0301C16 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明説明（1 ) 【發明所屬之技術領域】 本發明是關於氟氣產生裝置及氟氣產生方法以及氟 氣。特別是關於產生被使用在半導體等的製造工程中的不 純物極少的高純度氟氣的氟氣產生裝置及氟氣產生方法以 及藉由此裝置和方法所得到的氟氣。 【背景技術】 氟氣，例如是在半導體製造領域中所不可或缺的基本 氣體而被使用。而且，雖然也有使用氟氣本身的情況，最 近，以氟氣爲基礎，合成三氟化氮（以下稱爲nf3氣體） 等，將此種氣體作爲半導體的淸潔氣體或乾式鈾刻用氣體 來加以使用。又，氟化氖氣體（以下稱爲NeF氣體）、 氟化氬氣體（以下稱爲A rF氣體）、氟化氪氣體（以下 稱爲K r F氣體）等，係在半導體積體電路的圖案形成時 所被使用的激元激光器（excimer laser)振盪用氣體；該原 料大多使用稀有氣體和氟氣的混合氣體。 此氟氣，係在收容有由規定量的K F · H F所組成的 電解浴的電解槽中，以碳爲陽極 '以鎳爲陰極，進行電解 而產生。一般而言，被收容在電解槽中的KF · HF，最 初投入規定量的K F · H F，然後適當地供給H F，成爲 KF·2HF而被使用。此時，投入成爲KF·2HF所 不足量的KF · HF，然後藉由再度供給HF，調製出規 定量的電解浴。 電解浴的成分中的K F，吸濕性高，故在調製電解浴 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） (請先閱讀背面之注意事項再填寫本頁)0301C16 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (1) [Technical Field to which the Invention belongs] The present invention relates to a fluorine gas generating device, a fluorine gas generating method, and a fluorine gas. In particular, the present invention relates to a fluorine gas generating device and a fluorine gas generating method that generate high-purity fluorine gas with very few impurities used in manufacturing processes such as semiconductors, and the fluorine gas obtained by the device and method. BACKGROUND ART Fluorine gas is used, for example, as a basic gas indispensable in the field of semiconductor manufacturing. Furthermore, although fluorine gas itself is sometimes used, recently, based on fluorine gas, nitrogen trifluoride (hereinafter referred to as nf3 gas) was synthesized, and this gas was used as a semiconductor cleaning gas or a dry uranium engraving gas. Use it. Neon fluoride gas (hereinafter referred to as NeF gas), argon fluoride gas (hereinafter referred to as A rF gas), krypton fluoride gas (hereinafter referred to as K r F gas), and the like are patterns in semiconductor integrated circuits. An excimer laser oscillation gas is used for the formation; most of the raw materials are a mixed gas of a rare gas and a fluorine gas. This fluorine gas is generated by electrolysis in an electrolytic cell containing an electrolytic bath composed of a predetermined amount of K F · H F with carbon as the anode and nickel as the cathode. Generally, KF and HF stored in an electrolytic cell are initially charged with a predetermined amount of K F and H F, and then appropriately supplied with H F to be used as KF and 2HF. At this time, the amount of KF · HF which was insufficient to the amount of KF · 2HF was put in, and then the HF was supplied again to prepare a regular electrolytic bath. K F in the composition of the electrolytic bath has high hygroscopicity, so it is used in the preparation of the electrolytic bath. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page)
-5 - η 16 Α7 Β7 五、發明説明（2) 時，一般是含有水分的。我先前已經提出關於不純物少的 高純度氟產生裝置的內容的申請案（W〇 01/ 7 7 4 1 2 A 1 )。 然而，如此所產生的氟氣，初期所產生的氟氣中，含 有4 5〜5 5 %的氧。由於所產生的氟氣和電解浴中所含 有的水，如下述的反應式（1 )所示般地進行反應，通 常，氟氣中所含有的氧量減少。然而，其量難以降至 3000ppm以下。 2 F 2 + Η 2 0 —^F2〇+2HF · · · · (1) 前述激元激光器振盪用氣體、或是在激元激光器的稜 鏡（C a F 2單結晶）的表面處理中，需要高純度的氟氣。 該氟氣中所含有的氧濃度，作爲前者的激元激光器振盪用 氣體，爲1 0 0 0 p p m以下；而作爲後者的激元激光器 的稜鏡（C a F 2單結晶）的表面處理用氣體，則被要求在 5 0 0 p p m 以下。 本發明的目的爲提供一種能夠安定地產生氧含量非常 少之高純度的氟氣的氟氣產生裝置及氟氣產生方法以及氟 氣。 【發明的揭示】 爲了解決前述課題之本發明的氟氣產生裝置，係將由 K F · 2 H F組成的電解浴加以電解來產生高純度氟氣之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 『裝· 、1Τ 經濟部智慧財產局員工消費合作社印製 -6- J301C16 A7 ______ B7 _____ 五、發明説明（3) 形態的氟氣產生裝置，其特徵爲具備： 將KF或KF·HF調製成KF·2HF的調製系 統、 將H F供給至前述電解浴和前述調製系統中的H F供 給系統、及 將藉由前述調製系統所調製出來的K F · 2 H F加以 電解來產生氟氣的氟氣產生系統。 在密閉的調製系統內由KF或KF·HF調製成 K F · 2 H F之後，將調製成的K F · 2 H F投入與此調 製系統密閉連結的電解槽中。因此，被投入電解槽內的 K F · 2 H F ，不會吸收水分，亦即可以作成氧含量少的 電解浴。藉由此手段，在將此電解浴電解所得到的氟氣中 所含有的氧量，從產生初期的階段開始，便能夠非常少。 又，本發明的氟氣產生裝置，在前述調製系統中，附 設用來除去前述KF或KF·HF中的水分的水分除去手 段。 從K F或K F · H F調製K F · 2 H F時，能夠確實 地減少氧量。 又’本發明的氟氣產生裝置，其中所產生的氟氣中的 氧濃度爲2 %以下。 氟氣中的氧濃度減少至2 %以下，理想爲〇 . 2 %以 下（2000 ppm以下），更理想爲〇 · 〇2%以下 (2 0 0 p p m以下）。因此，能夠作爲激元激光器振盪 用氣體、或是激元激光器的稜鏡（C a F 2單結晶）的表面 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐) -- (請先閲讀背面之注意事項再填寫本頁) C· 、11 經濟部智慧財產局員工消費合作社印製 2 301C16 A7 _____ B7 五、發明説明（4 ) 處理用氣體來使用。 又，本發明的氟氣產生裝置，係將由K F · 2 H F組 成的電解浴加以電解來產生氟氣之形態的氟氣產生裝置， 其特徵爲： 具備：將KF或KF·HF調製成KF·2HF的調 製系統、 將H F供給至前述電解浴和前述調製系統中的η F供 給系統、及 將藉由前述調製系統所調製出來的K F · 2 H F加以 電解來產生氟氣的氟氣產生系統； 且設置用來調整前述調製系統、H F供給系統及氟氣 產生系統的各個系統或各系統全體的外部氣氛中的水分的 水分控制手段。 由於設置用來調整前述調製系統、H F供給系統及氟 氣產生系統的各個系統或各系統全體的外部氣氛中的水分 的水分控制手段，所以能夠確實地抑制氧的混入。 又，本發明的氟氣產生裝置，其中前述水分控制手 段，係可以收容前述各系統或各系統全體之能夠控制內部 的氣氛的框體。 水分控制手段，由於爲可以控制氣氛的框體，所以容 易進行各系統或各系統全體的氣氛溼度的調整。藉由此手 段，能夠確實地抑制氧的混入。 又5本發明的氟氣產生方法，係將由K F · 2 H F組 成的電解浴加以電解來產生氟氣之形態的氟氣產生方法， 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝- 訂 經濟部智慧財產局員工消費合作社印製 -8- 20030i：16 Α7 Β7 五、發明説明（5) 在附設有用來除去KF或KF·HF中的水分的水分除去 手段之將KF或KF·HF調製成KF·2HF的調製系 統中，以規定時間，在真空或非活性氣體氣氛下，將前述 K F或K F · H F加熱、脫氣之後，在真空或非活性氣體 氣氛下’冷卻至室溫’接著’從H F供給系統將氣化後的 H F供給至該g周製系統內，在前述調製系統內使前述κ f 或KF · HF與前述HF反應，產生KF · 2HF，將該 K F · 2 H F供給至氟氣產生系統的電解槽中之後，加以 電解，產生低氧濃度的氟氣。 