from three locations. 3 were fed at a flow rate of 5 / min each for a total of 15 / min. The reaction gas was post-treated in the same manner as in Examples 1 to 4, and the gas composition was analyzed by glass chromatography. The average gas composition was as follows.
O2 0.2％ N2 59.4％ NF3 39.3％ その他 1.1％O 2 0.2% N 2 59.4% NF 3 39.3% Other 1.1%
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小野 信博 群馬県渋川市1497 関東電化工業株式会 社渋川工場内 (72)発明者 斉藤 睦夫 群馬県渋川市1497 関東電化工業株式会 社渋川工場内 (58)調査した分野(Int.Cl.6，ＤＢ名) C01B 21/083 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Nobuhiro Ono 1497 Shibukawa-shi, Gunma Prefecture Shibukawa Plant of Kanto Denka Kogyo Co., Ltd. 58) Field surveyed (Int.Cl. 6 , DB name) C01B 21/083 CA (STN) REGISTRY (STN)
Claims (2)
複合塩とアンモニアとを50〜450℃の範囲で反応させる
ことを特徴とする三フッ化窒素の製造法。1. A process for producing nitrogen trifluoride, comprising reacting a metal fluoride and / or a complex salt of the metal fluoride with ammonia at a temperature of 50 to 450 ° C.
化アンモニウム金属フッ化物の再生反応と並行してフッ
素と反応させることを特徴とする特許請求の範囲第１項
記載の製造法。2. The method according to claim 1, wherein the reaction is carried out with fluorine in parallel with the regeneration reaction of the by-produced ammonium fluoride and ammonium acid fluoride metal fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1307242A JP2800838B2 (en) | 1989-11-27 | 1989-11-27 | Nitrogen trifluoride production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1307242A JP2800838B2 (en) | 1989-11-27 | 1989-11-27 | Nitrogen trifluoride production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03170306A JPH03170306A (en) | 1991-07-23 |
| JP2800838B2 true JP2800838B2 (en) | 1998-09-21 |
Family
ID=17966749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1307242A Expired - Lifetime JP2800838B2 (en) | 1989-11-27 | 1989-11-27 | Nitrogen trifluoride production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2800838B2 (en) |
-
1989
- 1989-11-27 JP JP1307242A patent/JP2800838B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03170306A (en) | 1991-07-23 |
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