JP4170140B2 - Method for producing xenon difluoride - Google Patents
Method for producing xenon difluoride Download PDFInfo
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- JP4170140B2 JP4170140B2 JP2003130924A JP2003130924A JP4170140B2 JP 4170140 B2 JP4170140 B2 JP 4170140B2 JP 2003130924 A JP2003130924 A JP 2003130924A JP 2003130924 A JP2003130924 A JP 2003130924A JP 4170140 B2 JP4170140 B2 JP 4170140B2
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- xenon
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- cooling
- xenon difluoride
- difluoride
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- BLIQUJLAJXRXSG-UHFFFAOYSA-N 1-benzyl-3-(trifluoromethyl)pyrrolidin-1-ium-3-carboxylate Chemical compound C1C(C(=O)O)(C(F)(F)F)CCN1CC1=CC=CC=C1 BLIQUJLAJXRXSG-UHFFFAOYSA-N 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 238000001816 cooling Methods 0.000 claims description 31
- 229910052724 xenon Inorganic materials 0.000 claims description 14
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 5
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 16
- RPSSQXXJRBEGEE-UHFFFAOYSA-N xenon tetrafluoride Chemical compound F[Xe](F)(F)F RPSSQXXJRBEGEE-UHFFFAOYSA-N 0.000 description 16
- 238000007711 solidification Methods 0.000 description 14
- 230000008023 solidification Effects 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- IGELFKKMDLGCJO-UHFFFAOYSA-N xenon difluoride Chemical compound F[Xe]F IGELFKKMDLGCJO-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- RXPRRQLKFXBCSJ-GIVPXCGWSA-N vincamine Chemical compound C1=CC=C2C(CCN3CCC4)=C5[C@@H]3[C@]4(CC)C[C@](O)(C(=O)OC)N5C2=C1 RXPRRQLKFXBCSJ-GIVPXCGWSA-N 0.000 description 1
- ARUUTJKURHLAMI-UHFFFAOYSA-N xenon hexafluoride Chemical compound F[Xe](F)(F)(F)(F)F ARUUTJKURHLAMI-UHFFFAOYSA-N 0.000 description 1
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Description
【0001】
【発明の属する技術分野】
本発明は、エレクトロニクス分野の中で半導体製造用ガスとして使用される二フッ化キセノンの製造方法に関するものである。
【0002】
【従来の技術および発明が解決しようとする課題】
二フッ化キセノン(XeF2)は、半導体製造用等方性エッチングガスとして利用され、その使用量は、年々増加している。そのため、現在、二フッ化キセノンを高純度でかつ効率よく製造するための技術が求められている。
【0003】
二フッ化キセノン製造方法としては、加熱、放電、光、γ線、電子照射を利用した方法がある。その中でも、加熱して製造する方法は、効率的でかつ簡便な装置で合成でき、量産には適した製造方法である(非特許文献1)。