藉由如此的構成，可以使所產生的氟氣中的氧濃度變 少’而能夠作爲激元激光器振盪用氣體、或是激元激光器 的稜鏡（C a F 2單結晶）的表面處理用氣體來使用。 又，本發明的氟氣產生方法，其中在前述調製系統 中’以200〜300 °C加熱前述KF或KF · HF，藉 以除去前述K F或K F · H F的吸附水及結晶水。 如此，能夠確實地除去K F或K F · H F中的水分。 藉此’可以除去含在水分中的氧，而能夠使所產生的氟氣 中的氧濃度，從氟氣產生初期的階段開始，便確實地減 少〇 又’本發明的氟氣，係在附設有用來除去KF或 KF·HF中的水分的水分除去手段之將Kf或KF· H F調製成κ F · 2 H F的調製系統中，以規定時間，在 真空或非活性氣體氣氛下，將前述K F或K F · H F加 熱、脫氣之後，在真空或非活性氣體氣氛下，冷卻至室 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） (請先閲讀背面之注意事項再填寫本頁) •裝- 經濟部智慧財產局員工消費合作社印製 -9- 0301C16 A7 B7 五、發明説明（6) 溫，接著，從H F供給系統將氣化後的H F供給至該調製 系統內，在前述調製系統內使前述KF或KF · HF與前 述HF反應，產生KF · 2HF，將該KF · 2HF供給 至氟氣產生系統的電解槽中之後，加以電解，所產生的氟 氣。因此，由於爲氧濃度極低的高純度氟氣，所以能夠作 爲半導體製造用的各種基本氣體來加以使用。 又，本發明的氟氣，其氧濃度在2%以下。 氟氣中的氧濃度減少至2 %以下，理想爲〇 . 2 %以 下（2000ppm以下），更理想爲0.02%以下 (2 0 〇 p p m以下）。因此，能夠作爲激元激光器振盪 用氣體、或是激元激光器的稜鏡（C a F 2單結晶）的表面 處理用氣體來使用。 【本發明的實施形態】 以下，根據第1圖來說明本發明的實施形態的一例。 本實施形態中的氟氣產生裝置G，係將由K F · 2 H F所組成的電解浴2 4，加以電解而產生高純度的氟氣 的裝置；其構成係具備··將K F或K F · H F調製成 K F · 2 H F的調製系統A、將H F供給至電解浴2 4和 調製系統Α中的H F供給系統Β、及將藉由調製系統Α所 調製成的K F · 2 H F加以電解而產生氟氣的氟氣產生系 統C。 在第1圖中，從KF或KF · HF調製成KF · 2 H F的調製系統a，係由··利用收容K F 1 0的N i製的 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝_ 、11 經濟部智慧財產局員工消費合作社印製 -10- J301C16 A7 B7 五、發明説明（7 ) 容器7 a和密閉此容器7 a的上蓋7 b所構成的KF · 2 HF調製裝置7、包覆此KF · 2HF調製裝置7的容器 7 a來加熱其內部的K F 1 〇的加熱器9、冷卻用的冷卻 水用管8、被設置在上蓋7 b上而與真空排氣系統D連結 的真空配管2、非活性氣體淸除用配管3、及被插入K F 1 0中且與H F供給系統B和氟氣產生系統C連結之H F 供給兼KF·2HF送出配管1，所構成。 將H F供給至此調製系統A中的H F供給系統B，其 被載置在測力器1 2上的H F鋼瓶1 1，被設置在框體 1 3中。此框體1 3，與未圖示的丙烯洗滌器（acryiic scrubber)連結。H F鋼瓶1 1的表面，被加熱器1 4所覆 蓋，來使H F鋼瓶1 1內能夠保持在規定的溫度。又，藉 由測力器1 2，測量H F鋼瓶1 1內的氣體量，藉以測量 供給至調製系統Α和氟*氣產生系統C的H F氣體供給量。 此H F鋼瓶1 1，藉由H F送出用配管5，與調製系統A 連結。 氟氣產生系統C，主要是由··由KF · 2HF系混合 溶解鹽所組成的電解浴2 4、收容此電解浴2 4的電解槽 2 0、及將電解浴2 4電解的陽極2 2和陰極2 3，所構 成。 電解槽2 0，係利用N i、蒙乃爾合金（Monel )、純 鐵、不銹鋼等的金屬，一體地形成。電解槽2 〇，係藉由 N i或冡乃爾合金所組成的隔壁2 7，被分離成陽極室 2 8和陰極室2 9。在陽極室2 8中，配置由低極化性碳 本紙張尺度適财關家料（CNS ) A4規格（卩歐撕公釐) ---- • 11 - (請先閱讀背面之注意事項再填寫本頁) -裝- 訂 經濟部智慧財產局員工消費合作社印製 J301C16 A7 B7 經濟部智慈財產局員工消費合作社印製 五、發明説明（8) 所組成的陽極2 2 ;而在陰極室2 9中，配置由N i或 F e所組成的陰極2 3。在電解槽2 0的上蓋3 0，配設 從陽極室2 8所產生的氟氣的排出口 2 5、及從陰極室 29所產生的氫氣的排出口 26。又，電解槽20，設置 加熱電解槽20內的加熱器31。再者，在加熱器31的 周圍，設置未圖示的隔熱材。加熱器3 1可以是螺旋狀或 鎳鉻合金線等，其形態並沒有特別地限定，但是理想爲包 覆電解槽2 0整個外周的形狀。 真空排氣系統D，係由分子篩1 6和真空泵1 7所構 成。而且，當利用加熱器9加熱被收容在調製系統a中的 K F 1 〇時’吸引從K F 1 〇解吸（desorption，脫離）出來 的水分。 接著，說明關於以上構成的氟氣產生裝置G的動作。 預先藉由加熱器9將調製系統A以2 5 0〜3 0 進行熱處理之後，在容器7 a內裝塡規定量的KF 1 〇。 而且，在真空或超高純度非活性氣體的淸除（purge)下，再度加熱至200〜250 °C，更理想爲25 ◦〜300 °C，保持2 4〜4 8小時，使K F 1 0乾燥。此時，打開 真空配管閥2 a '使閥3 a和閥4 b成爲關閉狀態，利用 真空排氣系統D，將容器7 a排氣。如此，使K F 1 〇在 超高純度非活性氣體的淸除下，再度加熱至2 5 〇〜 3 0 0 °C，藉由進行2 4〜4 8小時的熱處理，能夠使 K F 1 〇中的吸附水和結晶水，解吸出來。 進行K F的熱重量法（Thermogravimetry，以下稱爲 (請先閱讀背面之注意事項再填寫本頁) •裝·-5-η 16 Α7 Β7 5. In the description of the invention (2), it usually contains water. I have previously filed an application regarding the content of a high-purity fluorine generator with few impurities (WO 01/7 7 4 1 2 A 1). However, the fluorine gas generated in this way contains 45 to 55% of oxygen in the fluorine gas initially generated. Since the generated fluorine gas and water contained in the electrolytic bath react as shown in the following reaction formula (1), the amount of oxygen contained in the fluorine gas generally decreases. However, it is difficult to reduce the amount to less than 3000 ppm. 2 F 2 + Η 2 0 — ^ F2〇 + 2HF (1) The gas for oscillation of the excimer laser or the surface treatment of erbium (C a F 2 single crystal) of the excimer laser, High purity fluorine gas is required. The concentration of oxygen contained in this fluorine gas is 1000 ppm or less for the former excimer laser oscillation, and for the surface treatment of krypton (C a F 2 single crystal) for the latter excimer laser. Gas is required to be below 500 ppm. An object of the present invention is to provide a fluorine gas generating device, a fluorine gas generating method, and a fluorine gas that can stably generate high-purity fluorine gas having a very small oxygen content. [Disclosure of the invention] In order to solve the foregoing problem, the fluorine gas generating device of the present invention is produced by electrolyzing an electrolytic bath composed of KF · 2 HF to produce high-purity fluorine gas. The paper size of this paper applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) (Please read the precautions on the back before filling out this page.) "Installation · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -6- J301C16 A7 ______ B7 _____ V. Description of the invention (3) Form The fluorine gas generating device includes a modulation system that modulates KF or KF · HF to KF · 2HF, an HF supply system that supplies HF to the electrolytic bath and the modulation system, and uses the modulation system. The prepared KF · 2 HF is electrolyzed to produce fluorine gas. After the KF or KF · HF is modulated into K F · 2 H F in a closed modulation system, the prepared K F · 