JP4197783B2 - Method for producing fluorinated halogen compound - Google Patents
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- JP4197783B2 JP4197783B2 JP33095398A JP33095398A JP4197783B2 JP 4197783 B2 JP4197783 B2 JP 4197783B2 JP 33095398 A JP33095398 A JP 33095398A JP 33095398 A JP33095398 A JP 33095398A JP 4197783 B2 JP4197783 B2 JP 4197783B2
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【０００１】
【発明の属する技術分野】
本発明は、フッ素化剤、あるいは半導体産業におけるエッチングガス、クリーニングガスとして有用な七フッ化ヨウ素、五フッ化臭素、三フッ化塩素、一フッ化塩素等のフッ素化ハロゲン化合物の製造方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
五フッ化臭素、三フッ化塩素、一フッ化塩素等のフッ素化ハロゲン化合物の製造方法としては、フッ素と対応する当量数のハロゲン元素を気相、または液相で反応させることが知られている［例えば、L.Stein: J.Am.Chem.Soc.,81,1269(1959),H.E.Kluksdahl,G.H.Cady:J.Am.Chem.Soc.,81,5285(1959),J.W.Mellor(ed):A Comprehensive Treatise on Inorganic and Theoretical Chemistry,Supplement II,part I,(1956),147］。しかし、気相反応の場合、反応温度は 200℃以上が必要で、特に原料（フッ素以外のハロゲン元素またはフッ素化ハロゲン）とフッ素ガスの接触部分で局部的に反応が進行して、温度が上昇し、時には赤熱状態にまで達し、激しい反応器の腐食を生じる場合がある。また、液相反応の場合、原料溶液中に溶解したフッ素が爆発的に反応する危険性が高い。
さらに七フッ化ヨウ素のように最高原子価まで酸化されたフッ素化ハロゲン化合物の製造方法としては、加熱した五フッ素ヨウ素の液中にフッ素を吹き込み、フッ素に帯同された五フッ化ヨウ素とフッ素を 300℃の反応ゾーンへ導き、七フッ化ヨウ素を得ることが知られている［例えば、W.C.Schumb,M.A.Lynch Jr.,Ind.Eng.Chem.,42,1383(1950)］。この場合、五フッ化ヨウ素中に溶解したフッ素が爆発的に反応したり、高温の五フッ化ヨウ素液を保持する容器の腐食が起こる等の問題点があり、工業的に適した反応方法とは言えない。また、消費された五フッ化ヨウ素の補給のために反応を停止する必要もある。さらにまた、ヨウ素とフッ素の直接反応により製造する場合は、反応熱が大きく、反応の制御が難しい上、ヨウ素が固体であることからその取り扱い方法も容易ではない。
【０００３】
【課題を解決するための手段】
本発明の目的は、安全にかつ容易に連続的に七フッ化ヨウ素、五フッ化臭素、三フッ化塩素、一フッ化塩素等のフッ素化ハロゲン化合物を効率良く製造することにある。
本発明は、上述の課題を解決すべくなされた発明である。
即ち本発明は、以下の（１）〜（４）に述べるフッ素化ハロゲン化合物の製造方法である。
（１）100 〜 130 ℃に設定した蒸発器に導入したフッ素ガス気流中にフッ素以外のハロゲンを加え蒸発・混合させた後の混合ガスを、フッ素ガスとフッ素以外のハロゲンとの反応温度以上の温度に加熱された反応器に導入し、フッ素ガスとフッ素以外のハロゲンとを反応させることを特徴とするフッ素化ハロゲン化合物の製造方法。
（２）100 〜 130 ℃に設定した蒸発器に導入したフッ素ガス気流中にフッ素化ハロゲンを加え蒸発・混合させた後の混合ガスを、フッ素ガスとフッ素化ハロゲンとの反応温度以上の温度に加熱された反応器に導入し、フッ素ガスとフッ素化ハロゲンとを反応させることを特徴とするフッ素化ハロゲン化合物の製造方法。
（３）100 〜 130 ℃に設定した蒸発器に導入したフッ素ガス気流中にフッ素以外のハロゲン及びフッ素化ハロゲンを加え蒸発・混合させた後の混合ガスを、フッ素ガスとフッ素以外のハロゲン及びフッ素化ハロゲンとの反応温度以上の温度に加熱された反応器に導入し、フッ素ガスとフッ素以外のハロゲン及びフッ素化ハロゲンとを反応させることを特徴とするフッ素化ハロゲン化合物の製造方法。
（４）蒸発器内のフッ素ガスの線速度を30cm／sec.以下とし、反応器内のガス線速度を10cm／sec.以下とすることを特徴とする上記（１）、（２）又は（３）記載のフッ素化ハロゲン化合物の製造方法。
本発明では、緩やかに流れ、かつ原料（フッ素以外のハロゲン元素またはフッ素化ハロゲン）の沸点付近まで加熱されたフッ素ガス気流中に五フッ化ヨウ素等の反応原料を加え、蒸発・混合させた後に、これらのガスを高温の反応器に導入し、反応させることによって、効率良く、連続的に七フッ化ヨウ素等の目的物を得ることができる。これにより、原料とフッ素ガスの混合部の温度を原料の沸点付近程度（100 〜130 ℃）に抑えることができ、混合部の腐食を大幅に低減することができる。また、原料とフッ素ガスの混合部と反応部を分離し、十分に攪拌・混合および緩やかに加熱された化学量論量の原料を反応器に供給することによって爆発的な反応を防止することができる。
【０００４】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明は、七フッ化ヨウ素のみならず、その他のフッ素化ハロゲン物、例えば、五フッ化臭素、三フッ化塩素、一フッ化塩素等の製造方法にも有効に使用できる。