【0004】
一般に、加熱方法による二フッ化キセノンの製造方法は、流通式反応器を用いた方法がある。この方法は、フッ素ガスとキセノンガスを混合して、その混合ガスを250〜400℃程度に保持したニッケル製の反応器に流通させ、反応させる。さらに、触媒として、フッ化ニッケル、フッ化コバルトなどを用いると、フッ化キセノンの生成速度が増加することが知られている(非特許文献2)。生成した二フッ化キセノンは、反応器出口に設置された冷却捕集器で固化捕集される。
【0005】
しかしながら、二フッ化キセノンの昇華点は、114℃と高く、反応器出口から捕集器入口までを十分に保温する必要がある。保温が十分でなければ、配管で二フッ化キセノンが固化することで閉塞を起こし、連続的な製造ができなくなる。
【0006】
また、従来の加熱の方法による製造方法では、二フッ化キセノンの製造時に四フッ化キセノン(XeF4)が副生する。このため、四フッ化キセノンの副生を抑制する方法の開発も望まれている。
【0007】
本発明は、二フッ化キセノンの製造及び固化捕集が同一の容器で効率的に実施でき、さらに四フッ化キセノンの生成を抑制できる製造方法を提供することにある。
【0008】
【非特許文献1】
H.H.Classen J.Am.Chem.Soc.,84,3593,(1962)
【非特許文献2】
Zemba.B Inorg.Nucl.Chem.,173,(1976)
【0009】
【課題を解決するための手段】
本発明者らは、鋭意検討した結果、反応器の加熱ゾーンに冷却固化器を設置することで、二フッ化キセノンの製造と同時に固化捕集ができること、及び四フッ化キセノン生成を低減できることを見いだし本発明に到達した。
【0010】
すなわち、本発明は、反応器の加熱ゾーンに冷却固化器を有する反応器を用いてキセノンとフッ素を反応させると同時に該冷却固化器で固化捕集することを特徴とする二フッ化キセノンの製造方法で、さらには、触媒としてフッ化ニッケルまたはフッ化コバルトを用いることにより、低温でニフッ化キセノンを製造する方法を提供するものである。
【0011】
本発明において、用いる冷却固化器とは、冷却固化器内部に水等の冷媒を流通することができる構造のもので、それが反応器の加熱ゾーンに設置されているものであり、特に形状等に制限されるものではない。
【0012】
本発明の製造方法の有利性としては、(a)生成した二フッ化キセノンは反応器内で固化できるので捕集器が必要ない。よって、反応器と捕集器間の配管を保温することも必要なく、配管等への閉塞もない。(b)生成した二フッ化キセノンは反応器内で速やかに冷却固化される。このため、二フッ化キセノンのフッ素化により生成する四フッ化キセノン、六フッ化キセノンが抑制できる、等が挙げられる。なお、ここで単にフッ化キセノンと表記したものは、キセノンとフッ素からなる化合物(XeF2、XeF4、XeF6)を意味する。
【0013】
本発明において、冷却固化器が反応器の加熱ゾーンに設置されている冷却固化器付反応器を用いたときの反応速度及び固化量、二フッ化キセノン、四フッ化キセノンの選択性について検討した。
Xe(g) + F2(g)→ XeF2(g) (1)
XeF2(g) + F2(g)→ XeF4(g) (2)
XeF2(g)→ XeF2(s) (3)
【0014】
キセノンとフッ素を反応させると式(1)に示すキセノンの酸化反応が起こり、二フッ化キセノンが生成する。さらに、二フッ化キセノンは、フッ素と反応して式(2)に示す二フッ化キセノンの酸化反応が起こり、四フッ化キセノンが生成する。この式(1)及び式(2)の反応はともに、室温付近ではほとんど進行しないが、150〜200℃付近から徐々に反応速度が大きくなる。このため、二フッ化キセノンを合成する際には、四フッ化キセノンが副生する。四フッ化キセノン副生の低減には、550℃以上の高温でキセノン過剰の条件で反応させる方法がある。しかし、このような条件で無くても反応器の加熱ゾーンに冷却固化器を設けた反応器を用いることで、四フッ化キセノン副生の低減が可能であることがわかった。冷却固化器付反応器では、式(1)の反応が起きた後、式(3)に示すように速やかに冷却固化器表面で固化する。このとき、冷却水温度を室温付近にしておけば、式(2)の反応は起こらない。この四フッ化キセノン生成の抑制効果は、式(1)が起きる反応温度150℃以上であれば得ることが可能である。しかしながら、150〜400℃の領域では、式(1)の反応速度は小さく、効率的に二フッ化キセノンを製造するには、450℃以上の高い反応温度が好ましい。また、原料としてフッ素を使用しているので、ニッケルなど金属製反応器を用いて製造する際には、低い温度で製造することが望ましい。
【0015】
そこで、本発明者らは、反応器の加熱ゾーンに冷却固化器を有する反応器中に触媒を充填することで、150〜400℃の低温域においても十分な反応速度が得られ、且つ、四フッ化キセノンの生成を抑制可能な製造方法を見いだした。