2 H F is put into an electrolytic cell hermetically connected to the modulation system. Therefore, K F · 2 H F put into the electrolytic cell does not absorb water, that is, it can be used as an electrolytic bath with low oxygen content. By this means, the amount of oxygen contained in the fluorine gas obtained by electrolysis of this electrolytic bath can be very small from the initial stage of generation. Further, the fluorine gas generating device of the present invention is provided with a moisture removing means for removing the moisture in the KF or KF · HF in the modulation system. When K F · 2 H F is modulated from K F or K F · H F, the amount of oxygen can be reliably reduced. Further, the fluorine gas generating device of the present invention, wherein the oxygen concentration in the generated fluorine gas is 2% or less. The oxygen concentration in the fluorine gas is reduced to 2% or less, preferably 0.2% or less (2000 ppm or less), and more preferably 〇2% or less (200 p pm or less). Therefore, it can be used as an excimer laser oscillation gas, or a chirped (C a F 2 single crystal) surface of the excimer laser. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)-( Please read the notes on the back before filling this page) C ·, 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 301C16 A7 _____ B7 V. Description of the invention (4) Use of processing gas. In addition, the fluorine gas generating device of the present invention is a fluorine gas generating device that electrolyzes an electrolytic bath composed of KF · 2 HF to generate fluorine gas, and is characterized in that it includes: KF or KF · HF is modulated into KF · 2HF modulation system, HF supply to the electrolytic bath and the η F supply system in the modulation system, and fluorine gas generation system that electrolyzes KF · 2 HF modulated by the modulation system to generate fluorine gas; Moreover, a moisture control means is provided for adjusting the moisture in the external atmosphere of each of the aforementioned modulation system, HF supply system, and fluorine gas generation system, or the entire system. The moisture control means for adjusting the moisture in the external atmosphere of each of the modulation system, the HF supply system, and the fluorine gas generation system or the entire system is provided, so that the incorporation of oxygen can be reliably suppressed. Further, in the fluorine gas generating device of the present invention, the moisture control means is a frame that can house the respective systems or the entire system and can control the atmosphere inside. The moisture control means is a frame that can control the atmosphere, so it is easy to adjust the humidity of each system or the entire system. By this means, it is possible to reliably suppress the incorporation of oxygen. 5 The fluorine gas generation method of the present invention is a fluorine gas generation method in the form of fluorine gas by electrolysis of an electrolytic bath composed of KF · 2 HF. This paper standard is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling out this page) Binding-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Printed by the Consumer Consumption Cooperatives-8- 20030i: 16 Α7 Β7 5. Description of the Invention (5) It is used to remove KF or KF · HF Moisture Removal Means The KF or KF · HF is modulated into a KF · 2HF modulation system. The KF or KF · HF is heated and desorbed in a vacuum or inert gas atmosphere for a predetermined time. After the gas is supplied, it is 'cooled to room temperature' in a vacuum or an inert gas atmosphere, and then the gasified HF is supplied from the HF supply system into the g-cycle system, and the aforementioned κ f or KF is adjusted in the aforementioned modulation system. HF reacts with the aforementioned HF to generate KF · 2HF. After supplying this KF · 2 HF to an electrolytic cell of a fluorine gas generating system, electrolysis is performed to generate fluorine gas with a low oxygen concentration. With such a structure, the oxygen concentration in the generated fluorine gas can be reduced, and it can be used as an excimer laser oscillation gas or a holmium (C a F 2 single crystal) surface treatment for an excimer laser. Gas to use. In the fluorine gas generating method of the present invention, the KF or KF · HF is heated at 200 to 300 ° C in the modulation system to remove the KF or KF · H F adsorbed water and crystal water. In this way, the water in K F or K F · H F can be reliably removed. Thereby, 'the oxygen contained in the water can be removed, and the oxygen concentration in the generated fluorine gas can be reliably reduced from the initial stage of the fluorine gas generation.' The fluorine gas of the present invention is attached There is a water removal means for removing water in KF or KF · HF. In