583177 A7 ______ B7 五、發明説明（1 ) 本發明係有關四氟甲烷（以下稱「F c — 1 4」或「 CF4」。）之精製方法及其用途。 先行技術中，F C - 1 4係做爲如：半導體裝置製造 過程之蝕刻氣體或洗淨氣體使用者，因此，被期待爲高純 度品者。 有關此F C — 1 4之製造方自古被提出各種方法。具 體例如： (1 )於觸媒存在下，使二氯二氟甲烷與氟化氫進行 反應之方法， (2 )於觸媒存在下，使單氯三氟甲烷與氟化氫進行 反應之方法， (3 )使三氟甲烷與氟氣進行反應之方法， (4 )使碳與氟氣進行反應之方法， (5 )使四氟乙烯進行熱分解之方法， 等爲公知者。 惟，藉由此等方法進行製造F C - 1 4時，於反應所 生成之F C - 1 4中間體，副產物，或原於原料之不純物 等與目的物之F C - 1 4形成共沸混合物，類共沸混合物 ，因此，造成其分離極爲不易之問題點。因此，被提出將 含有不純物之三氟甲烷（CHF3)之F C - 1 4以沸石， 碳質吸附劑進行處理之精製方法（專利第2 9 2 4 6 6 0 號公報）。 惟，先行技術中，欲精製F C — 1 4中不純物之含乙 烯化合物類、烴基化合物類、一氧化碳及/或二氧化碳之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) 一 (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 583177 A7 B7 五、發明説明（2 ) F C 一 1 4後，取得幾乎不含此等不純物之高純度F C -1 4者，仍無一簡便且經濟型的有利工業之方法者。 本發明於此背景下以提供一種以吸附劑接觸F C -1 4後進行吸附去除此等不純物，經濟面佳且有利工業取 得高純度F C — 1 4之精製方法爲課題者。 本發明者爲解決該課題，進行精密硏討後結果發現， 於製造高純度F C - 1 4之方法中，以具有特定之平均細 孔徑及S i / A 1比之沸石及/或具有特定平均細孔徑之 碳質吸附劑（分子篩碳）所成之吸附劑與含有不純物之乙 烯化合物類、烴基化合物類、一氧化碳及/或二氧化碳之 F C - 1 4接觸後，可選擇性吸附去除該不純物後，取得 幾乎未含有不純物之高純度F C- 1 4者，進而完成本發 明。本發明係以下（1 )〜（1 4 )所示之四氟甲烷的精 製方法及其用途者。 (1 )以平均細孔徑爲3 · 4 A〜1 1 A、 S i / A 1比爲1 · 5以下之沸石及/或平均細孔徑爲 3·4A〜11A之碳質吸附劑與含有不純物之乙烯化合 物類、烴基化合物類、一氧化碳及/或二氧化碳之四氟甲 烷進行接觸後，降低該不純物者爲特徴之精製四氟甲烷方 法者。 (2 )以液相使含有該不純物之四氟甲烷與該沸石及 /或該碳質吸附劑相互接觸之該（1 )所載的四氟甲院精 製方法。 (3 )該沸石爲至少1種選自MS — 4A、MS — 5 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -裝-- (請先閲讀背面之注意事項再填寫本頁) 訂 έ 經濟部智慧財產局員工消費合作社印製 583177 A7 _________ B7 _ 五、發明説明（3 ) A、MS — 1 0X及MS—l 3X所成群之該（1)或（ 2 )所載之四氟甲烷精製方法。 (請先閲讀背面之注意事項再填寫本頁) (4 )該碳質吸附劑爲分子篩碳4A 及/或分子篩 碳5A之該（1)或（2)所載之四氟甲烷精製方法。 (5 )該乙烯化合物類係至少1種選自乙烯、氟乙烯 '二氟乙烯及四氟乙烯所成群之化合物之該（1)或（2 )所的四氟甲烷精製方法。 (6 )該乙烯化合物類爲乙嫌及/或四氟乙烯之該（ 5)所載的四氟甲烷精製方法。 (7 )該烴基化合物類係至少1種選自甲烷、乙烷及 丙烷所成群化合物之該（1)或（2)所載的四氟甲烷精 製方法。 (8 )該烴基化合物類爲甲烷及/或乙烷之該（7 ) 所載的四氟甲烷精製方法。 (9)該（1 )或（2)所載之降低含於四氟甲烷中 之乙烯化合物類、烴基化合物類、一氧化碳及二氧化碳總 含量爲3 p pm以下之四氟甲烷精製方法。 經濟部智慧財產局員工消費合作社印製 (1 0 )含有不純物之乙烯化合物類、烴基化合物類 、一氧化碳及/或二氧化碳之四氟甲院藉由三氟甲院與氟 氣反應後直接氟化法後，製造四氟甲烷之該（1 )或（2 )所載的四氟甲烷精製方法。 (1 1 )含有不純物之乙烯化合物類、烴基化合物類 、一氧化碳及/或二氧化碳之四氟甲烷藉由碳與氟氣反應 後直接氟化法後，製造四氟甲烷之該（1 )或（2 )所載 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6 - · 583177 A7 ____ B7 _____ 五、發明説明（4 ) 之四氟甲烷精製方法。 (請先閲讀背面之注意事項再填寫本頁) (1 2 )藉由該（1 )〜（1 1 )任一所載之方法精 製後取得純度爲9 9 · 9 9 9 7質量％以上者爲特徵之四 氟甲烷製品。 (1 3 )該（1 2 )所載之含有四氟甲烷製品之蝕刻 氣體。 (1 4 )該（1 2 )所載之含有四氟甲烷製品之洗淨 氣體。 亦即，本發明係「使含有不純物之乙烯化合物類、烴 基類、一氧化碳及/或二氧化碳之F C— 1 4藉由與平均 細孔徑爲3 · 4 A〜1 1人、S i / A 1比爲1 · 5以下 之沸石及/或平均細孔徑爲3 · 4人〜1 1人之碳質吸著 劑接觸後，降低該不純物者爲特徴之精製四氟甲烷的方法 」、「藉由該方法進行精製取得純度爲99.9997質量％以上 者爲特徵之四氟甲烷製品」及「含該四氟甲烷製品之蝕刻 氣體及洗淨氣體」者。 經濟部智慧財產局員工消費合作社印製 〔發明實施之形態〕 做爲F C — 1 4製造方法者如公知者之將三氟甲烷與 氟氣反應之方法、使碳與氟氣反應之方法、或使四氟乙烯 進行熱分解之方法、等例。使用此等方法時，所取得之 F C - 1 4中，藉由原料中之不純物如：有機微量不純物 、微量氧、微量水份等、不純物例如：含有乙烯化合物類 、烴基化合物類、一氧化碳及/或二氧化碳者。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583177 A7 _____B7 五、發明説明（5 ) 做爲乙烯化合物類者係含有至少1種選自乙烯（Η 2二 C c Η 2 )、單氟乙烯（CH2=CHF)、二氟乙烯（ c Η 2 = C F 2 )、四氟乙烯（CF2=CF2)之化合物者 〇 做爲烴基化合物者係含有至少1種選自甲烷（C Η 4 ) 、乙烷（C 2 Η 6 )、丙烷（C 3 Η 8 )之化合物者。 表1代表目的物之F C - 1 4與此等不純物於大氣壓 下之沸點。 〔表1〕 化合物名 化學式 沸點（°c ) 一氧化碳 CO -191.5 甲烷 ch4 -161.5 F C - 1 4 cf4 -128 乙烯 ch2 = ch2 -103.7 乙烷 CH3CH3 -89 二氟乙烯 ch2 = cf2 -83 二氧化碳 C〇2 -78.5 四氟乙烯 cf2 = cf2 -76.3 單氟乙烯 ch2 = chf -72 丙烷 CH3CH2CH3 -42.1 目的物之F C - 1 4與此等不純物由於形成類共沸之 混合物，或由表1可確定接近沸點、等理由，於蒸餾操作 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） _ g - (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 583177 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（6 ) 下爲極不易分離之物質者。因此，一般之蒸餾操作中爲極 力降低不純物，意圖採取增加蒸餾塔之段數，使蒸餾塔之 根數增多等對策，惟，此經濟面不理想，而且，極爲不易 製造出不含此等不純物之局純度F C - 1 4者。 本發明中，爲選擇性吸附去除F C — 1 4中此等不純 物類，以平均細孔徑爲3 · 4 A〜1 1 A之沸石及/或平 均細孔徑爲3 · 4 A〜1 1 A之碳質吸附劑（分子篩碳= )做爲吸附劑使用之。做爲測定平均細孔徑之方法例如： 使用A r氣體之氣體吸附法例。 做爲更理想之吸附劑者係於（1 )平均細孔徑爲 3 · 4人〜1 1人、S i / A 1比爲1 · 5以下之沸石、 (2 )平均細孔徑爲3 · 4 A〜1 1 A之碳質吸附劑（分 子篩碳）、（3 )平均細孔徑爲3 · 4 A〜1 1 A、 S i / A 1比爲1 · 5以下之沸石中添加平均細孔徑爲 3 . 4 A〜1 1 A之碳質吸附劑所成之吸附劑者。其中， S i / A 1比代表原子比。 做爲利用此等吸附劑後可去除之F C - 1 4中的不純 物類者，具體例如：不飽和化合物類有乙烯、單氟乙烯、 二氟乙烯、四氟乙烯之例，烴基化合物類之例如：甲烷、 乙烷、丙烷之例。又，含氧化合物例如：一氧化碳、二氧 化碳之例。此等不純物類以乙烯、四氟乙烯、甲烷、乙烷 、一氧化碳或二氧化碳者宜，更佳者爲乙烯或乙烷。 目的物之F C - 1 4與此等不純物之分子徑差極小， 藉由分子徑之差極不易選擇性吸附去除F C — 1 4中之不 (請先閱讀背面之注意事項再填寫本頁) 4 •項再填· 裝- 訂 it 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ g _ 583177 A7 B7 五、發明説明（7 ) 純物類。因此，本發明考量吸附劑之極性、細孔徑等後’ 可使用以下3種吸附劑做爲可選擇性去除該不純物物類之 吸附劑者。 第1之吸附劑其平均細孔徑爲3 · 4 A〜1 1 A之沸 石、較佳者其S i/Al比爲1 · 5以下之沸石者。具體 例：MS — 4A之例者，MS — 4A爲具有3 · 5A左右 之平均細孔徑者，S i / A 1比爲1 · 0者。使用此沸石 進行吸附操作後，可降低含不純物之乙烯、四氟乙烯、甲 烷、乙烷、一氧化碳及二氧化碳等之含量。依沸石種類不 同，可使不純物含量減爲5 p P m以下，取得高純度F C -1 4 者。 當平均細孔徑小於3 · 4 A時，則S i / A 1比即使 爲1 · 5以下，則具有3 · 2 A左右細孔徑之沸石仍未出 現降低不純物含量。 S i / A 1比爲1 . 5以下則即使平均細孔徑大於 1 1 A之沸石仍未降低不純物含量。 又，平均細孔徑即使爲3 · 4 A〜1 1 A者，而 S i / A 1比爲1 · 5以上之沸石則仍未降低不純物含量 〇 第2吸附劑其平均細孔徑爲3 · 4 A〜1 1 A之碳質 吸附劑（分子篩碳）者。例如：具有4 A左右之平均細孔 徑的碳質吸附劑與該沸石相同，可降低該不純物含量爲5 p pm以下，取得高純度F C— 1 4者。 惟，平均細孔徑大於1 1 A之碳質吸附劑中未出現降 —. r ^-----^ 批衣-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -1〇 - 583177 A7 B7 五、發明説明（8 ) 低不純物，如：具有一般所使用具強力吸附能之3 5 A左 右的平均細孔徑之活性碳幾乎未出現降低不純物。 (請先閱讀背面之注意事項再填寫本頁) 第3吸附劑係於平均細孔徑爲3 . 4 A〜1 1 A、 S i / A 1比爲1 · 5以下之沸石（第1吸附劑）中添加 (混合）平均細孔徑爲3 · 4 A〜1 1 A之碳質吸附劑（ 第2吸附劑）後所成之吸附劑者。依此吸附劑之種類而異 ，可使不純物含量降低至3 p p m以下，可取得更高純度 之F C - 1 4。此乃該沸石特別具一氧化碳、二氧化碳等 良好的吸附能力，另外，碳質吸附劑特別具有良好的不飽 和化合物等吸附能力，而考量混合兩吸附劑所使用之雙重 效果者。 該沸石及碳質吸附劑可以1種單獨使用，亦可合倂2 種以上任意比例組合使用之。又，第3吸附劑時，沸石與 碳質吸附劑之混合比可因應不純物類之濃度進行變動之。 