【0016】
本発明において、用いる触媒は、フッ化ニッケル(NiF2)またはフッ化コバルト(CoF3)である。フッ化ニッケルやフッ化コバルトを充填して製造すると、低温域で十分な反応速度が得られ、四フッ化キセノンの生成も抑制できた。このときの混合比は、キセノンとフッ素の混合比が当モルもしくは若干量でもキセノンが過剰であればよい。反応圧力条件もまた、特に限定されないが、大気圧以下でも十分である。
【0017】
冷却固化器が反応器の加熱ゾーンに設置されている冷却固化器付反応器を用いた二フッ化キセノン製造では、生成した二フッ化キセノンは反応器内で固化できるため、流通方法で問題となる配管、捕集器等での閉塞がなく、安定して製造することができる。連続的な製造方法の一例を挙げると、まず、反応開始時に所定圧力、所定混合比で原料を仕込み、反応を開始すると、生成物の固化により反応分だけ圧力低下するので、このとき圧力が一定になるように原料を供給する。そうすれば、連続的に安定して製造することができる。
【0018】
一方、冷却器への固化容量が大きい程、1回の操作で固化できる量が増えて、効率性が上がる。固化容量を増大させる方法として、冷却固化器にフィンを付けて表面積を増やすことが挙げられる。反応器内部温度が200℃以下にならなければ、物理的に可能な限りフィン等で冷却面を増やすことができる。
【0019】
以上に示す方法で製造した二フッ化キセノン中に少量の四フッ化キセノンが含まれているときは、初留パージ等で四フッ化キセノンを昇華させ、二フッ化キセノンと分離することで、さらに純粋な二フッ化キセノンが得られる。
【0020】
【実施例】
以下、本発明を実施例により詳細に説明するが、係る実施例に限定されるものではない。
【0021】
比較例1〜8、実施例1〜8
図1は、本発明に用いたニフッ化キセノンの製造装置の概略図である。二フッ化キセノン反応器2は、ニッケル製の円筒縦型反応器を用いた。反応器2は、内径80mmφ、高さ500mmのものを用いた。また、冷却固化器1は、ニッケル製で、反応器径方向の中心に位置し、寸法は、内径30mmφ、高さ400mmのものを用いた。内部には、冷却水を流通できる構造とした。冷却管入口の水温は、二フッ化キセノンを固化するのに十分な温度である25℃〜30℃で導入し、このときの冷却管出口水温は25℃〜30℃であった。原料ガスを供給する供給口は、天板に備え付けており、供給口ノズルは、反応器底から30mmの位置に配した。ガスの排出口は、天板面に備え付けた。反応器外周には、電気ヒーター3を配し反応器2を所定の温度に保った。反応器外壁温度を150〜550℃にした後、反応器2を真空にした。その後、排出口の弁を閉じて、供給口の弁を開けて大気圧まで原料ガスを仕込み(仕込みのモル比;キセノン/フッ素=2及び8)、反応を開始させた。このとき天板などはリボンヒーターで120℃以上に保温した。原料ガスを仕込んでから1分経過後、反応ガスをHeパージガスと共に抜き出し、そのガスをFT−IRによって分析した。また、生成したフッ化キセノンは、−78℃に冷却されたトラップにより捕集した。その捕集重量から、生成速度を算出した。結果を表1に示す。また、比較例は、冷却固化器を設けなかった以外は、実施例1〜8と同様の方法で行った。なお、表1〜3の生成速度は、フッ化キセノンの生成速度である。
【0022】
反応温度が150℃、270℃である比較例1、2、5、6、実施例1、2、5、6では、生成速度が非常に小さかった。冷却固化管がない比較例と冷却管がある実施例を比較すると、反応温度、仕込みモル比が同じ条件では、フッ化キセノンの生成速度は、ほぼ同程度であった。一方、不純物である四フッ化キセノンの選択率は、反応温度、仕込みモル比が同じ条件では、いずれの条件でも、冷却固化管がある実施例で低くなった。
【0023】
【表1】
【0024】
実施例9〜20
反応器の底にフッ化ニッケルを6g充填した以外は、実施例1〜8と同様の方法で二フッ化キセノンを合成した。結果を表2に示す。また、反応器の底にフッ化コバルトを6g充填した以外は、実施例1〜8と同様の方法で二フッ化キセノンを合成した。結果を表2に示す。
【0025】
触媒を充填していない実施例1〜8と比較すると、反応温度、仕込み比が同じ条件では、フッ化キセノンの生成速度は上がり、不純物濃度は同程度であった。
【0026】
【表2】
【0027】
実施例19、20
実施例19では、実施例9〜16で使用した冷却固化器付反応器にフッ化ニッケルを6g充填した。実施例20では、実施例9〜16で使用した冷却固化器付反応器の冷却管にフィン管を付けてフッ化ニッケルを6g充填した。フィンは、肉厚2mmのニッケル製縦フィンで、幅5mm、長さ400mmのフィンを16本付けた。
【0028】