a modulation system that modulates Kf or KF · HF to κ F · 2 HF, the aforementioned KF is adjusted in a vacuum or an inert gas atmosphere for a predetermined time. Or KF · HF after heating and degassing, and cooling to room temperature under vacuum or inert gas atmosphere. The paper size of the paper is applicable to China National Standard (CNS) A4 specification (210 × 297 mm). (Please read the notes on the back before filling (This page) • Equipment-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy -9- 0301C16 A7 B7 V. Description of the invention (6) The temperature is then supplied from the HF supply system to the modulation system after gasification, In the modulation system, the KF or KF · HF is reacted with the HF to generate KF · 2HF, and the KF · 2HF is supplied to an electrolytic cell of a fluorine gas generating system, and then the electrolyzed fluorine gas is generated. Therefore, since it is a high-purity fluorine gas having an extremely low oxygen concentration, it can be used as various basic gases for semiconductor manufacturing. The fluorine gas of the present invention has an oxygen concentration of 2% or less. The oxygen concentration in the fluorine gas is reduced to 2% or less, preferably 0.2% or less (2000ppm or less), and more preferably 0.02% or less (200p pm or less). Therefore, it can be used as a gas for excimer laser oscillation or a gas for surface treatment of krypton (C a F 2 single crystal) of an excimer laser. [Embodiment of the present invention] An example of an embodiment of the present invention will be described below with reference to Fig. 1. The fluorine gas generating device G in this embodiment is a device for generating high-purity fluorine gas by electrolyzing an electrolytic bath 24 composed of KF · 2 HF; its structure is provided by ·· KF or KF · HF modulation KF · 2 HF modulation system A, HF is supplied to electrolytic bath 24 and HF supply system B of modulation system A, and KF · 2 HF prepared by modulation system A is electrolyzed to generate fluorine gas. The fluorine gas generation system C. In the first figure, the modulation system a modulated from KF or KF · HF to KF · 2 HF is made of ··· This paper standard made of Ni using KF 1 0 accommodates the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) (Please read the notes on the back before filling out this page) Packing _, 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -10- J301C16 A7 B7 V. Description of the invention (7) Container 7 a and hermetically sealed KF · 2 HF modulation device 7 constituted by the upper lid 7 b of this container 7 a, a container 7 a covering the KF · 2HF modulation device 7 to heat the KF 1 inside the heater 9, and cooling water for cooling A pipe 8, a vacuum pipe 2 provided on the upper cover 7b and connected to the vacuum exhaust system D, an inert gas purging pipe 3, and inserted into KF 10 and generated with the HF supply system B and fluorine gas System C is composed of HF supply and KF · 2HF delivery piping 1. H F is supplied to the H F supply system B of the modulation system A, and the H F cylinder 11 placed on the load cell 12 is set in the housing 13. This frame body 1 3 is connected to an acrylic scrubber (not shown). The surface of the H F cylinder 11 is covered with a heater 14 to keep the inside of the H F cylinder 11 at a predetermined temperature. Further, the amount of gas in the H F cylinder 11 is measured by the load cell 12 to measure the amount of H F gas supplied to the modulation system A and the fluorine * gas generation system C. The H F cylinder 11 is connected to the modulation system A via the H F delivery pipe 5. The fluorine gas generating system C is mainly composed of an electrolytic bath 2 composed of KF · 2HF-based mixed dissolved salts, an electrolytic cell 20 containing the electrolytic bath 24, and an anode 2 2 which electrolyzes the electrolytic bath 2 4 And cathode 2 3, constituted. The electrolytic cell 20 is integrally formed using a metal such as Ni, Monel, pure iron, and stainless steel. The electrolytic cell 20 is separated into an anode chamber 28 and a cathode chamber 29 by a partition wall 27 composed of Ni or a quinol alloy. In the anode chamber 28, a low-polarity carbon paper-size paper (CNS) A4 size (卩 Euro tear-off mm) is configured ---- • 11-(Please read the precautions on the back before (Fill in this page)-Binding-Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs J301C16 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Anode 2 2 composed of the invention description (8); and in the cathode room In 2 9, a cathode 2 3 composed of Ni or Fe is disposed. The upper cover 30 of the electrolytic cell 20 is provided with a discharge port 25 for the fluorine gas generated from the anode chamber 28 and a discharge port 26 for the hydrogen gas generated from the