經濟部智慧財產局員工消費合作社印製 做爲含於F C - 1 4中之不純物者並未特別限定乙烯 化合物類、烴基化合物類、一氧化碳及/或二氧化碳之濃 度，一般以0 · 1質量％以下者宜，更佳者爲0 · 05質 量％以下者。 又，於目的之F C — 1 4中混入上述以外之不純物， 如：全氟化物之FC—116 (CF3CF3) 、FC— 2 1 8 ( C 3 F 8 )等時，於使用該吸附劑之任意處理步驟 中進行蒸餾操作則可分離去除全氟化合物。 本發明F C — 1 4之精製方法中，使含有不純物之 F C - 1 4接觸吸附劑之方法並無特別限定，如：於氣相 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) :” _ " 583177 A7 B7 五、發明説明（9 ) 進行接觸之方法，於氣液進行接觸之方法，或於液相進行 接觸之方法中任意方法均可，其中又以於液相進行接觸之 方法者其效率爲最理想者。 於液相進行接觸之方法中，可使用分批式、連續式等 公知之方法，而，工業上如：使固定床式吸附塔設置2基 、另外，一般只要達到飽和吸附使此進行切換再生之方法 者。 又，含不純物之F C - 1 4接觸吸附劑時，其處理溫 度，處理量及處理壓力並無特別限定，一般，處理溫度以 低溫者宜，爲一 5 0 °C〜5 0 °C之範圍溫度者佳。又，處 理壓力當液相時只要維持液相即可，氣相時並無特別限定 〇 如以上說明，利用本發明之精製方法則可有效吸附去 除含於F C - 1 4中之乙烯化合物類、烴基化合物類、一 氧化碳及/或二氧化碳，取得高純度之F C - 1 4。又， 所取得之FC — 14純度爲99 · 9997質量％以上者 ，做爲純度99 .9997 質量％以上之FC — 14製 品的分析方法者可使用（1 )氣體層析法（G C )之T C D法，F I D法（均含預切法）、E C D法，（2 )氣體 層析法質量分析計（G C - MS )等之分析器者。 又，高純度之F C - 1 4於半導體裝置製造步驟中之 蝕刻步驟中可做爲飩刻氣使用之。又’半導體裝置製造步 驟中之洗淨步驟中亦可做爲洗淨氣使用。L S 1、 TFT等之半導體裝置製造過程中，使用CVD法、濺射 i紙張尺度適用中ii家標準（CNS ) A4規格（210x297公釐） (請先閱讀背面之注意事項再填‘ :寫本頁) 經濟部智慧財產局員工消費合作社印製 583177 A7 B7 五、發明説明（10 ) 法' 或蒸鍍法等形成薄膜、厚膜後，爲形成電路模型進行 倉虫刻。又’形成薄膜、厚膜之裝置中，爲去除堆積於裝置 內壁、冶具等之不必要堆積物進行洗淨。此係生成不必要 堆積物將造成產生剝落之原因，因此，欲製造良質膜務必 隨時去除該不必要堆積物。 其中，使用F C - 1 4之蝕刻方法可於等離子蝕刻、 微波蝕刻等各種乾蝕刻條件下進行之，亦可以適當比例混 合FC— 14與He、N2、Ar等不活性氣體或HC1、 〇2、幵2等氣體後，使用之。 〔實施例〕 以下，藉由實施例與比較例進行本發明更詳細之說明 ’惟，本發明並非僅限於此等實施例中。 〔F C - 1 4之原料例1〕 使碳與氟氣於稀釋氣體之存在下進行反應後，去除未 反應之氟氣後，以公知方法藉由分別蒸餾進行精製！τ C 一 1 4豐沛生成之氣體，於氣體層析法進行分析後，取得具 有表2所示組成之F C - 1 4。 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐） J----- (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製583177 A7 ______ B7 V. Description of the invention (1) The present invention relates to a method for refining tetrafluoromethane (hereinafter referred to as "F c — 1 4" or "CF4") and its use. In the prior art, F C-1 4 is used as an etching gas or a cleaning gas user in the manufacturing process of semiconductor devices, so it is expected to be a high-purity product. Various methods have been proposed by the manufacturers of this F C — 1 4 since ancient times. Specific examples: (1) a method of reacting dichlorodifluoromethane with hydrogen fluoride in the presence of a catalyst, (2) a method of reacting monochlorotrifluoromethane with hydrogen fluoride in the presence of a catalyst, (3) A method of reacting trifluoromethane with fluorine gas, (4) a method of reacting carbon with fluorine gas, (5) a method of thermally decomposing tetrafluoroethylene, and the like are known. However, when FC-14 is produced by these methods, the FC-14 intermediate, by-products, or impurities derived from the raw materials, etc., form an azeotropic mixture with the target FC-14, It is azeotrope-like, so it makes it difficult to separate. Therefore, a purification method has been proposed in which F C-14 containing trifluoromethane (CHF3) containing impurities is treated with a zeolite and a carbonaceous adsorbent (Patent No. 2 9 2 4 6 60). However, in the prior art, the paper size of ethylene-containing compounds, hydrocarbon-based compounds, carbon monoxide, and / or carbon dioxide to be refined in FC-14 is applicable to China National Standard (CNS) A4 specifications (210X297 mm). Read the precautions on the back before filling this page) ~ ^ Packing and printing 583177 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) After FC-14, it is almost free of such impurities There is still no simple and economical method to facilitate industrial use of high-purity FC-14. Under this background, the present invention aims to provide a refining method for removing impurities by contacting F C-1 4 with an adsorbent, which is economical and advantageous for industrially obtaining high-purity F C-1 4. In order to solve this problem, the present inventors conducted detailed investigations and found that, in the method for manufacturing high-purity FC-14, a zeolite having a specific average pore diameter and a Si / A1 ratio and / or having a specific average After the adsorbent formed by the pore-size carbonaceous adsorbent (molecular sieve carbon) is in contact with FC-14 containing ethylene compounds, hydrocarbon-based compounds, carbon monoxide and / or carbon dioxide containing impurities, after selectively removing the impurities, Those who have obtained a high-purity F C-14 containing almost no impurities are further completed the present invention. The present invention relates to a method for purifying tetrafluoromethane as shown in the following (1) to (1 4) and uses thereof. (1) A zeolite having an average pore diameter of 3.4 A to 1 1 A and a ratio of Si / A 1 to 1.5 or less and / or a carbonaceous adsorbent having an average pore diameter of 3.4 to 11 A and containing impurities After contacting the tetrafluoromethane of ethylene compounds, hydrocarbon compounds, carbon monoxide and / or carbon dioxide, the person who reduces the impurities is a special method of purifying tetrafluoromethane. (2) The method for refining tetrafluoromethane contained in (1) in which the tetrafluoromethane containing the impurity and the zeolite and / or the carbonaceous adsorbent are brought into contact with each other in a liquid phase. (3) The zeolite is at least one selected from