実施例19、20ともに、反応器を450℃、真空状態にした。その後、排出口は閉止した状態で、キセノンを1.0NL/min、フッ素を0.5NL/minで供給口から反応器に供給した。反応器圧力が大気圧に到達した後、キセノン、フッ素供給を停止した。直ちに、二フッ化キセノン生成・固化により、反応器圧力が下がり始めた。このとき、反応・固化した分だけキセノンとフッ素を供給して反応器圧力を一定に保った。このときのキセノンとフッ素の供給比は、反応等量の1:1にした。冷却管が有する固化容量に到達した後、フッ化キセノン固化による圧力減少は無くなった。この結果を表3に示す。
【0029】
実施例19、20ともに固化速度及び不純物四フッ化キセノン濃度は同程度であった。冷却固化量は、フィンを付けた実施例20の方が多くなった。
【0030】
【表3】
【0031】
【発明の効果】
本発明によれば、冷却固化器を備えた反応装置を用いることにより、エレクトロニクス分野用途の二フッ化キセノンを効率的に製造することが可能となる。
【図面の簡単な説明】
【図1】本発明に用いたニフッ化キセノンの製造装置の概略図である。
【符号の説明】
1・・・・冷却固化器
2・・・・反応器
3・・・・触媒
4・・・・ヒーター[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing xenon difluoride used as a semiconductor production gas in the electronics field.
[0002]
[Background Art and Problems to be Solved by the Invention]
Xenon difluoride (XeF 2 ) is used as an isotropic etching gas for semiconductor production, and the amount of its use is increasing year by year. Therefore, at present, there is a demand for a technique for producing xenon difluoride with high purity and efficiency.
[0003]
As a method for producing xenon difluoride, there is a method using heating, discharge, light, γ-ray, and electron irradiation. Among them, the method of producing by heating is a production method that can be synthesized with an efficient and simple apparatus and is suitable for mass production (Non-Patent Document 1).
[0004]
In general, a method of producing xenon difluoride by a heating method includes a method using a flow reactor. In this method, fluorine gas and xenon gas are mixed, and the mixed gas is circulated through a nickel reactor maintained at about 250 to 400 ° C. for reaction. Furthermore, it is known that the production rate of xenon fluoride increases when nickel fluoride, cobalt fluoride, or the like is used as a catalyst (Non-patent Document 2). The produced xenon difluoride is solidified and collected by a cold collector installed at the outlet of the reactor.
[0005]
However, the sublimation point of xenon difluoride is as high as 114 ° C., and it is necessary to sufficiently keep the temperature from the reactor outlet to the collector inlet. If the heat insulation is not sufficient, the xenon difluoride is solidified in the pipe, causing clogging and continuous production cannot be performed.