cathode chamber 29. The electrolytic cell 20 is provided with a heater 31 for heating the inside of the electrolytic cell 20. A heat insulator (not shown) is provided around the heater 31. The heater 31 may have a spiral shape or a nickel-chromium alloy wire. The shape is not particularly limited, but it is preferably a shape that covers the entire periphery of the electrolytic cell 20. The vacuum exhaust system D is composed of a molecular sieve 16 and a vacuum pump 17. Further, when K F 1 0 stored in the modulation system a is heated by the heater 9, 'water is desorbed from K F 1 0 by desorption. Next, an operation of the fluorine gas generating device G having the above-mentioned configuration will be described. After the modulation system A is previously heat-treated by the heater 9 at 250 to 30, a predetermined amount of KF 1 0 is filled in the container 7 a. In addition, under vacuum or purge of ultra-high purity inert gas, reheat it to 200 ~ 250 ° C, more preferably 25 ◦ ~ 300 ° C, keep it for 2 4 ~ 4 8 hours to make KF 1 0 dry. At this time, the vacuum piping valve 2a 'is opened to make the valves 3a and 4b closed, and the vacuum exhaust system D is used to exhaust the container 7a. In this way, KF 1 0 can be re-heated to 250 to 300 ° C under the purge of an ultra-high-purity inert gas, and heat treatment can be performed in KF 1 0 for 24 to 48 hours. Water and crystal water are adsorbed and desorbed. Perform K F thermogravimetry (Thermogravimetry, hereinafter referred to (please read the precautions on the back before filling out this page)
、1T 一 本紙張尺度適用中國國家標準（CMS ) A4規格（210X297公釐） -12- 2 經濟部智慧財產局員工消費合作社印製 301C16 A7 _ _B7___ 五、發明説明（9) T G )、微差熱分析法（Differential Thermal Analysis ’ 以 下稱爲D ΤΑ)的結果，觀察到43 · 41、64 · 4 • °C、9 0 . 8 °C及1 5 1 . 6 °C的吸熱高峰。其中’ 4 3 · 4 °C、6 4 · 4 °C、9 0 · 8 °C處的吸熱高峰係由 於吸附水，而1 5 1 · 6 t的吸熱高峰則是由於結晶水的 解吸所造成。作爲原料的K F的吸附水，被認爲會根據前 述的反應式（1 )所示的反應，而容易地被分解。但是’ 對應出現在D T A的1 5 1 . 6 °C的吸熱高峰之結晶水’ 由於與K F之間的相互作用強、電解浴中主要成份的H F 由於氫結合而形成網目結構，所以此結晶水若微量’被認 爲難以擴散、排除。因此，如前所述，利用將K F在超高 純度非活性氣體的淸除（purge)下，再度加熱至2 5 0〜 3 00 °C，預先進行24〜48小時，理想爲10〜30 小時的熱處理，可以使結晶水解吸。 然後，冷卻至室溫，關閉閥2 a之後，打開閥4 b和 閥3 a。此時，預先利用管線加熱器1 5，將高純度非活 性氣體用配管4，加熱至3 0〜3 5 °C。而且，藉由加熱 器1 4，加熱H F鋼瓶1 1，使H F氣體化，一旦打開閥 5 a，H F緩慢地被導入調製系統Α的K F 1 〇中。此 時，K F 1 0和H F的反應激烈而發熱，使水流過冷卻水 用管8來冷卻KF · 2HFg周製裝置7 ’防止溫度超過 .1 〇 〇°C。這是由於一旦溫度超過1 〇 0°c而到達2 0 0 °C時，則H F產生激烈的突沸而呈現出爆發似的狀態。 如此地將H F持續導入調製系統Α中，相對於 (請先閱讀背面之注意事項再填寫本頁) 一裝·、 1T A paper size applies the Chinese National Standard (CMS) A4 specification (210X297 mm) -12- 2 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 301C16 A7 _ __B7___ V. Description of the invention (9) TG) As a result of Differential Thermal Analysis (hereinafter referred to as D ΤΑ), endothermic peaks of 43 · 41, 64 · 4 • ° C, 90.8 ° C, and 15 1.6 ° C were observed. Among them, the endothermic peaks at '4 3 · 4 ° C, 6 4 · 4 ° C, 9 0 · 8 ° C are due to the adsorption of water, and the endothermic peak at 1 5 1 · 6 t is caused by the desorption of crystal water. . The K F adsorbed water as a raw material is considered to be easily decomposed by the reaction shown in the aforementioned reaction formula (1). However, the crystal water corresponding to the endothermic peak at 1 5 1.6 ° C of DTA is a crystal structure due to the strong interaction with KF and the main structure of HF in the electrolytic bath due to hydrogen bonding. If a trace amount 'is considered difficult to diffuse and exclude. Therefore, as described above, KF is re-heated to 250 ~ 300 ° C under the purging of ultra-high purity inert gas, and it is performed for 24 ~ 48 hours in advance, ideally 10 ~ 30 hours. The heat treatment can make the crystals hydrolyze and absorb. Then, cool to room temperature, and after closing valve 2a, open valve 4b and valve 3a. At this time, the high-purity inert gas piping 4 is heated in advance by a line heater 15 to 30 to 35 ° C. Further, the H F cylinder 11 is heated by the heater 14 to vaporize the H F. Once the valve 5 a is opened, the H F is slowly introduced into K F 1 0 of the modulation system A. At this time, the reaction between K F 1 0 and H F is intense and heat is generated, and water is caused to flow through the cooling water. The tube 8 is used to cool the KF 2HFg cycle device 7 ′ to prevent the temperature from exceeding .100 ° C. This is because once the temperature exceeds 100 ° C and reaches 200 ° C, H F will generate a sharp bump and become explosive. In this way, H F is continuously introduced into the modulation system A, as opposed to (please read the precautions on the back before filling this page)