MS-4A, MS-5. This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm)-Packing-(Please read the precautions on the back before filling in this Page) Order Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 583177 A7 _________ B7 _ V. Description of the Invention (3) A, MS — 1 0X and MS — 13X are grouped by this (1) or (2) The method of refining tetrafluoromethane. (Please read the precautions on the back before filling out this page) (4) The carbonaceous adsorbent is molecular sieve carbon 4A and / or molecular sieve carbon 5A. The method of refining tetrafluoromethane contained in (1) or (2). (5) The ethylene compound is a method of refining tetrafluoromethane of (1) or (2), which is at least one compound selected from the group consisting of ethylene, fluoroethylene, difluoroethylene, and tetrafluoroethylene. (6) The method for refining the tetrafluoromethane contained in (5), wherein the ethylene compounds are ethylene and / or tetrafluoroethylene. (7) The hydrocarbon-based compound is a method for purifying the tetrafluoromethane contained in (1) or (2), which is at least one compound selected from the group consisting of methane, ethane, and propane. (8) The method for purifying the tetrafluoromethane contained in (7), wherein the hydrocarbon-based compound is methane and / or ethane. (9) The method for refining tetrafluoromethane contained in (1) or (2), which reduces the total content of ethylene compounds, hydrocarbon compounds, carbon monoxide and carbon dioxide contained in tetrafluoromethane to 3 p pm or less. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (10). Tetrafluoromethane institutes containing impure substances such as ethylene compounds, hydrocarbon-based compounds, carbon monoxide and / or carbon dioxide are directly fluorinated by reacting trifluoromethane institutes with fluorine Then, the tetrafluoromethane refining method described in (1) or (2) is used to manufacture tetrafluoromethane. (1 1) Tetrafluoromethane containing impure substances such as ethylene compounds, hydrocarbon-based compounds, carbon monoxide and / or carbon dioxide is produced by the direct fluorination method after the reaction of carbon with fluorine gas, which (1) or (2) The dimensions of this paper are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -6-· 583177 A7 ____ B7 _____ V. Refining method of tetrafluoromethane according to the invention description (4). (Please read the precautions on the back before filling in this page) (1 2) Those purified by any of the methods (1) ~ (1 1) to obtain a purity of 9 9 · 9 9 9 7 mass% or more Tetrafluoromethane products are featured. (1 3) The etching gas contained in the product of (1 2) containing a tetrafluoromethane product. (1 4) The cleaning gas contained in the product of (1 2) containing tetrafluoromethane. That is, the present invention is "to make FC-14 containing impure ethylene compounds, hydrocarbon groups, carbon monoxide, and / or carbon dioxide by an average pore diameter of 3 · 4 A ~ 1 1 person, S i / A 1 ratio A method for refining tetrafluoromethane which is a special kind of zeolite and / or a carbonaceous sorbent with an average pore diameter of 3,4 to 1 and 1 to reduce the impurities to 1,5 or less "," The method was refined to obtain a tetrafluoromethane product characterized by a purity of 99.9997% by mass or more "and" an etching gas and a cleaning gas containing the tetrafluoromethane product ". Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Forms of Invention Implementation] As a method of FC-14 manufacturing methods such as known methods for reacting trifluoromethane with fluorine gas, methods for reacting carbon with fluorine gas, or Methods and other examples of thermal decomposition of tetrafluoroethylene. When using these methods, in the obtained FC-14, the impurities in the raw materials such as organic trace impurities, trace oxygen, trace moisture, etc., impurities such as ethylene compounds, hydrocarbon compounds, carbon monoxide and / Or carbon dioxide. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 583177 A7 _____B7 V. Description of the invention (5) As vinyl compounds, it contains at least one selected from ethylene (Η 2 二 C c Η 2) Compounds of monofluoroethylene (CH2 = CHF), difluoroethylene (c Η 2 = CF 2), and tetrafluoroethylene (CF2 = CF2). As hydrocarbon-based compounds, they contain at least one member selected from methane (C C 4), compounds of ethane (C 2 Η 6), propane (C 3 8). Table 1 represents the boiling points of the target F C-1 4 and these impurities at atmospheric pressure. [Table 1] Compound name Chemical formula Boiling point (° c) Carbon monoxide CO -191.5 Methane ch4 -161.5 FC-1 4 cf4 -128 Ethylene ch2 = ch2 -103.7 Ethane CH3CH3 -89 Difluoroethylene ch2 = cf2 -83 Carbon dioxide C2 -78.5 Tetrafluoroethylene cf2 = cf2 -76.3 Monofluoroethylene ch2 = chf -72 propane CH3CH2CH3 -42.1 FC-1 of the target substance and these impure substances form azeotrope-like mixtures, or it can be determined from Table 1 that the boiling point, For reasons such as distillation, this paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm) _ g-(Please read the precautions on the back before filling this page) Printed 583177 