[0006]
Moreover, in the manufacturing method by the conventional heating method, xenon tetrafluoride (XeF 4 ) is by-produced during the production of xenon difluoride. For this reason, development of a method for suppressing by-product generation of xenon tetrafluoride is also desired.
[0007]
An object of the present invention is to provide a production method in which the production and solidification collection of xenon difluoride can be efficiently carried out in the same container, and the production of xenon tetrafluoride can be suppressed.
[0008]
[Non-Patent Document 1]
HHClassen J.H. Am. Chem. Soc. , 84, 3593, (1962)
[Non-Patent Document 2]
Zemba.B Inorg. Nucl. Chem. , 173, (1976)
[0009]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that by installing a cooling solidifier in the heating zone of the reactor, solidification and collection can be performed simultaneously with the production of xenon difluoride, and xenon tetrafluoride production can be reduced. We found out and reached the present invention.
[0010]
That is, the present invention is a process for producing xenon difluoride characterized in that xenon and fluorine are reacted using a reactor having a cooling and solidifying device in a heating zone of the reactor and simultaneously solidified and collected by the cooling and solidifying device. The present invention further provides a method for producing xenon difluoride at a low temperature by using nickel fluoride or cobalt fluoride as a catalyst.
[0011]
In the present invention, the cooling solidifier to be used has a structure in which a refrigerant such as water can be circulated inside the cooling solidifier, and is installed in the heating zone of the reactor. It is not limited to.
[0012]
As an advantage of the production method of the present invention, (a) the produced xenon difluoride can be solidified in the reactor, so that no collector is required. Therefore, it is not necessary to keep the piping between the reactor and the collector warm, and there is no blockage to the piping. (B) The produced xenon difluoride is quickly cooled and solidified in the reactor. For this reason, xenon tetrafluoride and xenon hexafluoride produced by fluorination of xenon difluoride can be suppressed. Here, what is simply expressed as xenon fluoride means a compound composed of xenon and fluorine (XeF 2 , XeF 4 , XeF 6 ).
[0013]
In the present invention, the reaction rate and solidification amount when using a reactor with a cooling solidifier installed in the heating zone of the reactor as a cooling solidifier, and the selectivity of xenon difluoride and xenon tetrafluoride were examined. .
Xe (g) + F 2 (g) → XeF 2 (g) (1)
XeF 2 (g) + F 2 (g) → XeF 4 (g) (2)
XeF 2 (g) → XeF 2 (s) (3)
[0014]
When xenon and fluorine are reacted, an oxidation reaction of xenon represented by the formula (1) occurs to generate xenon difluoride. Furthermore, xenon difluoride reacts with fluorine to cause an oxidation reaction of xenon difluoride represented by the formula (2) to produce xenon tetrafluoride. Both the reactions of the formulas (1) and (2) hardly proceed near room temperature, but the reaction rate gradually increases from around 150 to 200 ° C. For this reason, when xenon difluoride is synthesized, xenon tetrafluoride is by-produced. In order to reduce xenon tetrafluoride by-product, there is a method of reacting at a high temperature of 550 ° C. or higher under an excess of xenon. However, it was found that xenon tetrafluoride by-product can be reduced by using a reactor provided with a cooling and solidifying device in the heating zone of the reactor even under such conditions. In the reactor with a cooling solidifier, after the reaction of formula (1) occurs, it quickly solidifies on the surface of the cooling solidifier as shown in formula (3). At this time, if the cooling water temperature is set to around room temperature, the reaction of the formula (2) does not occur. This inhibitory effect on the formation of xenon tetrafluoride can be obtained if the reaction temperature at which the formula (1) occurs is 150 ° C. or higher. However, in the region of 150 to 400 ° C., the reaction rate of the formula (1) is low, and a high reaction temperature of 450 ° C. or higher is preferable for efficiently producing xenon difluoride. Further, since fluorine is used as a raw material, it is desirable to produce at a low temperature when producing using a metal reactor such as nickel.