本発明に使用される製造装置は、三フッ化臭素、五フッ化ヨウ素、臭素等の原料を蒸発させ、かつ、フッ素ガスと混合させる蒸発器（塩素の場合には予備加熱器で良い）とフッ素化反応を行う反応器の二つから成り立っている。
蒸発器と反応器の材質は、ニッケル、インコネル、ハステロイ、モネル、アルミニウム、銅、鉄等が使用できるが、ニッケル、インコネル、モネル等が最も望ましい。
【０００５】
蒸発器は、一定の温度に保てるように加熱と冷却が可能なジャケット式の保温装置を備えたものが望ましい。蒸発器内のフッ素ガスの線速度は、30cm／sec.以下、望ましくは５cm／sec.以下に押さえる必要がある。さもなくば、フッ素と原料の急激な反応が起こり、その反応熱により蒸発器の腐食が発生する可能性がある。
【０００６】
一方、反応器中のガス線速度は、反応に必要な滞留時間が取れるように設定されるが、10cm／sec.以下に押さえることが望ましい。また、反応器内には、ガスの攪拌・混合が効率良くなされるような構造とすることが好ましく、例えば、ジャマ板等が設置される。
【０００７】
【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が、本発明はこれらに限定されるものではない。
実施例１（三フッ化塩素の製造）
図１に示す反応装置を用い、 100℃に設定したニッケル製の予備加熱器にフッ素ガスを１cm／sec.の線速度になるように導入し、この気流中に塩素ガスを0.31cm／sec.の線速度になるように導入した。この混合ガスを 300℃に加熱した反応器に２cm／sec.の線速度で導入した。８時間反応を続け、反応器より排出されたガスを冷却捕集し、分析を行ったところ、三フッ化塩素が塩素基準の収率95％で得られた。1000時間反応を行っても、蒸発器及び反応器には、腐食現象が全く見られず、爆発も観測されず、安定した反応を行うことができた。
【０００８】
比較例１
実施例１の反応器より予備加熱器を除き、同様の条件で反応を行った。この場合には、反応開始直後より、反応温度が急激に上昇し、塩素とフッ素の混合部が赤熱状態まで温度上昇した。さらに反応が円滑に持続せず、ハンチングによって系内圧力および流量が大きく変化し、反応を続けることができなかった。
【０００９】
実施例２（五フッ化臭素の製造）
100℃に設定したニッケル製の蒸発器にフッ素ガスを２cm／sec.の線速度になるように導入し、この気流中に臭素を0.35cm／sec.の線速度になるように滴下した。この混合ガスを 200℃に加熱した反応器に 3.5cm／sec.の線速度で導入した。６時間反応を継続して、反応器より排出されたガスを冷却捕集し、分析を行ったところ、五フッ化臭素が臭素基準の収率90％で得られた。この場合にも、反応を30時間行っても蒸発器及び反応器には、腐食現象、爆発現象が全く観測されず、安定した反応を行うことができた。この場合、臭素に変えて、三フッ化臭素を 130℃に設定したニッケル製の蒸発器中のフッ素気流中に滴下しても同様の結果が得られた。
【００１０】
比較例２
実施例２の反応器より蒸発器を取り除き、他は同様の条件で反応を行った。この時、反応開始後、30分で臭素の導入口付近が赤熱状態まで上昇し、反応を続行することができなくなった。
【００１１】
実施例３（七フッ化ヨウ素の製造）
120℃に設定したニッケル製の蒸発器にフッ素ガスを２cm／sec.の線速度になるように導入し、この気流中に五フッ化ヨウ素を 1.9cm／sec.の線速度になるように滴下した。この混合ガスを 300℃に加熱した反応器に 5.6cm／sec.の線速度で導入した。８時間反応を行い、反応器より排出されたガスを冷却捕集し、分析を行ったところ、七フッ化ヨウ素が五フッ化ヨウ素基準の収率60％で得られた。この場合にも、反応を50時間行っても蒸発器及び反応器には、腐食現象、爆発現象が全く観測されず、安定した反応を行うことができた。
【００１２】
比較例３
実施例３の反応器より蒸発器を取り除き、他は同様の条件で反応を行った。この場合も反応開始直後より五フッ化ヨウ素の導入口付近が赤熱状態まで上昇し、反応を続行することができなくなった。
【図面の簡単な説明】
【図１】 本発明に方法に用いる反応装置の一例を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a fluorinated halogen compound such as iodine heptafluoride, bromine pentafluoride, chlorine trifluoride, chlorine monofluoride and the like useful as a fluorinating agent, or as an etching gas or cleaning gas in the semiconductor industry.
[0002]
[Prior art and problems to be solved by the invention]