、1T —0· 本紙張尺度適用中國國家標準（CNS) Α4規格（2丨〇><297公釐） -13- 〇 16 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明説明（1〇) K F 1 0的H F，能夠提高H F的供給速度，使得比 K F · H F的莫耳比高。而且，藉由H F供給系統Β的測 力器1 2，確認規定量的H F被供應給調製系統Α中之 後，關閉閥5 a同時打開閥4 a，使高純度非活性氣體從 配管1導入，而從非活性氣體淸除用配管3排氣。這是爲 了要防止配管1中的H F，被急劇地吸收在由K F 1 〇所 調製成KF·2HF的KF·2HF中，所導致的KF· 2 H F逆流固化在配管1中的情況發生。 而且，在適當時間利用非活性氣體將調製系統Α淸除 之後，關閉閥4 b。接著，從非活性氣體淸除用配管3供 給非活性氣體。與此同時，打開閥1 8和閥1 9。調製系 統A，利用從非活性氣體淸除用配管3所導入的非活性氣 體的壓力，將調製成的KF · 2HF，從配管1送至氟氣 產生系統C的電解槽2 0內。此時，電解槽2 0預先以 2 5 0〜3 5 0 °C進行熱處理，使吸附水等解吸 (desorption ) 〇 如此，在本發明的氟氣產生裝置中，能夠使水分吸附 量少的高純度K F · 2 H F，不會與空氣接觸而供給至氟 氣產生裝置的電解槽內，能夠在電解槽中形成高純度的電 解浴K F · 2 H F。藉由此手段，電解浴的氧濃度降低至 極低程度。 又，也可以做成將調製系統A、H F供給系統Β及氟 氣產生系統C的各個系統，收容在可以控制氣氛的框體 內。藉由此手段，能夠調整各系統的外部氣氛的溼度，且 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公着） I---.--J--^裝------訂------0、 (請先閲讀背面之注意事項再填寫本頁) -14 - 0301C16 A7 B7 經濟部智慧財產局員工消費合作社印製 •五、發明説明（ii) 能夠抑制混入各系統內的氧。又，也能夠將各系統全體也 就是氟氣產生裝置G，收容在一個框體內。再者，利用將 這些系統全部設置在潔淨室內，能夠得到與收容在可以控 制氣氛的框體內相同的效果。如此，藉由抑制氧混入各系 統內，可以更加確實地減少所產生的氟氣中的氧濃度。 再者，關於本發明的氟氣產生裝置及氟氣產生方法， 並不被限定於上述實施形態的例子中。 (實施例） 以下，根據實施例，具體地說明關於本發明的氟氣產 生裝置。 (實施例1 ) 第1圖所示的氟氣產生裝置G，預先藉由加熱器9將 調製系統A以2 5 0〜3 0 0 t進行熱處理之後，將K F 1 0裝塡入容器7 a內，以純度9 9 · 9 9 9 9 %的高純 度N 2氣體的淸除（purge)下，再度加熱至250〜300 °C，保持2 4〜4 8小時，使K F 1 〇乾燥。然後，冷卻 •至室溫，將H F導入調製系統A的K F 1 〇中。此時，使 水流過冷卻水用管8來冷卻K F · 2 H F調製裝置7，使 溫度爲1 0 〇 °C以下。而且，藉由H F供給系統Β的測力 器1 2，確認已經供給規定量的H F至調製系統a之後， 利用高純度N 2氣體，以適當時間淸除調製系統a內之後， 供給高純度N 2氣體，利用其氣體壓力，將所調製的κ F · (請先閲讀背面之注意事項再填寫本頁) 一裝. 訂， 1T —0 · This paper size is in accordance with China National Standard (CNS) A4 specification (2 丨 〇 < 297mm) -13- 〇16 Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (10) The HF of KF 10 can increase the supply rate of HF, so that the molar ratio is higher than that of KF · HF. Furthermore, after confirming that a predetermined amount of HF is supplied to the modulation system A by the load cell 12 of the HF supply system B, the valve 5 a is closed and the valve 4 a is opened to introduce a high-purity inert gas from the pipe 1. The exhaust gas is purged from the inert gas purge pipe 3. This is to prevent the H F in the piping 1 from being abruptly absorbed in the KF · 2HF modulated by K F 1〇 to KF · 2HF, and the KF · 2 H F caused to solidify in the piping 1 countercurrently. Further, after the modulation system A 淸 is removed with an inert gas at an appropriate time, the valve 4b is closed. Next, the inert gas is supplied from the inert gas scavenging pipe 3. At the same time, valves 18 and 19 are opened. The modulation system A uses the pressure of the inert gas introduced from the inert gas purging pipe 3 to send the prepared KF · 2HF from the pipe 1 to the electrolytic cell 20 of the fluorine gas generation system C. At this time, the electrolytic cell 20 is previously heat-treated at 250 to 350 ° C to desorb the adsorbed water and the like. Thus, in the fluorine gas generating device of the present invention, it is possible to increase the amount of adsorbed water with a small amount. The purity KF · 2 HF can be supplied into the electrolytic cell of the fluorine gas generator without coming into contact with air, and a high-purity electrolytic bath KF · 2 HF can be formed in the electrolytic cell. By this means, the oxygen concentration of the electrolytic bath is reduced to an extremely low level. Alternatively, each of the modulation system A, the HF supply system B, and the fluorine gas generation system C may be configured to be housed in a housing capable of controlling the atmosphere. By this means, the humidity of the external atmosphere of each system can be adjusted, and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297) I ---.-- J-^ equipment ----- -Order ------ 0 、 (Please read the notes on the back before filling out this page) -14-0301C16 A7 B7 Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs • V. Description of the invention (ii) It can suppress mixing Oxygen in each system. Furthermore, the entire system, that is, the fluorine gas generating device G, can also be housed in a single housing. Furthermore, by installing all these systems in a clean room, it is possible to obtain the same effects as if they were housed in a casing that can control the atmosphere. In this way, by suppressing the incorporation of oxygen into each system, the oxygen concentration in the generated fluorine gas can be reduced more reliably. It should be noted that the fluorine gas generating device and the fluorine gas generating method of the present invention are not limited to the examples of the above embodiment. (Example) Hereinafter, the fluorine gas generating device of the present invention will be specifically described based on examples. (Example 1) The fluorine gas generating device G shown in FIG. 1 heat-processes the modulation system A at 2 50 to 3 0 0 by a heater 9 in advance, and then puts KF 10 into a container 7 a Then, under the purging of a high-purity N 2 gas having a purity of 99.9999%, it was heated again to 250-300 ° C, maintained for 2 to 4-8 hours, and KF 10 was dried. Then, it is cooled to room temperature, and H F is introduced into K F 1 0 of the modulation system A. At this time, the K F · 2 H F modulator 7 is cooled by flowing water through a cooling water pipe 8 to a temperature of 100 ° C or lower. Furthermore, after confirming that a predetermined amount of HF has been supplied to the modulation system a by the dynamometer 12 of the HF supply system B, the high purity N 2 gas is used to eliminate the inside of the modulation system a at an appropriate time, and then high purity N is supplied. 2 gas, use its gas pressure to pack the κ F · (Please read the precautions on the back before filling this page)