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (6) is a substance that is not easy to separate. Therefore, in the ordinary distillation operation, in order to reduce the impurities as much as possible, it is intended to take measures such as increasing the number of distillation columns and increasing the number of distillation columns. However, this economic aspect is not ideal, and it is extremely difficult to produce such impurities The purity of the round FC-1. In the present invention, in order to selectively remove such impurities in FC-14, zeolites having an average pore diameter of 3 · 4 A to 1 1 A and / or zeolites having an average pore diameter of 3 · 4 A to 1 1 A Carbonaceous adsorbent (molecular sieve carbon =) is used as the adsorbent. As a method for measuring the average pore diameter, for example, a gas adsorption method using Ar gas is used. As a more ideal adsorbent, (1) zeolite with an average pore diameter of 3 · 4 ~ 1 1 person, S i / A 1 ratio of 1.5 or less, (2) average pore diameter of 3 · 4 A ~ 1 1 A carbonaceous adsorbent (molecular sieve carbon), (3) average pore diameter of zeolite with an average pore diameter of 3 · 4 A ~ 1 1 A, S i / A 1 or less is 1.5 3.4 A ~ 1 1 A carbonaceous adsorbent. Here, the S i / A 1 ratio represents an atomic ratio. As the impurities in FC-14 which can be removed by using these adsorbents, specific examples include unsaturated compounds such as ethylene, monofluoroethylene, difluoroethylene, and tetrafluoroethylene, and hydrocarbon-based compounds such as : Examples of methane, ethane, and propane. Examples of the oxygen-containing compound include carbon monoxide and carbon dioxide. These impurities are preferably ethylene, tetrafluoroethylene, methane, ethane, carbon monoxide or carbon dioxide, and more preferably ethylene or ethane. The FC-1 4 of the target substance has a very small molecular diameter difference with these impurities. It is extremely difficult to selectively remove FC — 1 4 by the difference in molecular diameter (please read the precautions on the back before filling this page) 4 • Item refilling · binding-order it This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ g _ 583177 A7 B7 V. Description of the invention (7) Pure materials. Therefore, after considering the polarity, pore size, etc. of the adsorbent according to the present invention, the following three adsorbents can be used as adsorbents that can selectively remove the impurities. The first adsorbent has a zeolite having an average pore diameter of 3 · 4 A to 1 1 A, and a zeolite having a Si / Al ratio of 1.5 or less is preferred. Specific example: For example, MS-4A, MS-4A is an average pore diameter of about 3.5A, and the ratio of Si / A1 is 1.0. The adsorption operation using this zeolite can reduce the content of ethylene, tetrafluoroethylene, methane, ethane, carbon monoxide and carbon dioxide containing impurities. Depending on the type of zeolite, the impurity content can be reduced to 5 p P m or less, and high purity F C -1 4 can be obtained. When the average pore diameter is less than 3 · 4 A, even if the S i / A 1 ratio is 1 · 5 or less, zeolite with a pore size of about 3 · 2 A does not appear to reduce the impurity content. If the ratio of S i / A 1 is 1.5 or less, the content of impurities is not reduced even if the zeolite with an average pore diameter larger than 1 1 A. In addition, even if the average pore diameter is 3 · 4 A to 1 1 A, the zeolite with a Si / A 1 ratio of 1 · 5 or more does not reduce the impurity content. The second adsorbent has an average pore diameter of 3 · 4 A ~ 1 1 A carbonaceous adsorbent (molecular sieve carbon). For example, a carbonaceous adsorbent having an average pore diameter of about 4 A is the same as the zeolite, which can reduce the content of the impurities to 5 p pm or less, and obtain a high-purity F C-14. However, there was no drop in carbonaceous adsorbents with an average pore diameter greater than 1 1 A—. R ^ ----- ^ Batch of clothes-(Please read the precautions on the back before filling this page) Order the intellectual property of the Ministry of Economic Affairs The paper size printed by the Bureau ’s Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 583177 A7 B7 V. Description of the invention (8) Low impurities, such as strong adsorption energy for general use Activated carbon with an average pore diameter of about 3 5 A shows almost no reduction in impurities. (Please read the precautions on the back before filling this page) The third adsorbent is a zeolite with an average pore diameter of 3.4 A ~ 1 1 A and a ratio of S i / A of 1.5 or less (the first adsorbent ) The carbonaceous adsorbent (second adsorbent) with an average pore diameter of 3 · 4 A to 1 1 A (mixed) is added. Depending on the type of this adsorbent, the content of impurities can be reduced to less than 3 p p m, and higher purity F C-1 4 can be obtained. This is because the zeolite has particularly good adsorption capacity for carbon monoxide, carbon dioxide, etc. In addition, the carbonaceous adsorbent especially has good adsorption capacity for unsaturated compounds, and the dual effect of mixing the two adsorbents is considered. The zeolite and the carbonaceous adsorbent may be used singly or in combination of two or more kinds in any ratio. In the case of the third adsorbent, the mixing ratio of zeolite and carbonaceous adsorbent may be changed in accordance with the concentration of impurities. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs as impure substances contained in FC-14 are not particularly limited to the concentration of ethylene compounds, hydrocarbon-based compounds, carbon monoxide and / or carbon dioxide, which is generally below 0.1% by mass It is preferably, and more preferably, 0.05 mass% or less. In addition, in the purpose of FC-14, impurities other than the above are mixed, such as perfluoride FC-116 (CF3CF3), FC-2 1 8 (C3F8), etc. Distillation in the processing step can separate and remove perfluorinated compounds. In the method for refining FC-14 of the present invention, there is no particular limitation on the method for bringing FC-14 containing impurities into contact with the adsorbent. For example, the Chinese national standard (CNS) A4 specification (210X297 mm) is applied to the paper scale of the gas phase. : "_ &Quot; 583177 A7 B7 V. Description of the invention (9) Any method of contacting, gas-liquid contacting, or liquid-phase contacting is acceptable, and the liquid-phase contacting is also possible. For the method, the efficiency is the most ideal. In the method of contacting in the liquid phase, known methods such as batch type and continuous type can be used. In the industry, for example, a fixed bed adsorption tower is provided with 2 groups. In addition, Generally, as long as the method of saturated adsorption is used to switch the regeneration method. In addition, when the FC-14 containing impurities is in contact with the adsorbent, its processing temperature, processing volume and processing pressure are not particularly limited. Generally, the processing temperature is low. It is preferably a temperature in the range of 50 ° C to 50 ° C. In addition, when the processing pressure is in the liquid phase, it is only necessary to maintain the liquid phase, and the gas phase is not particularly limited. As described above, use the present invention The purification method can effectively remove and remove the ethylene compounds, hydrocarbon compounds, carbon monoxide and / or carbon dioxide contained in FC-14, and obtain FC-14 with high purity. Moreover, the purity of FC-14 obtained is 99 · 9997 mass% or more, as the analytical method of FC-14 products with a purity of 99.99997 mass% or more can use (1) TCD method of gas chromatography (GC) method, FID method (both pre-cut method) , ECD method, (2) Gas chromatography mass spectrometer (GC-MS), etc. In addition, high-purity FC-14 can be used as an etching gas in the etching step in the manufacturing process of semiconductor devices. Use it. It can also be used as a cleaning gas in the cleaning step in the manufacturing process of semiconductor devices. LS 1. In the manufacturing process of semiconductor devices such as TFT, CVD method and sputtering are used. (CNS) A4 size (210x297 mm) (Please read the notes on the back before filling in ': write this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 583177 A7 B7 V. Description of Invention (10) Law or Steam Thin film, thick After the film, the worm is carved to form a circuit model. In the device that forms a thin film or a thick film, it is cleaned to remove unnecessary deposits that have accumulated on the inner wall of the device, molds, etc. This is to generate unnecessary deposits. The reason for the spalling is that if you want to make a good film, you must remove the unnecessary deposit at any time. Among them, the etching method using FC-14 can be performed under various dry etching conditions such as plasma etching and microwave etching, and it can also be appropriate. Mix FC-14 with inert gas such as He, N2, Ar or HC1, 02, Krypton 2 and so on. [Examples] Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the present invention is not limited to these examples. [Raw material example 1 for F C-1 4] After reacting carbon and fluorine gas in the presence of a diluent gas, after removing unreacted fluorine gas, it is purified by separate distillation by a known method! τ C-1 4 The abundantly generated gas was analyzed by gas chromatography to obtain F C-1 4 having the composition shown in Table 2. The size of this paper is applicable. National Standard (CNS) A4 (210X297 mm) J ----- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
