1242545 A7 _ __________ 五、發明説明（1) 技術領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關八氟化丙烷之製造方法，八氟化丙烷產 品及其用途。 先行技術 八氟化丙烷係用作例如半導體裝置製程中之乾式鈾刻 氣體，洗淨氣體等。其製造方法已知有， (1 )將六氟丙烯以氟氣直接氟化反應之方法（日本 專利特公昭6 2 — 6 1 5 7 2號公報） (2 )六氟丙烯於氟化氫中電解氟化之方法（特公昭 6 2 — 6 1 1 1 5號公報） (3 )六氟丙烯與氟於觸媒存在下反應之方法（特公 平1 一 45455號公報） (4 )以六氟丙烯與高級金屬氟化物反應之方法（特 公昭62—54777號公報） 等。 經濟部智慧財產局員工消費合作社印製 然而，這些方法中，四氟甲烷（CF4)，六氟乙烷（ C 2 F 6 )等副產物之經裂解產生，經自由基加成產生 C 6 F i 2，c 6 F i 4等，或環化加成產生四員環等，均使 目標八氟化丙烷之收率及選擇率下降。而且這些雜質中， 有難以藉蒸餾分離之化合物，隨之有難以製得高純度八氟 化丙烷之問題。尤以用六氟丙烯爲起始原料時，所含雜質 氯五氟乙烷（CFC - 1 1 5 )幾乎不與氟氣反應，混在 目標之八氟化丙烷中，因沸點接近難藉蒸餾分離，難以製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -4- 1242545 A7 B7 五、發明説明（2) 取高純度八氟化丙烷。 發明所欲解決之課題 (請先閱讀背面之注意事項再填寫本頁) 本發明即在此一背景下完成，係以提供用於半導體裝 置之製程的八氟化丙院之製造方法，高純度八氟化丙烷及 其用途爲本發明之課題。 用以解決課題之手段 本發明人等’對上述課題之解決精心探討，結果發現 若用包括（1 )於氟化觸媒存在下，以六氟丙烯與氟化氫 於氣相1 5 0至4 5 0 °C反應，得2H -七氟丙烷之步驟 ’及（2)無觸媒下使步驟（1 )所得之2H -七氟丙烷 於氣相2 5 0至5 0 0 °C反應得八氟化丙烷之步驟之製造 方法’即可製得筒純度八氟^化丙院，而完成本發明。 經濟部智慧財產局員工消費合作社印製 亦即，本發明（I )係其特徵爲··包括（1 )於氟化 觸媒存在下，以六氟丙烯與氟化氫於氣相1 5 0至4 5 0 t反應，得2H -七氟丙烷之步驟，及（2 )無觸媒下使 步驟（1 )所得之2H -七氟丙烷於氣相2 5 0至5 0 0 °C反應得八氟化丙烷之步驟的製造方法，本發明（I )中 ，六氟丙烯係以含至少1種選自二氯二氟曱烷，氯二氟甲 烷，氯五氟乙烷，氯四氟乙烷及氯三氟乙烯所成群之化合 物，步驟（1 )中，氟化觸媒係以鉻氧化物爲主要成分， 添加選自銦，鋅及鎳所成群之至少1種之块狀觸媒，而氟 化氫/六氟丙烯之莫耳比在0·8至3之範圍爲較佳實施 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1242545 A7 B7 五、發明説明（3) 形態。 (請先閲讀背面之注意事項再填寫本頁) 又’本發明（I )係以步驟（2 )之前，包含去除2 Η -七氟丙院所含雜質之步驟，該雜質係至少1種選自四 氟甲烷，三氟甲烷，氯三氟甲烷，六氟乙烷及五氟乙烷所 成群之化合物’該雜質去除步驟係蒸餾步驟，且2 η -七 氟丙烷中所含氯化合物在〇.〇1體積％以下爲較佳實施 形態。 又，本發明（I )係以步驟（2 )是於稀釋氣體存在 下進行，該稀釋氣體係選自氟化氫，四氟甲烷，六氟乙院 及八氟化丙烷所成群之至少1種，步驟（2 )中，氟氣/ 2Η-七氟丙烷之莫耳比在〇·9至1.5之範圍，反應 器入口 2 Η -七氟丙烷濃度在8莫耳％以下爲較佳實施形 態。 經濟部智慧財產局員工消費合作社印製 並且，本發明（〗）係以包含將步驟（2 )之出口氣 體的至少一部份循環再使用作步驟（2 )之稀釋氣體，及 使步驟（2 )之出口氣體的至少一部份與氫氟碳類反應， 以去除出口氣體中所含未反應氟氣之步驟，該氫氟碳類係 至少1種選自三氟甲烷，四氟乙烷，五氟乙烷，2Η 一七 氟丙烷所成群之化合物，將含於步驟（2 )之出口氣體的 氟化氫分離，將分離出之氟化氫送返步驟（1 )及/或步 驟（2)，從已分離出氟化氫之氣體分離出至少一部份之 八氟化丙烷，其餘氣體送返步驟（1 )及/或步驟（2) 爲較佳實施形態。 本發明（I I )係，其特徵爲：純度9 9 . 9 9 5體 本^張尺度適用中國國家標準（〇呢）八4規格（210乂297公釐） -6 - 1242545 Α7 Β7 五、發明説明（4) 積％以上之八氟化丙烷產品，係以分子內含氯原子之化合 物及运狀化合物總星在5 0體積p p m以下爲較佳實施形 肯皂〇 又，本發明（I I I )係其特徵爲：含上述八氟化丙 烷產品之蝕刻氣體，而本發明（I V )係其特徵爲：含上 述氟化丙烷產品之洗淨氣體。 發明之實施形態 以下詳細說明本發明。 本發明（I )所用之六氟丙烯（C F 3 C F二C F 2 ) ，係例如以氯二氟甲烷（C H C 1 F 2 )之熱裂解製造四氟 乙烯（C F 2二C F 2 )之製程中的副產物，或如特開平4 - 1 4 5 0 3 3號公報所記載，以丙烷，丙烯或部份鹵化 之C 3非環狀烴類之氯氟化脫鹵化方法等製得。然而，這 些方法所得之六氟丙烯，大多混有二氯二氟甲院，氯二氟 甲烷，氯五氟乙烷，氯四氟乙烷，氯三氟乙烯等分子內含 氯原子之化合物之雜質。本發明係在提供，即使含這些雜 質之六氟丙烯亦可用作起始原料的八氟化丙烷之製造方法 ，在此，將中間體2 Η -七氟丙烷，目標產物八氟化丙烷 及各雜質之沸點示於表1。