Lt 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） -15- 0301C16 經濟部智慧財產局員工消t合作社印製 A7 B7 五、發明説明（θ 2HF從配管1送出至氟氣產生系統C的電解槽2 0內’ 建立浴量7 <的電解浴。而且，在氟氣產生系統C中，陽 極使用碳電極、陰極使用N i電極，以1 〇 A/dm2的施加 電流密度，進行定電流電解。而且，在大約1 0 0 Ahr的 通電量的時點，利用氣相色譜儀（gas chromatography)，測 量所產生氟氣中的〇2量的結果，約爲6 5 0 P pm。 (實施例2 ) 使用與實施例1同樣的K F · 2 H F作爲電解浴，在 氟氣產生系統C中，陽極使用碳電極、陰極使用N i電 極，以1 5 A/dm2的施加電流密度，進行定電流電解。而 且，在大約1 0 0 Ahr的通電量的時點，利用氣相色譜 儀，測量所產生氟氣中的〇2量的結果，約爲4 5 0 ρ p m 〇 (實施例3 ) 使用與實施例1同樣的K F · 2 H F作爲電解浴，在 氟氣產生系統C中，陽極使用碳電極、陰極使用N i電 極’以2 A/dm2的施加電流密度，進行定電流電解。而 且，在大約1 0 0 Ahr的通電量的時點，利用氣相色譜 儀，測量所產生氟氣中的0 2量的結果，約爲9 5 0 P P m 〇 (實施例4 ) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐） (請先閱讀背面之注意事項再填寫本頁) •裝. 訂 -16- B7 五、發明説明（4 (請先閲讀背面之注意事項再填寫本頁) 使用與實施例1同樣的K F · 2 H F作爲電解浴，將 氟氣產生系統C收容在水分控制手段也就是框體內，將框 體內部的溼度控制在4 0 %，陽極使用碳電極、陰極使用 N i電極，以2 0 A/dm2的施加電流密度，進行定電流電 解。而且，在大約1 0 0 Ahr的通電量的時點，利用氣相 色譜儀，測量所產生氟氣中的〇2量的結果，約爲7 0 p p m 〇 (比較例1 ) 使用以習知的方法所調製的K F · 2 H F作爲電解 浴，在氟氣產生系統C中，陽極使用碳電極、陰極使用 N i電極，以1 〇 A/dm2的施加電流密度，進行定電流電 解。而且，在大約1 0 0 Ahr的通電量的時點，利用氣相 色譜儀，測量所產生氟氣中的〇2量的結果，約爲 30000ppm〇 (比較例2 ) 經濟部智慧財產局員工消費合作社印製 使用以習知的方法所調製的K F · 2 H F作爲電解 浴，在氟氣產生系統C中，陽極使用碳電極、陰極使用 N i電極，以1 5 A/dm2的施加電流密度，進行定電流電 解。而且，在大約1 〇 0 Ahr的通電量的時點，利用氣相 色譜儀，測量所產生氟氣中的〇 2量的結果，約爲 25000ppm。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 0301C16 經濟部智慧財產局員工消費合作社印製 Α7 Β7 .五、發明説明（Μ (比較例3 ) 使用與實施例1同樣的K F · 2 H F作爲電解浴，在 氟氣產生系統C中，陽極使用碳電極、陰極使用ν i電 極，以1 A/dm2的施加電流密度，進行定電流電解。而 且，在大約1 0 0 Ahr的通電量的時點，利用氣相色譜 儀，測量所產生氟氣中的0 2量的結果，約爲2 1 〇 〇 〇 p p m 〇 在第2圖中，表示前述實施例1與比較例1、3的情 況的通電量、及氟氣中的0 2量的關係。 * 如第2圖所示，可知將K，F乾燥使水分解吸（去吸 附）之後，將調製成K F · 2 H F使用在電解浴中的實施 例1，從氟氣產生初期開始，氟氣中的氧量少。 【產業上的利用可能性】 本發明，如以上的構成，藉由使用將K F乾燥，使表 面的吸附水和結晶水等解吸之後所調製成的K F · 2 H F ’可以從氟氣產生的初期，便能夠安定地產生所含 的氧濃度非常低的氯氣。 【圖面的簡單說明】 第1圖係關於本發明的氟氣產生裝置的模式圖。 第2圖係表示實施例1及比較例1、3的情況的通電 量、與氟氣中的氧量之間的關係的圖。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） I - ^IT (請先閲讀背面之注意事項再填寫本頁) -18- 2 301C16 kl B7 五、發明説明（0 【符號說明】 (請先閲讀背面之注意事項再填寫本頁) A :調製系統 B : H F供給系統 C :氟氣產生系統 D :真空排氣系統 G :氟氣產生裝置 1 : HF供給兼KF · 2HF送出配管 2:真空配管 2 a :真空配管閥 3 :非活性氣體淸除用配管 3a、4a、4b、5a、18、19:閥 4:高純度非活性氣體用配管 . 5:HF送出用配管 7:KF.2HF調製裝置 8 :冷卻水用管 9、1 4、3 1 :加熱器 1 1 : H F鋼瓶 經濟部智慧財產局員工消費合作社印製 1 2 :測力器 1 3 :框體 1 5 :管線加熱器 1 6 :分子篩 17:真空泵 * 2 0 :電解槽 2 2 :陽極 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -19- 2 301C16 A7 B7五、發明説明（θ 2 3 :陰極 2 4 :電解浴 2 5 :氟氣的排出口 2 6 :氫氣的排出口 2 7 :隔壁 2 8 :陽極室 * 2 9 :陰極室 (請先閱讀背面之注意事項再填寫本頁) 裝 -1- 經濟部智慧財產局員工消費合作社印製 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -20-Lt This paper size applies Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) -15- 0301C16 Employees of Intellectual Property Bureau of the Ministry of Economy printed A7 B7 Cooperative cooperatives V. Description of invention (θ 2HF sent from pipe 1 to fluorine In the electrolytic cell 20 of the gas generating system C, an electrolytic bath having a bath amount of 7 < is established. In the fluorine gas generating system C, a carbon electrode is used for the anode and a Ni electrode is used for the cathode, and the application is performed at 10 A / dm2. Constant current electrolysis was performed at a current density. Also, at a time point of about 100 Ahr, gas chromatography was used to measure the amount of 02 in the generated fluorine gas, which was about 6 50. P pm (Example 2) The same KF · 2 HF as that used in Example 1 was used as an electrolytic bath. In the fluorine gas generation system C, a carbon electrode was used as the anode and a Ni electrode was used as the cathode. The application was performed at 15 A / dm2. Constant current electrolysis was performed at a current density. At the point of energization at about 100 Ahr, the amount of 02 in the generated fluorine gas was measured with a gas chromatograph, which was about 4 50 ρ pm 〇 ( Example 3) The same KF · 2 HF as in Example 1 was used Unbath, in the fluorine gas generation system C, a carbon electrode is used for the anode and a Ni electrode is used for the cathode, and constant current electrolysis is performed at an applied current density of 2 A / dm2. In addition, at a time point of about 100 Ahr Using a gas chromatograph to measure the amount of 02 in the fluorine gas produced, it was about 950 PP m (Example 4) This paper size applies the Chinese National Standard (CNS) A4 specification (210X29? Mm) ) (Please read the precautions