583177 A7 B7 五、發明説明（11 ) 〔表2 Ί 化合物名 化學式 純度 皙量％ ) F c - 1 4 cf4 /|'Tj \ / U J 9 9 9 fi 8 8 一氧化碳 CO 0 0006 二氧化碳 C02 \J · \J \J \j \J 0 005 6 甲烷 ch4 0.0012 乙烯 ch2=ch2 0 0 112 四氟乙烯 cf2 = cf2 \J · \J L L 〇 002 8 乙烷 CH3CH3 0.0098 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局S工消費合作社印製 〔F C - 1 4之原料例2〕 於稀釋氣體之存在下反應二氟甲烷（CH2F2)與氣 氣後’將反應氣體導入驗洗淨塔後，去除生成之氟化氫及 少量之未反應氟氣體。以公知方法藉由分別蒸餾進行精製 F C - 1 4豐沛生成之氣體，於氣體層析法進行分析後， 取得具有表3所示組成之F C〜1 4。 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） -14 - 583177 A7 ___B7 五、發明説明（12 ) 〔表3〕 化合物名 化學式 純度（質量％ ) F C - 1 4 cf4 99.9722 一氧化碳 CO 0.0005 二氧化碳 C〇2 0.0025 甲烷 ch4 0.0004 單氟乙烯 ch2 = chf 0.0056 二氟乙烯 C H 2= C F 2 0.0038 四氟乙烯 cf2 = cf2 0.0108 三氟甲烷 chf3 0.0042 1.-------裝-- (請先閲讀背面之注意事項再填寫本頁) 訂 (實施例1 ) 於容積2 0 Om 1之不銹鋼製圓筒中塡入2 0 g之沸 石〔分子篩4 A ( union昭和股份公司製：平均細孔徑 3 · 5 A、S i / A 1比=1 )〕後，真空乾燥之後，進 行冷卻圓筒之同時，塡入約7 0 g之原料例1 F C — 經濟部智慧財產局員工消費合作社印製 1 4後，維持溫度於-2 0 t下同時隨時攪拌之，約8小 時後’於氣體層析法進行分析液相部。分析結果示於表4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15 583177 A7 B7 五 、發明説明（13 Γ 矣 /1 、 化合物名 化學式 cf4 _-- CO <〇^00〇J___ 一氧化碳 C〇2 __<〇^〇_〇〇i___ 甲烷 ch4 乙烯 ch2 = ch2 <^〇〇〇l^-- 四氟乙烯 C F 2= C F 2 __o^ooj^.—— 乙烷 CH3CH3 _〇^〇〇〇l_^- I.-------^装-- (請先閱讀背面之注意事項存填寫本頁) 經濟部智慧財產局員工消費合作社印製 由表4結果證明，以平均細孔徑爲3 · 5 A、 S i / A 1比爲1之沸石做爲吸附劑使用後，可降低F C 一 1 4中之不純物類，可使其含量爲1 〇 p pm以下者。 (實施例2 ) 於容積2 0 Om 1之不銹鋼製圓筒中塡入2 0 g之沸 石〔分子篩1 3 X ( uni no昭和股份公司製：平均細孔徑 10A，Si/Al比=1.23)〕，真空乾燥後，冷 卻圓筒之同時塡充約7 0 g之原料例1 f C— 1 4，室溫 (約1 8 °C )下隨時攪拌之同時，約8小時後，以氣體層 析法進行分析液相部。分析結果示於表5。 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ297公廣） -16- 583177 B7 五、發明説明（U ) 〔表5〕 化合物名 化學式 純度（質量％ ) F C - 1 4 cf4 99.999 1 一氧化碳 CO <0.0001 二氧化碳 C〇2 <0.0001 甲烷 ch4 <0.0001 乙烯 ch2=ch2 0.000 3 四氟乙烯 cf2=cf2 0.000 2 乙烷 CH3CH3 0.0001 (請先閲讀背面之注意事項再填寫本頁) 由表5結果證明’以平均細孔徑爲1 0 A、 S i / A 1比爲1 · 2 3之沸石做爲吸附劑使用後’可減 低F C - 1 4中之不純物類，可使其含量爲1 〇 P P m以 下者& (實施例3 ) 經濟部智慧財產局員工消費合作社印製 於容積2 0 〇m 1之不銹鋼製圓筒中塡入2 0 g之碳 質吸附劑〔分子篩碳、武田藥品工業股份公司製：平均細 孔徑4 A〕，進行真空乾燥後，冷卻圓筒之同時塡入約 7 0 g之原料例2 F C — 1 4，室溫（約1 8 °C )下隨時 攪拌，約8小時後，以氣體層析法進行分析液相部。分析 結果w於表6。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 583177 A7 B7 五、發明説明（15 ) 〔表6〕 化合物名 化學式 純度（質量％ ) F C - 1 4 cf4 99.9992 一氧化碳 CO 0.0001 二氧化碳 C02 0.0002 甲烷 ch4 0.0001 單氟乙烯 ch2 = chf <0.0001 二氟乙烯 ch2 = cf2 <0.0001 四氟乙烯 cf2 = cf2 <0.0001 二氟甲烷 chf3 0.0001 (請先閱讀背面之注意事項再填寫本頁) ί裝· 由表6結果證明，以平均細孔徑爲4 A之碳質吸附劑 〔分子篩碳〕做爲吸附劑使用後，可減低F C — 1 4 P之 不純物類，可使其含量做成1 〇 p p m以下。 (實施例4 ) 於容積2 0 Om 1之不銹鋼製圓筒中塡入1 5 g之沸 石〔分子篩4 A ( unino昭和股份公司製：平均細孔徑 3 · 5 A、S i / A 1比=1 )〕與1 5 g之碳質吸附劑 〔分子篩碳、武田藥品工業股份公司製：平均細孔徑4 A 〕混合後，真空乾燥之後，冷卻圓筒之同時，塡入約7 0 g之原料例1 F C — 1 4，室溫（約1 8 °C )下隨時攪 拌約8小時後，以氣體層析法進行分析液相部。分析結果 示於表7。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） _ j a _ 訂 經濟部智慧財產局員工消費合作社印製 583177 A7 B7 五、發明説明（16 ) 〔表7〕 化合物名 化學式 純度（質量％ ) F C — 1 4 cf4 99.9994 一氧化碳 CO <0.0001 二氧化碳 C02 <0.0001 甲烷 ch4 <0.0001 乙烯 ch2 = ch2 <0.0001 四氟乙烯 cf2 = cf2 <0.0001 乙烷 CH3CH3 <0.0001 (請先閲讀背面之注意事項再填寫本頁) 爲更求取微量不純物含量，利用做爲微量分析法之氣 體層析法之T C D法，F I D法（含預切法），E C D法 ，氣體層析法質量分析計（GC/MS )等分析器後，進 行純度之算取，結果示於表8。 經濟部智慧財產局員工消費合作社印製 〔表8〕 化合物名 化學式 純度（質量％ ) F C - 1 4 cf4 99.9998 一氧化碳 CO <0.4ppm 二氧化碳 C〇2 <0.4ppm 甲烷 ch4 <0.3ppm 乙烯 ch2 = ch2 <0.1 ppm 四氟乙烯 cf2=cf2 <0.2ppm 乙烷 CH3CH3 <0.2ppm 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 19 - 583177 A7 B7 五、發明説明（17 ) 由表8結果證明’所取得F C — 1 4之純度爲 99.9997質量％以上者。 (請先閲讀背面之注意事項再填寫本頁) (比較例1 ) 於容積2 0 〇m 1之不銹鋼製圓筒中，塡入2 0 g之 沸石〔分子篩XH - 9 ( unino昭和股份公司製：平均細孔 徑3 · 2 A、S i / A 1比=1 )〕後，進行真空乾燥後 ，冷卻圓筒之同時塡入約7 0 . g之原料例1 F C - 1 4， 室溫（約1 8 °C )下，隨時攪拌，約8小時後，以氣體層 析法進行分析液相部。分析結果不於表9。 〔表9〕 化合物名 化學式 純度（質量％ ) F C - 1 4 cf4 99.9698 一氧化碳 CO 0.0004 二氧化碳 C〇2 0.0051 甲烷 ch4 0.0012 乙烯 ch2 = ch2 0.0111 四氟乙烯 cf2 = cf2 0.0027 乙烷 CH3CH3 0.0097 經濟部智慧財產局員工消費合作社印製 由表9結果證明，S i / A 1比即使爲1 ’其平均細 孔徑爲3 · 4 A以下之沸石仍無法降低不純物類。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） _ 2〇 - 583177 A7 B7 五、發明説明（18 ) (比較例2 ) (請先閱讀背面之注意事項再填寫本頁) 於容積2 ◦ 〇 m 1之不銹鋼製圓筒中，塡入2 〇 g之 沸石〔H— ZSM — 5(Ν·Ε — Chemceat 股份公司製： 平均細孔徑6 A、S i / A 1比=7 5 )〕，真空乾燥後 ，冷卻圓筒之同時塡入約7 〇 g之原料例1 F C — 1 4， 室溫下（約1 8 °C )隨時攪拌約1 8小時後，以氣體層析 法進行分析液相部。分析結果不於表1 0。 〔表 1 0〕 化合物名 化學式 純度（質量％ ) F C - 1 4 cf4 99.9733 一氧化碳 CO 0.0003 二氧化碳 C〇2 0.0047 甲烷 ch4 0.0009 乙烯 ch2 = ch2 0.0098 四氟乙儲 cf2 = cf2 0.0021 乙烷 CH3CH3 0.0089 經濟部智慧財產局員工消費合作社印製 由表1 0結果證明，即使平均細孔徑爲6 A， S i / A 1比大於1 . 5之沸石仍無法降低不純物類。 (比較例3 ) 於容積2 0 Om 1之不銹鋼製圓筒中，塡入2 〇 g之 碳質吸附劑〔活性碳：粒狀自s a g i K L ’武田藥品 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） _ 21 - 583177 A7 B7 五、發明説明（19 ) 工業股份公司製’平均細孔徑3 5 A〕，進行真空乾燥後 ，冷卻圓筒之同時塡入7 0g之原料例2fc— 14，安 溫（約1 8 °C)下’隨時攪拌’約8小時後，以氣體層析 法進行分析液相部。分析結果如表1 i所$。 〔表 1 1〕 化合物名 化學式 純度（質量％ ) F C - 1 4 cf4 99.9795 一氧化碳 CO 0.0004 二氧化碳 C〇2 0.0021 甲烷 ch4 0.0003 單氟乙烯 ch2 = chf 0.0038 二氟乙烯 ch2 = cf2 0.0026 四氟化乙烯 cf2 = cf2 0.0079 三氟化甲烷 chf3 0.0034 由表1 1結果證明，平均細孔徑大於1 1 A之碳質吸 附劑，無法降低不純物類。 〔發明效果〕 根據本發明，藉由平均細孔徑爲3 · 4 A〜1 1 A、 S i / A 1比爲1 . 5以下之沸石及/或平均細孔徑爲 3 · 4A〜1 1A、之碳質吸附劑接觸先行極困難之四氟 甲烷中不純物，特別含乙烯化合物類、烴基化合物類、一 (請先閲讀背面之注意事 1· 項再填. 裝-- :寫本頁)583177 A7 B7 V. Description of the invention (11) [Table 2 Ί Chemical formula of compound name Purity%) F c-1 4 cf4 / | 'Tj \ / UJ 9 9 9 fi 8 8 Carbon monoxide CO 0 0006 Carbon dioxide C02 \ J · \ J \ J \ j \ J 0 005 6 Methane ch4 0.0012 Ethylene ch2 = ch2 0 0 112 Tetrafluoroethylene cf2 = cf2 \ J · \ JLL 〇002 8 Ethane CH3CH3 0.0098 (Please read the precautions on the back before filling in this Page) Printed by the Industrial and Commercial Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [FC-1 4 Raw Material Example 2] After reacting difluoromethane (CH2F2) and gas in the presence of diluent gas, the reaction gas is introduced into the inspection and cleaning tower Remove the generated hydrogen fluoride and a small amount of unreacted fluorine gas. F C-1 4 was abundantly purified by a known method by separate distillation, and after gas chromatography analysis, F C-14 having a composition shown in Table 3 was obtained. This paper size applies to Chinese National Standard (CNS) A4 (210x297 mm) -14-583177 A7 ___B7 V. Description of the invention (12) [Table 3] Chemical formula purity of compound name (mass%) FC-1 4 cf4 99.9722 Carbon monoxide CO 0.0005 Carbon dioxide CO2 0.0025 Methane ch4 0.0004 Monofluoroethylene ch2 = chf 0.0056 Difluoroethylene CH 2 = CF 2 0.0038 Tetrafluoroethylene cf2 = cf2 0.0108 Trifluoromethane chf3 0.0042 1 .