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） r— (請先閱讀背面之注意事項再填寫本頁)1242545 A7 _ __________ 5. Description of the invention (1) Technical field (please read the precautions on the back before filling out this page) The present invention relates to the production method of octafluoropropane, octafluoropropane products and their uses. Prior art Propane octafluoride is used as, for example, dry uranium engraving gas and cleaning gas in semiconductor device manufacturing processes. The manufacturing method is known as (1) a method for directly fluorinating hexafluoropropylene with fluorine gas (Japanese Patent Publication No. 6 2-6 1 5 7 2) (2) electrolysis of fluorine in hexafluoropropylene in hydrogen fluoride Method for chemical conversion (Japanese Patent Publication No. 6 2-6 6 1 1 1 5) (3) Method for reacting hexafluoropropylene with fluorine in the presence of a catalyst (Japanese Patent Publication No. 4545) (4) hexafluoropropylene and Methods for the reaction of advanced metal fluorides (Japanese Patent Publication No. 62-54777). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, in these methods, tetrafluoromethane (CF4), hexafluoroethane (C 2 F 6) and other by-products are produced by cracking, and C 6 F is produced by addition of free radicals. i 2, c 6 F i 4 or the like, or cyclization addition to produce a four-membered ring, etc., all reduce the yield and selectivity of the target propane octafluoride. In addition, among these impurities, there is a problem that it is difficult to separate the compounds by distillation, and consequently, it is difficult to obtain high-purity octafluoropropane. Especially when using hexafluoropropene as the starting material, the impurity chloropentafluoroethane (CFC-1 15) hardly reacts with fluorine gas, and is mixed in the target propane octafluorofluoride. It is difficult to separate by distillation due to the boiling point. It is difficult to make this paper. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) -4- 1242545 A7 B7 5. Description of the invention (2) Take high-purity propane octafluoride. The problem to be solved by the invention (please read the precautions on the back before filling out this page) The present invention is completed under this background, which is to provide a method for manufacturing propylene fluoride octafluoride for semiconductor device manufacturing process with high purity Propane octafluoride and its use are the subject of the present invention. Means for Solving the