[0015]
Therefore, the present inventors can obtain a sufficient reaction rate even in a low temperature range of 150 to 400 ° C. by filling a catalyst in a reactor having a cooling and solidifying device in the heating zone of the reactor. We have found a production method that can suppress the formation of xenon fluoride.
[0016]
In the present invention, the catalyst used is nickel fluoride (NiF 2 ) or cobalt fluoride (CoF 3 ). When filled with nickel fluoride or cobalt fluoride, a sufficient reaction rate was obtained in a low temperature range, and generation of xenon tetrafluoride could be suppressed. The mixing ratio at this time may be an excess of xenon even if the mixing ratio of xenon and fluorine is an equimolar amount or a slight amount. The reaction pressure condition is also not particularly limited, but a pressure below atmospheric pressure is sufficient.
[0017]
In the production of xenon difluoride using a reactor with a cooling solidifier, where the cooling solidifier is installed in the heating zone of the reactor, the generated xenon difluoride can be solidified in the reactor, so there is a problem in the distribution method. There is no blockage in the piping, collector and the like, and it can be manufactured stably. An example of a continuous production method is as follows. First, the raw material is charged at a predetermined pressure and a predetermined mixing ratio at the start of the reaction, and when the reaction is started, the pressure decreases by the amount of the reaction due to solidification of the product. Supply raw materials to become If it does so, it can manufacture continuously and stably.
[0018]
On the other hand, the larger the solidification capacity in the cooler, the more the amount that can be solidified in one operation, and the higher the efficiency. As a method for increasing the solidification capacity, it is possible to increase the surface area by attaching fins to the cooling solidifier. If the internal temperature of the reactor does not become 200 ° C. or lower, the cooling surface can be increased with fins or the like as physically as possible.
[0019]
When a small amount of xenon tetrafluoride is contained in the xenon difluoride produced by the method shown above, the xenon tetrafluoride is sublimated by an initial distillation purge or the like, and separated from xenon difluoride, Further pure xenon difluoride is obtained.
[0020]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not limited to the Example which concerns.
[0021]
Comparative Examples 1-8, Examples 1-8
FIG. 1 is a schematic view of an apparatus for producing xenon difluoride used in the present invention. As the xenon difluoride reactor 2, a cylindrical cylindrical reactor made of nickel was used. A reactor 2 having an inner diameter of 80 mmφ and a height of 500 mm was used. The cooling solidifier 1 was made of nickel, located at the center in the reactor radial direction, and had dimensions of an inner diameter of 30 mmφ and a height of 400 mm. Inside, the cooling water can be circulated. The water temperature at the inlet of the cooling pipe was introduced at 25 ° C. to 30 ° C., which is sufficient to solidify xenon difluoride, and the water temperature at the outlet of the cooling pipe at this time was 25 ° C. to 30 ° C. The supply port for supplying the raw material gas was provided on the top plate, and the supply port nozzle was arranged at a position 30 mm from the bottom of the reactor. A gas outlet was provided on the top plate. An electric heater 3 was disposed on the outer periphery of the reactor to keep the reactor 2 at a predetermined temperature. After the reactor outer wall temperature was 150 to 550 ° C., the reactor 2 was evacuated. Thereafter, the valve at the discharge port was closed, the valve at the supply port was opened, and the raw material gas was charged up to atmospheric pressure (the molar ratio of the charge; xenon / fluorine = 2 and 8) to start the reaction. At this time, the top plate and the like were kept at 120 ° C. or more with a ribbon heater. One minute after the source gas was charged, the reaction gas was extracted together with the He purge gas, and the gas was analyzed by FT-IR. The produced xenon fluoride was collected by a trap cooled to -78 ° C. The production rate was calculated from the collected weight. The results are shown in Table 1. Moreover, the comparative example was performed by the method similar to Examples 1-8 except not having provided the cooling solidifier. The production rates in Tables 1 to 3 are the production rates of xenon fluoride.