As a method for producing a fluorinated halogen compound such as bromine pentafluoride, chlorine trifluoride, or chlorine monofluoride, it is known to react fluorine and a corresponding equivalent number of halogen elements in a gas phase or a liquid phase. [For example, L. Stein: J. Am. Chem. Soc., 81 , 1269 (1959), HEKluksdahl, GHCady: J. Am. Chem. Soc., 81 , 5285 (1959), JWMellor (ed): A Comprehensive Treatise on Inorganic and Theoretical Chemistry, Supplement II, part I, (1956), 147]. However, in the case of a gas phase reaction, the reaction temperature needs to be 200 ° C. or higher, and the reaction proceeds locally at the contact portion of the raw material (halogen other than fluorine or fluorinated halogen) and fluorine gas, and the temperature rises However, sometimes it reaches a red hot condition and may cause severe reactor corrosion. In the liquid phase reaction, there is a high risk that fluorine dissolved in the raw material solution reacts explosively.
Furthermore, as a method for producing a fluorinated halogen compound that has been oxidized to the maximum valence, such as iodine heptafluoride, fluorine is blown into a heated pentafluoro iodine solution, and iodine pentafluoride and fluorine associated with fluorine are used. It is known to lead to a reaction zone at 300 ° C. to obtain iodine heptafluoride [eg WCSchumb, MALynch Jr., Ind. Eng. Chem., 42, 1383 (1950)]. In this case, there is a problem that fluorine dissolved in iodine pentafluoride reacts explosively or corrosion of a container holding a high-temperature iodine pentafluoride solution occurs. I can't say that. It is also necessary to stop the reaction to replenish consumed iodine pentafluoride. Furthermore, in the case of producing by direct reaction of iodine and fluorine, the reaction heat is large, the reaction is difficult to control, and the handling method is not easy because iodine is solid.
[0003]
[Means for Solving the Problems]
An object of the present invention is to efficiently and efficiently produce fluorinated halogen compounds such as iodine heptafluoride, bromine pentafluoride, chlorine trifluoride, and chlorine monofluoride continuously and safely.
The present invention has been made to solve the above-described problems.
That is, the present invention is a method for producing a fluorinated halogen compound described in the following (1) to (4).
(1) The mixed gas after the halogen gas other than fluorine is added to the fluorine gas stream introduced into the evaporator set to 100 to 130 ° C and evaporated and mixed is made to exceed the reaction temperature of fluorine gas and halogen other than fluorine. A method for producing a fluorinated halogen compound, which is introduced into a reactor heated to a temperature and reacts a fluorine gas with a halogen other than fluorine.