Problem The present inventors and others' carefully discussed the solution to the above-mentioned problems, and found that if the use of (1) in the presence of a fluorinated catalyst includes hexafluoropropylene and hydrogen fluoride in the gas phase 1 50 to 4 5 0 ° C reaction to obtain 2H-heptafluoropropane 'and (2) the step of reacting the 2H-heptafluoropropane obtained in step (1) in a gas phase at 250 to 500 ° C without a catalyst The manufacturing method 'can be used to obtain the tube purity octafluorofluoride, and complete the present invention. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, that is, the present invention (I) is characterized by including: (1) in the presence of a fluorinated catalyst, hexafluoropropylene and hydrogen fluoride in the gas phase 1 50 to 4 50 t reaction to obtain 2H-heptafluoropropane, and (2) the step of reacting the 2H-heptafluoropropane obtained in step (1) in a gas phase at 250 to 500 ° C without catalyst In the manufacturing method of the present invention (I), the hexafluoropropylene is based on a compound containing at least one selected from the group consisting of dichlorodifluoromethane, chlorodifluoromethane, chloropentafluoroethane, chlorotetrafluoroethane and chlorotrifluoroethylene. In the group of compounds, in step (1), the fluorinated catalyst is based on chromium oxide, and at least one kind of block catalyst selected from the group consisting of indium, zinc, and nickel is added, and hydrogen fluoride / six The molar ratio of fluoropropylene is in the range of 0.8 to 3, which is better to implement. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1242545 A7 B7. 5. Description of the invention (3) Form. (Please read the precautions on the back before filling in this page.) Also, the invention (I) is the step of removing the impurities contained in 2Η-Heptafluoropropane before step (2). This impurity is at least one kind of choice. Compounds grouped from tetrafluoromethane, trifluoromethane, chlorotrifluoromethane, hexafluoroethane and pentafluoroethane. The impurity removal step is a distillation step, and the chlorine compounds contained in 2η-heptafluoropropane are in the range of 0.1%. 0.001% by volume or less is a preferred embodiment. In addition, the present invention (I) is carried out in the step (2) in the presence of a diluent gas, the diluent gas system being selected from at least one of the group consisting of hydrogen fluoride, tetrafluoromethane, hexafluoroethane, and octafluoropropane. In step (2), the molar ratio of fluorine gas to 2Η-sevofluoropropane is in the range of 0.9 to 1.5, and the concentration of 2Η-sevofluoropropane at the inlet of the reactor is 8 mol% or less is a preferred embodiment. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and the present invention () is to reuse at least part of the outlet gas of step (2) as the diluent gas of step (2), and make step (2) A step of reacting at least a part of the outlet gas with HFCs to remove unreacted fluorine gas contained in the outlet gas, the HFCs are at least one selected from trifluoromethane, tetrafluoroethane, Pentafluoroethane, a compound of 2Η heptafluoropropane, separates the hydrogen fluoride contained in the outlet gas of step (2), and returns the separated hydrogen fluoride to step (1) and / or step (2). The hydrogen fluoride-producing gas separates at least a portion of the propane octafluoride, and the remaining gas is returned to step (1) and / or step (2) as a preferred embodiment. The present invention (II) is characterized in that the purity is 99.9.95. The size of the original sheet is applicable to the Chinese national standard (0?) 8 4 specifications (210 乂 297 mm) -6-1242545 Α7 Β7 V. Invention Explanation (4) The propane fluorofluoride product with a volume of more than 100% is based on compounds containing chlorine atoms and transport compounds in the molecule. The total amount of stars is less than 50 vol. Ppm. Also, the present invention (III) It is characterized by: an etching gas containing the above-mentioned octafluoropropane product, and the present invention (IV) is characterized by: a cleaning gas containing the above-mentioned fluorinated propane product. Embodiments of the Invention The present invention will be described in detail below. The hexafluoropropylene (CF 3 CF di CF 2) used in the present invention (I) is, for example, a process for producing tetrafluoroethylene (CF 2 di CF 2) by thermal cracking of chlorodifluoromethane (CHC 1 F 2). By-products, or chlorofluorinated dehalogenation methods such as propane, propylene, or partially halogenated C 3 acyclic hydrocarbons, as described in Japanese Patent Application Laid-Open No. 4-1 4 5 0 3, etc. However, most of the hexafluoropropylene obtained by these methods are mixed with dichlorodifluoromethane, chlorodifluoromethane, chloropentafluoroethane, chlorotetrafluoroethane, and chlorotrifluoroethylene. Impurities. The