on the back before filling this page) • Pack. Order -16- B7 V. Description of the invention (4 (Please read the precautions on the back before filling out this page) Use the same KF as in Example 1 · 2 HF is used as an electrolytic bath. The fluorine gas generating system C is housed in a moisture control means, that is, a frame, and the humidity inside the frame is controlled to 40%. The anode uses a carbon electrode and the cathode uses a Ni electrode. Constant current electrolysis was performed at an applied current density of dm2. Furthermore, at a time point of about 100 Ahr, a gas chromatograph was used to measure the amount of 02 in the generated fluorine gas, which was about 70 ppm. (Comparative Example 1) Using K modulated by a conventional method F · 2 HF is used as an electrolytic bath. In the fluorine gas generating system C, a carbon electrode is used for the anode and a Ni electrode is used for the cathode. The current is applied at a constant current of 10 A / dm2. At the time of Ahr's energization, the gas chromatograph was used to measure the amount of 02 in the generated fluorine gas, which was about 30,000 ppm. (Comparative Example 2) Printed for use by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The KF · 2 HF prepared by the method was used as an electrolytic bath. In the fluorine gas generating system C, a carbon electrode was used for the anode, and a Ni electrode was used for the cathode, and constant current electrolysis was performed at an applied current density of 15 A / dm2. Further, at a time point of about 1,000 Ahr, a gas chromatograph was used to measure the amount of 02 in the generated fluorine gas, which was about 25,000 ppm. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 0301C16 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7. V. Description of the invention (M (Comparative Example 3)) Use and Example 1 The same KF · 2 HF is used as an electrolytic bath. In the fluorine gas generation system C, a carbon electrode is used for the anode and a ν i electrode is used for the cathode, and constant current electrolysis is performed at an applied current density of 1 A / dm 2. At the time point of the energization of 0 Ahr, a gas chromatograph was used to measure the amount of 02 in the generated fluorine gas, which was approximately 21,000 ppm. In the second figure, the foregoing Example 1 and Comparative Example are shown. The relationship between the amount of electricity in cases 1 and 3 and the amount of 02 in fluorine gas. * As shown in Figure 2, it can be seen that after drying K and F to decompose and desorb water (desorption), it will be adjusted to KF · 2 HF In Example 1 used in the electrolytic bath, the amount of oxygen in the fluorine gas was small from the initial stage of the generation of fluorine gas. [Industrial Applicability] The present invention, as described above, dries KF by using it to make the surface Adjusted after desorption of adsorbed water and crystal water The resulting KF · 2 HF 'can stably produce chlorine gas with a very low oxygen concentration from the initial stage of the fluorine gas generation. [Brief description of the drawing] Fig. 1 is about the fluorine gas generating device of the present invention. Schematic diagram. The second diagram is a diagram showing the relationship between the amount of electricity and the amount of oxygen in fluorine gas in the case of Example 1 and Comparative Examples 1 and 3. This paper size applies the Chinese National Standard (CNS) A4 specification ( 210X 297mm) I-^ IT (Please read the precautions on the back before filling out this page) -18- 2 301C16 kl B7 V. Description of the invention (0 [Symbol description] (Please read the precautions on the back before filling out this (Page) A: Modulation system B: HF supply system C: Fluorine gas generation system D: Vacuum exhaust system G: Fluorine gas generation device 1: HF supply and KF · 2HF delivery piping 2: Vacuum piping 2 a: Vacuum piping valve 3 : Inactive gas removal pipe 3a, 4a, 4b, 5a, 18, 19: Valve 4: High purity inactive gas pipe. 5: HF delivery pipe 7: KF. 2HF modulation device 8: Cooling water pipe 9, 1 4, 3 1: Heater 1 1: HF Cylinder Bureau of Intellectual Property Bureau, Consumer Consumption Cooperative of Employees System 1 2: Force gauge 1 3: Frame 1 5: Line heater 1 6: Molecular sieve 17: Vacuum pump * 2 0: Electrolyzer 2 2: Anode This paper size applies to China National Standard (CNS) Α4 specification (210X297) -19- 2 301C16 A7 B7 V. Description of the invention (θ 2 3: cathode 2 4: electrolytic bath 2 5: outlet of fluorine gas 2 6: outlet of hydrogen 2 7: partition wall 2 8: anode chamber * 2 9: Cathodic Chamber (Please read the notes on the back before filling this page) Packing -1- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) Α4 size (210X 297 mm) -20-