(2) the 100 ~ 130 ° C. mixed gas after fluorination halogen was added and evaporated and mixed into the fluorine gas stream introduced to the set evaporator, the reaction temperature above the temperature of fluorine gas and fluorine halogen A method for producing a fluorinated halogen compound, which is introduced into a heated reactor and reacts a fluorine gas and a fluorinated halogen.
(3) Fluorine gas introduced into an evaporator set to 100 to 130 ° C, and then the mixture gas after the halogen gas other than fluorine and fluorinated halogen is added and evaporated and mixed into the fluorine gas stream is mixed with fluorine gas and halogen other than fluorine and fluorine. A method for producing a fluorinated halogen compound, comprising introducing into a reactor heated to a temperature equal to or higher than a reaction temperature with a halogenated fluoride, and reacting a fluorine gas with a halogen other than fluorine and a fluorinated halogen.
(4) The linear velocity of the fluorine gas in the evaporator is 30 cm / sec or less, and the gas linear velocity in the reactor is 10 cm / sec or less, (1), (2) or ( 3) The manufacturing method of the fluorinated halogen compound of description.
In the present invention, after adding a reaction raw material such as iodine pentafluoride in a fluorine gas stream heated to near the boiling point of the raw material (halogen element other than fluorine or fluorinated halogen), and evaporating and mixing the raw material By introducing these gases into a high-temperature reactor and allowing them to react, the desired product such as iodine heptafluoride can be obtained efficiently and continuously. Thereby, the temperature of the mixing part of the raw material and the fluorine gas can be suppressed to around the boiling point of the raw material (100 to 130 ° C.), and the corrosion of the mixing part can be greatly reduced. In addition, the mixing part and the reaction part of the raw material and fluorine gas are separated, and an explosive reaction can be prevented by supplying a stoichiometric amount of raw material that is sufficiently stirred and mixed and gently heated to the reactor. it can.
[0004]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The present invention can be effectively used not only for iodine heptafluoride but also for other fluorinated halides such as bromine pentafluoride, chlorine trifluoride and chlorine monofluoride.
The production apparatus used in the present invention includes an evaporator (a preheater may be used in the case of chlorine) that evaporates raw materials such as bromine trifluoride, iodine pentafluoride, and bromine, and mixes with fluorine gas. It consists of two reactors that perform the fluorination reaction.
As materials for the evaporator and the reactor, nickel, inconel, hastelloy, monel, aluminum, copper, iron and the like can be used, but nickel, inconel, monel and the like are most desirable.
[0005]
The evaporator is preferably provided with a jacket-type heat retaining device capable of heating and cooling so as to maintain a constant temperature. The linear velocity of the fluorine gas in the evaporator needs to be suppressed to 30 cm / sec. Or less, preferably 5 cm / sec. Or less. Otherwise, a rapid reaction between the fluorine and the raw material occurs, and the reaction heat may cause corrosion of the evaporator.
[0006]
On the other hand, the gas linear velocity in the reactor is set so that the residence time required for the reaction can be obtained, but it is desirable to suppress it to 10 cm / sec or less. Further, it is preferable that the reactor has a structure that allows gas to be efficiently stirred and mixed. For example, a jammer plate or the like is installed.
[0007]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these.
Example 1 (Production of chlorine trifluoride)
Using the reactor shown in FIG. 1, fluorine gas was introduced into a nickel preheater set at 100 ° C. so as to have a linear velocity of 1 cm / sec., And chlorine gas was introduced into this air stream at 0.31 cm / sec. Introduced to achieve a linear velocity of. This mixed gas was introduced into a reactor heated to 300 ° C. at a linear velocity of 2 cm / sec. The reaction was continued for 8 hours, and the gas discharged from the reactor was collected by cooling and analyzed. As a result, chlorine trifluoride was obtained in a yield of 95% based on chlorine. Even when the reaction was performed for 1000 hours, no corrosion phenomenon was observed in the evaporator and the reactor, no explosion was observed, and a stable reaction could be performed.
[0008]
Comparative Example 1
The reaction was carried out under the same conditions except that the preheater was removed from the reactor of Example 1. In this case, immediately after the start of the reaction, the reaction temperature rapidly increased, and the temperature of the mixed portion of chlorine and fluorine increased to a red hot state. Furthermore, the reaction did not continue smoothly, and the system pressure and flow rate changed greatly due to hunting, and the reaction could not be continued.