present invention provides a method for producing hexafluoropropane which can be used as a starting material even with hexafluoropropene containing these impurities. Here, intermediate 2 Η-heptafluoropropane, the target product propane fluorofluoride, and various impurities are provided. The boiling points are shown in Table 1. This paper size applies to Chinese National Standard (CNS) Α4 size (210X297 mm) r— (Please read the precautions on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製 1242545 Α7 Β7 五、發明説明（5) 表1 化合物名稱 結構式 沸點 氯二氟甲烷 CHC1F2 -4 1 °C 氯五氟乙烷 CF3CCIF2 ~ 3 9 . 3 °C 八氟化丙烷 CF3CF2CF3 - 3 6 · 7 t： 二氯二氟甲院 CCI2F2 -2 9 . 2 °C 六氟丙烯 CF3CF = CF2 -2 9 °C 氯三氟乙烯 cf2=ccif -2 7 . 9 °C 2 Η -七氟丙烷 CF.3 CHFCF3 -1 5 . 2 °C 氯四氟乙烷 CF3CHCIF -1 2 t： (請先閱讀背面之注意事項再填寫本頁) 如由表1所示之沸點可知，起始原料六氟丙烯中所含 ，分子內有氯原子之化合物，其沸點接近八氟化丙院之沸 點，難以僅藉蒸餾分離。 爲此，本發明（I )八氟化丙烷之製造方法，係先進 行於氟化觸媒存在下，以六氟丙烯與氟化氫於氣相1 5 〇 至4 5 0 °C反應，製得2 Η -七氟丙烷之步驟（i )。步 驟（1 )有以下二個要點。即， 經濟部智慧財產局員工消費合作社印製 〔1〕 使六氟丙烯以氟氣直接氟化反應時，或於觸媒， 高級金屬氟化物等之存在下，與氟氣直接氟化反應時，經 碳-碳鍵之斷裂反應，自由基加成反應，環化加成反應等 產生種種副產物。因此，不僅收率，選擇率低，高純度八 氟化丙烷之取得也困難。本發明則係在觸媒存在下，於六 氟丙烯以氟化氫加成，可得收率，選擇率佳之中間體2 Η -七氟丙烷，可藉其反應抑制副產物之產生。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -8- 1242545 A7 B7 五、發明説明（6) (請先閲讀背面之注意事項再填寫本頁) 〔2〕 如上述’六氮丙烯大多含分子內有氯原子之化合 物雑貝，迫些化合物難以藉蒸餾分離。本發明係以氟化氫 加成於/、氟丙烯，得中間體2 H 一七氟丙烷的反應之同時 ’以氯化氨將分子內含氯原子之化合物氟化，可轉化爲易 於蒸餾分離之化合物。 於六氯丙烯以氟化氫加成之反應，係於氟化觸媒之存 在下，依下式（1 )進行。 CF3CF = CF2 + HF->CF3CHFCF3 (1) 氟化觸媒可用通常使用之鉻系觸媒。六氟丙烯含氯系 雜質’將該氯系雜質氟化成其它化合物時，因反應溫度較 高，活性（性能），安定性（壽命）優之觸媒，係以主要 成分爲鉻之氧化物，添加銦，鋅及鎳之至少1種的块狀觸 媒爲佳。載持型觸媒（例如氧化鋁載體）亦可，唯基於活 性，安定性仍以块狀觸媒爲佳。這些觸媒用於反應以前， 可藉氟化氫作氟化處理進行活化，再使用於反應。 步驟（1 )中，雖隨六氟丙烯中雜質之種類，含量而 異，反應溫度係在1 5 0至4 5 CTC之範圍，以2 0 0至 經濟部智慧財產局員工消費合作社印製 3 50 °C爲較佳。六氟丙烯中含雜質CFC - 1 1 5時， 反應溫度宜在3 5〇至4 5〇°C之範圍，以3 5 ◦至 4 0 0 /C爲較佳。反應溫度在4 5 0 °C以上時，觸媒安定 性趨於下降而不佳。若在1 5 0 °C以下則目標反應之轉化 率低，雜質化合物之氟化反應慢，亦不佳。 又，氟化氫與六氟丙烯（F C - 1 2 1 6)之莫耳比 (HF/FC — 1216)以在 〇 . 8 至 3 . 0 爲佳， 本紙張尺度適用中國國家標準㈤奶:^料見格⑺^撕公瘦） -9 - 1242545 A7 B7 五、發明説明（7) 1 . 0至2 _ 0爲更佳。氟化氫與六氟丙烯之莫耳比在 (請先閲讀背面之注意事項再填寫本頁) 〇· 8以下時，六氟丙烯之轉化率低，在3 . 0以上時有 未反應H F之回收設備等成本需求而不佳。 如上述，原料六氟丙烯中可含雜質，分子內有氯原子 之化合物，這些雜質通常難以藉蒸餾分離。分子內含氯原 子之化合物有氯二氟甲烷，氯五氟乙烷，二氯二氟甲烷， 氯三氟乙烯，氯四氟乙烷等。本發明（I )係於氟化觸媒 存在下，以主要反應六氟丙烯與氟化氫反應得2 Η -七氟 丙烷之步驟，將這些含氯化合物轉換爲易於蒸餾分離之其 它含氟化合物。 例如’可經下式（2 )至（5 )之反應，將氯化合物 轉化爲其它含氟化合物。 CHC1 F2 + HF-> C Η F a + Η C 1 (2) CF2=CC 1 F+HF^CFaCHC 1 F ( 3 ) CF3CHC 1 F+HF~^CF3CHF2 + HC 1 (4) CF3CC 1 F2 + HF->CF3CF3 + HC 1 (5) 經濟部智慧財產局員工消費合作社印製 迫些經赢化之化合物及中間體2 H -七氟丙院之沸點 示於表2。