------- install-- (- Please read the precautions on the back before filling in this page.) Order (Example 1) Put 20 g of zeolite in a stainless steel cylinder with a volume of 20 Om 1 [Molecular sieve 4 A (manufactured by Union Showa Corporation: average pore size) 3 · 5 A, S i / A 1 ratio = 1)], after vacuum drying, while cooling the cylinder, inject about 70 g of raw material Example 1 FC — printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs After 14 hours, maintain the temperature at -20 t while stirring at any time, and after about 8 hours, analyze the liquid phase by gas chromatography. The analysis results are shown in Table 4. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -15 583177 A7 B7 5. Description of the invention (13 Γ 矣 / 1, compound name chemical formula cf4 _-- CO < 〇 ^ 00〇J ___ carbon monoxide C〇2 __ < 〇 ^ 〇_〇〇i ___ methane ch4 ethylene ch2 = ch2 < ^ 〇〇〇l ^-tetrafluoroethylene CF 2 = CF 2 __o ^ ooj ^ .-- ethane CH3CH3 _〇 ^ 〇〇〇〇l _ ^-I .------- ^ install-- (Please read the precautions on the back and fill in this page) Printed by Table 4 It was proved that the use of zeolite with an average pore size of 3.5 A and S i / A 1 as an adsorbent can reduce the impurities in FC-14 and its content can be less than 10 pm (Example 2) 20 g of zeolite [molecular sieve 1 3 X (made by Uni no Showa Corporation: average pore diameter 10A, Si / Al ratio = 1.23) was poured into a stainless steel cylinder having a volume of 20 Om 1. ] After vacuum drying, the cylinder is filled with about 70 g of raw material example 1 f C-14, while stirring at any time at room temperature (about 18 ° C), about 8 hours Then, the liquid phase was analyzed by gas chromatography. The analysis results are shown in Table 5. The paper size is in accordance with Chinese National Standard (CNS) A4 (21〇297297) -16- 583177 B7 V. Description of the invention (U ) [Table 5] Compound name Chemical formula purity (mass%) FC-1 4 cf4 99.999 1 carbon monoxide CO < 0.0001 carbon dioxide C〇2 < 0.0001 methane ch4 < 0.0001 ethylene ch2 = ch2 0.000 3 tetrafluoroethylene cf2 = cf2 0.000 2 Ethane CH3CH3 0.0001 (Please read the precautions on the back before filling out this page) The results in Table 5 prove that 'the zeolite with an average pore diameter of 10 A and S i / A 1 ratio of 1. 2 3 was used as the adsorbent After use 'can reduce impurities in FC-14, and its content can be less than 10 pp m & (Example 3) Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed on the volume of 20,000 m 1 20 g of carbonaceous adsorbent [molecular sieve carbon, manufactured by Takeda Pharmaceutical Industry Co., Ltd .: average pore size 4 A] was poured into a stainless steel cylinder. After vacuum drying, about 70 g of raw material was poured while cooling the cylinder. Example 2 FC — 1 4, room temperature (about 1 Stir at any time at 8 ° C). After about 8 hours, analyze the liquid phase by gas chromatography. The analysis results are shown in Table 6. This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 583177 A7 B7 V. Description of the invention (15) [Table 6] Compound name Chemical formula Purity (mass%) FC-1 4 cf4 99.9992 Carbon monoxide CO 0.0001 Carbon dioxide C02 0.0002 Methane ch4 0.0001 Monofluoroethylene ch2 = chf < 0.0001 Difluoroethylene ch2 = cf2 < 0.0001 Tetrafluoroethylene cf2 = cf2 < 0.0001 Difluoromethane chf3 0.0001 (Please read the precautions on the back before filling this page)装 Installation · It is proved from the results in Table 6 that using carbonaceous adsorbent [molecular sieve carbon] with an average pore size of 4 A as the adsorbent can reduce the impurities of FC — 1 4 P, and the content can be made into 1 〇ppm or less. (Example 4) 15 g of zeolite [molecular sieve 4 A (manufactured by Unino Showa Corporation: average pore diameter 3 · 5 A, S i / A 1 ratio = 1) was poured into a stainless steel cylinder having a volume of 20 Om 1 )] After mixing with 15 g of carbonaceous adsorbent [Molecular sieve carbon, Takeda Pharmaceutical Industry Co., Ltd .: average pore size 4 A] After vacuum drying, after cooling the cylinder, inject about 70 g of raw material example 1 FC—14. After stirring at room temperature (about 18 ° C) for about 8 hours at any time, the liquid phase was analyzed by gas chromatography. The analysis results are shown in Table 7. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ ja _ Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives 583177 A7 B7 V. Description of the invention (16) [Table 7] Chemical formula of the compound name Purity (mass%) FC — 1 4 cf4 99.9994 carbon monoxide CO < 0.0001 carbon dioxide C02 < 0.0001 methane ch4 < 0.0001 ethylene ch2 = ch2 < 0.0001 tetrafluoroethylene cf2 = cf2 < 0.0001 ethane CH3CH3 < 0.0001 (please (Please read the notes on the back before filling this page.) To obtain the trace impurity content, the TCD method, FID method (including precut method), ECD method, and gas chromatography method are used as the gas chromatography method for micro analysis. The purity is calculated after an analyzer such as a mass analyzer (GC / MS), and the results are shown in Table 8. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 8] Compound name Chemical formula Purity (mass%) FC-1 4 cf4 99.9998 Carbon monoxide CO < 0.4ppm Carbon dioxide C02 < 0.4ppm Methane ch4 < 0.3ppm Ethylene ch2 = ch2 < 0.1 ppm tetrafluoroethylene cf2 = cf2 < 0.2ppm ethane CH3CH3 < 0.2ppm This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) _ 19-583177 A7 B7 V. Description of the invention (17) It is proved from the results in Table 8 that the obtained FC-14 has a purity of 99.9997% by mass or more. (Please read the precautions on the back before filling in this page) (Comparative Example 1) In a stainless steel cylinder with a volume of 200 m 1, 20 g of zeolite [molecular sieve XH-9 (made by Unino Showa Corporation: Average pore diameter 3 · 2 A, S i / A 1 ratio = 1)], and then vacuum-dried, while cooling the cylinder, pour about 7 0. G of raw material example 1 FC-1 4, room temperature (about 18 ° C), stirring at any time, and after about 8 hours, the liquid phase was analyzed by gas chromatography. The analysis results are not shown in Table 9. [Table 9] Compound name Chemical formula purity (mass%) FC-1 4 cf4 99.9698 carbon monoxide CO 0.0004 carbon dioxide C〇2 0.0051 methane ch4 0.0012 ethylene ch2 = ch2 0.0111 tetrafluoroethylene cf2 = cf2 0.0027 ethane CH3CH3 0.0097 intellectual property bureau of the Ministry of Economic Affairs Printed by employee consumer cooperatives. The results in Table 9 prove that even if the S i / A 1 ratio is 1 ', zeolites with an average pore size of 3 · 4 A or less still cannot reduce impurities. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ 20- 583177 A7 B7 V. Description of the invention (18) (Comparative Example 2) (Please read the precautions on the back before filling this page ) In a stainless steel cylinder with a volume of 2 ◦ 0 m, 20 g of zeolite [H — ZSM — 5 (N · E — Chemceat Co., Ltd.): average pore diameter 6 A, S i / A 1 ratio = 7 5)], after vacuum drying, about 70 g of raw material example 1 FC-14 was poured while cooling the cylinder, and stirred at room temperature (about 18 ° C) for about 18 hours at any time, followed by a gas layer Analytical method was performed to analyze the liquid phase. The analysis results are not in Table 10. [Table 1 0] Compound name Chemical formula purity (mass%) FC-1 4 cf4 99.9733 carbon monoxide CO 0.0003 carbon dioxide C〇2 0.0047 methane ch4 0.0009 ethylene ch2 = ch2 0.0098 tetrafluoroethane storage cf2 = cf2 0.0021 ethane CH3CH3 0.0089 wisdom of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Property Bureau, the results from Table 10 prove that even with an average pore size of 6 A, zeolites with S i / A 1 ratio greater than 1.5 still cannot reduce impurities. (Comparative example 3) In a stainless steel cylinder with a volume of 20 Om 1, 200 g of a carbonaceous adsorbent [activated carbon: granular from sagi KL 'Takeda Pharmaceutical Co., Ltd.] This paper applies the Chinese national standard (CNS) A4 Specifications (210 X 297 mm) _ 21-583177 A7 B7 V. Description of the invention (19) Industrial company's average pore size 3 5 A] After vacuum drying, 70 g of raw materials are poured while cooling the cylinder. Example 2fc-14, after stirring at room temperature (about 18 ° C) for about 8 hours, the liquid phase was analyzed by gas chromatography. The analysis results are shown in Table 1i. [Table 1 1] Compound name Chemical formula purity (mass%) FC-1 4 cf4 99.9795 carbon monoxide CO 0.0004 carbon dioxide C〇2 0.0021 methane ch4 0.0003 monofluoroethylene ch2 = chf 0.0038 difluoroethylene ch2 = cf2 0.0026 ethylene tetrafluoride cf2 = cf2 0.0079 Methane trifluoride chf3 0.0034 The results in Table 1 1 show that carbonaceous adsorbents with an average pore size greater than 1 1 A cannot reduce impurities. [Effects of the Invention] According to the present invention, a zeolite having an average pore size of 3.4 A to 1 A, and a ratio S i / A 1 of 1.5 or less, and / or an average pore diameter of 3.4 A to 11 A, The carbonaceous adsorbent is extremely difficult to contact with impurities in tetrafluoromethane, especially ethylene compounds, hydrocarbon-based compounds, and one (please read the notes on the back 1 and then fill in. Fill-: write this page)
1T 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22 - 583177 A7 B7 五、發明説明（20 ) 氧化碳及/或二氧化碳之四氟甲烷後，可降低該不純物。 且，被精製之高純度四氟甲烷可做爲鈾刻氣體或洗淨氣體 使用之。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 23 -1T Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standards (CNS) A4 (210X297 mm) -22-583177 A7 B7 V. Description of the invention (20) Carbon oxide and / or carbon dioxide tetrafluoro After methane, this impurity can be reduced. In addition, the purified high-purity tetrafluoromethane can be used as a uranium etching gas or a cleaning gas. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 23-