[0009]
Example 2 (Production of bromine pentafluoride)
Fluorine gas was introduced into a nickel evaporator set at 100 ° C. so as to have a linear velocity of 2 cm / sec., And bromine was dropped into this air stream so as to have a linear velocity of 0.35 cm / sec. This mixed gas was introduced into a reactor heated to 200 ° C. at a linear velocity of 3.5 cm / sec. The reaction was continued for 6 hours, and the gas discharged from the reactor was collected by cooling and analyzed. As a result, bromine pentafluoride was obtained in a yield of 90% based on bromine. In this case, even if the reaction was performed for 30 hours, no corrosion phenomenon or explosion phenomenon was observed in the evaporator and the reactor, and a stable reaction could be performed. In this case, the same result was obtained when bromine trifluoride was dropped into a fluorine stream in a nickel evaporator set at 130 ° C. instead of bromine.
[0010]
Comparative Example 2
The evaporator was removed from the reactor of Example 2, and the reaction was performed under the same conditions as the others. At this time, 30 minutes after the start of the reaction, the vicinity of the bromine inlet rose to a red hot state, and the reaction could not be continued.
[0011]
Example 3 (Production of iodine heptafluoride)
Fluorine gas is introduced into a nickel evaporator set at 120 ° C so that the linear velocity is 2 cm / sec., And iodine pentafluoride is dropped into this air stream so that the linear velocity is 1.9 cm / sec. did. This mixed gas was introduced into a reactor heated to 300 ° C. at a linear velocity of 5.6 cm / sec. When the reaction was carried out for 8 hours, the gas discharged from the reactor was collected by cooling and analyzed, iodine heptafluoride was obtained in a yield of 60% based on iodine pentafluoride. Also in this case, even if the reaction was carried out for 50 hours, no corrosion phenomenon or explosion phenomenon was observed in the evaporator and the reactor, and a stable reaction could be carried out.
[0012]
Comparative Example 3
The evaporator was removed from the reactor of Example 3, and the reaction was carried out under the same conditions as above. Also in this case, immediately after the start of the reaction, the vicinity of the iodine pentafluoride inlet rose to a red hot state, and the reaction could not be continued.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a reaction apparatus used in the method of the present invention.
Claims (4)
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| JP33095398A JP4197783B2 (en) | 1998-11-20 | 1998-11-20 | Method for producing fluorinated halogen compound |
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| JP33095398A JP4197783B2 (en) | 1998-11-20 | 1998-11-20 | Method for producing fluorinated halogen compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4693823B2 (en) | 2007-06-18 | 2011-06-01 | セントラル硝子株式会社 | Production method of iodine heptafluoride |
| JP5163190B2 (en) * | 2008-03-10 | 2013-03-13 | セントラル硝子株式会社 | Method for producing oxygen-containing halogenated fluoride |
| WO2010055769A1 (en) * | 2008-11-12 | 2010-05-20 | セントラル硝子株式会社 | Inter-halogen compound synthesis method |
| JP2010116281A (en) * | 2008-11-12 | 2010-05-27 | Central Glass Co Ltd | Method for producing interhalogen compound |
| JP2010116280A (en) * | 2008-11-12 | 2010-05-27 | Central Glass Co Ltd | Method for synthesizing interhalogen compound |
| JP6201496B2 (en) * | 2013-08-02 | 2017-09-27 | セントラル硝子株式会社 | IF7-derived iodine fluoride compound recovery method and recovery device |
| JP6210039B2 (en) | 2014-09-24 | 2017-10-11 | セントラル硝子株式会社 | Deposit removal method and dry etching method |
| JP6467955B2 (en) * | 2015-01-30 | 2019-02-13 | セントラル硝子株式会社 | Method for producing iodine pentafluoride |
| CN112537755A (en) * | 2020-12-16 | 2021-03-23 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method and device of iodine pentafluoride |
| CN114314513B (en) * | 2021-12-31 | 2023-05-12 | 四川红华实业有限公司 | Method for fluoridation of low-valence fluoride by using chlorine trifluoride |
| CN115448256B (en) * | 2022-09-16 | 2023-03-21 | 福建德尔科技股份有限公司 | Method and reaction device for synthesizing chlorine trifluoride by one-step method |
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1998
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