[0022]
In Comparative Examples 1, 2, 5, and 6 and Examples 1, 2, 5, and 6 where the reaction temperature was 150 ° C. and 270 ° C., the production rate was very low. Comparing the comparative example without a cooling solidification tube and the example with a cooling tube, under the same reaction temperature and charged molar ratio, the xenon fluoride production rate was almost the same. On the other hand, the selectivity of xenon tetrafluoride, which is an impurity, was low in the examples with the cooling and solidification tube under the same conditions for the reaction temperature and the charged molar ratio.
[0023]
[Table 1]
[0024]
Examples 9-20
Xenon difluoride was synthesized in the same manner as in Examples 1 to 8, except that 6 g of nickel fluoride was charged at the bottom of the reactor. The results are shown in Table 2. Further, xenon difluoride was synthesized in the same manner as in Examples 1 to 8, except that 6 g of cobalt fluoride was charged at the bottom of the reactor. The results are shown in Table 2.
[0025]
Compared with Examples 1 to 8 in which the catalyst was not charged, under the same reaction temperature and charge ratio, the xenon fluoride production rate increased and the impurity concentration was comparable.
[0026]
[Table 2]
[0027]
Examples 19 and 20
In Example 19, 6 g of nickel fluoride was charged into the reactor with a cooling solidifier used in Examples 9 to 16. In Example 20, a fin pipe was attached to the cooling pipe of the reactor with a cooling solidifier used in Examples 9 to 16, and 6 g of nickel fluoride was charged. The fins were nickel vertical fins with a thickness of 2 mm, and 16 fins with a width of 5 mm and a length of 400 mm were attached.
[0028]
In both Examples 19 and 20, the reactor was evacuated at 450 ° C. Thereafter, with the discharge port closed, xenon was supplied to the reactor from the supply port at 1.0 NL / min and fluorine at 0.5 NL / min. After the reactor pressure reached atmospheric pressure, the supply of xenon and fluorine was stopped. Immediately, the reactor pressure began to drop due to the formation and solidification of xenon difluoride. At this time, the reactor pressure was kept constant by supplying xenon and fluorine for the amount of reaction and solidification. At this time, the supply ratio of xenon and fluorine was 1: 1 of reaction equivalent. After reaching the solidification capacity of the cooling tube, the pressure decrease due to solidification of xenon fluoride disappeared. The results are shown in Table 3.
[0029]
In Examples 19 and 20, the solidification rate and impurity xenon tetrafluoride concentration were similar. The amount of cooling solidification was greater in Example 20 with fins.
[0030]
[Table 3]
[0031]
【The invention's effect】
According to the present invention, it is possible to efficiently produce xenon difluoride for use in the electronics field by using a reactor equipped with a cooling and solidifying device.
[Brief description of the drawings]
FIG. 1 is a schematic view of an apparatus for producing xenon difluoride used in the present invention.
[Explanation of symbols]
1 ... Cooling solidifier 2 ... Reactor 3 ... Catalyst 4 ... Heater
Claims (2)
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| JP6252214B2 (en) * | 2014-02-06 | 2017-12-27 | セントラル硝子株式会社 | Method for producing iodine heptafluoride |
| JP6372340B2 (en) * | 2014-12-17 | 2018-08-15 | セントラル硝子株式会社 | Method for producing iodine heptafluoride |
| JP6467955B2 (en) * | 2015-01-30 | 2019-02-13 | セントラル硝子株式会社 | Method for producing iodine pentafluoride |
| JP6792151B2 (en) * | 2016-10-11 | 2020-11-25 | セントラル硝子株式会社 | Manufacturing method of chlorine trifluoride |
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