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -10- 1242545 Α7 Β7 五、發明説明（8) 表2 化 入 σ 物 名 稱 結構式 沸點 四 氟 甲 院 CF4 -1 2 8 °C 三 氟 甲 烷 CHF3 -8 4 _ 4 °C 氯 三 氟 甲 焼 CC1F3 一 8 1 • 4 °c Γ . /、 氟 乙 烷 CF3CF3 一 7 8 1 °c 五 氟 乙 院 CFsCHFi -4 8 • 5 °c 2 Η — 七 氟丙烷 CF3CHFCF3 -1 5 _ 2 °c (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 如由表2可知，中間體2 Η -七氟丙烷與經上述反應 氟化之化合物其沸點之差大幅加大，可輕易以蒸餾分離。 其次，得自步驟（1)，主要成分爲2Η -七氟丙烷 之氣體’係導入將氟化氫及未反應之氟化氫分離之脫酸步 驟。氟化氫及氟化氫再以蒸餾分離，以鹼水溶液作氯化氫 之中和處理。又，氟化氫可送回六氟丙烯之氟化步驟，亦 可用鹼水溶液作中和處理。於脫酸步驟分離氯化氫及氟化 氫後，以2 Η -七氟丙烷爲主要成分之氣體接著進行步驟 (2)，但以之前先導入蒸餾塔，去除2Η-七氟丙烷中 所含雜質爲佳。 含於2 Η -七氟丙烷之雜質，有四氟甲烷，三氟曱烷 ，氯三氟甲烷，六氟丙烯，五氟乙烷等，這些雜質係以藉 蒸I留去除爲佳。於熬餾塔，有低沸分四氟甲院，三氟甲院 ，氯三氟甲烷，六氟乙烷，五氟乙烷由塔頂取出，2Η-七氟丙烷由塔底取出。以2 Η -七氟丙烷爲主要成分之氣 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公餐） -11 - 1242545 A7 B7 五、發明説明（9) 體可用作以氟氣直接氟化反應之原料，但無論脫酸步驟是 否蒸餾，2 Η -七氟丙烷中所含之氯化合物雜質之在 (請先閲讀背面之注意事項再填寫本頁) 0 · 01體積％以下爲佳，0 . 005體積％以下爲更佳 0 其次說明步驟（2 )。 步驟（2 )係將得自上述步驟（1 )之氟化步驟的 2 Η -七氟丙烷與氟氣在無觸媒下，於氣相反應溫度 2 5 0至5 0 0°C反應，得八氟化丙烷之直接氟化反應步 驟，有以下三要點。即，〔1〕以氫氟碳化物與氟氣反應 製造全氟碳化物時，伴隨有非常大之反應熱。反應熱與每 分子所反應之氟的莫耳數成正比，氟量愈多反應熱愈大， 易起碳-碳鍵之斷裂，聚合，環化加成，甚至有時會爆炸 ，收率降低而成爲工業製造，操作上之問題。因此，抑制 直接氟化法中激烈產生反應熱之方法，有以其它惰性氣體 (例如氮，氯等）將氟稀釋之方法，及利用基質有機物稀 釋之方法。氮，氦等惰性氣體，從以蒸餾與目標物全氟碳 化物分離’純化等及成本考量，並非有利方法，本發明（ 經濟部智慧財產局員工消費合作社印製 1 )因用選自氟化氫，四氟甲院，六氟乙院，八氟化丙院 之至少1種作爲稀釋氣體，可以解決上述問題。 〔2〕 本發明（I )係將反應基質2H -七氟丙烷之反 應器入口濃度以稀釋氣體調爲爆炸範圍以下進行反應，具 體言之係在8莫耳％以下進行反應。如上述使用氟氣之直 接氟化反應，因用反應性極高之氟氣，基質有機化合物（ 尤以含氫之化合物）有因氟氣更具燃燒或爆炸之危險性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 1242545 A7 ____B7 五、發明説明（ (請先閲讀背面之注意事項再填寫本頁) 步驟（2 )中因用含氫原子之2 Η -七氟丙烷作爲基質， 防止2 Η -七氟丙烷與氟氣之爆炸成爲要點。爲防爆炸， 混合氣體組成須在爆炸範圍外，本發明人等對2 η -七氟 丙烷及氟氣之爆炸範圍加以探討得知，2 Η -七氟丙烷之 爆炸範圍下限値係在8莫耳％以下，可將2 Η -七氟丙烷 之反應器入口濃度設定於安全範圍內。 〔3〕 以2Η -七氟丙烷與氟氣反應之直接氟化反應， 雖相對於氟氣使用過量之2 Η -七氟丙烷，而不需去除氟 氣之步驟，然而卻爲其後之分離純化帶來極大困難。本發 明（I )之步驟（2 )，爲提高反應效率可相對於2 Η -七氟丙烷使用過量莫耳之氟氣，使用過量莫耳之氟氣時， 由反應步驟流出之反應產物氣體主要含全氟碳化物，及氟 化氫以外的過量氟氣。剩餘氟氣之處理方法，已知有以氧 化鋁，鹼石灰等無機氧化物反應之方法，該方法因反應中 產生水，成爲裝置材料之腐蝕等之原因而不佳。本發明（ I )係，對於過量之氟氣，以化學當量比1 . 1倍莫耳之 氫氟碳化物接觸，即可去除過剩之氟氣。 經濟部智慧財產局員工消費合作社印製 2 Η -七氟丙烷與氟氣反應之直接氟化反應，係依下 式（6 )進行。 CF3CHFCF3+F2— CF3CF2CF3 + HF (6) 該反應可用觸媒，但無觸媒亦可進行。又，如上述， 氫氟碳化物與氟氣反應之直接氟化反應其反應熱大，而以 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13- 1242545 A7 B7 五、發明説明（1) 在稀釋氣體存在下進行反應爲佳。稀釋氣體可用選自氟化 氫，四氟甲院，六氟乙烷，八氟化丙烷之至少1種，以氟 (請先閲讀背面之注意事項再填寫本頁) 化氫及/或八氟化丙烷爲較佳，以用富含氟化氫之氣體爲 更佳。 稀釋氣體之導入方法，係在將2 Η -七氟丙烷及氟氣 導入反應器以前，其任一或二者先以稀釋氣體稀釋後導入 反應器。基質2 Η -七氟丙烷之反應器入口濃度以在爆炸 範圍以下之8莫耳％以下爲佳，6 %以下爲更佳。氟氣的 反應器入口濃度，係以氟氣/2 Η -七氟丙烷莫耳比在 〇 _ 9至1 · 5之範圍的濃度爲佳，〇 . 9至1 . 2之範 圍爲更佳。氟氣/2 Η -七氟丙烷莫耳比在〇 · 9以下時 之氟氣濃度，因2Η-七氟丙烷之轉化率低，而1.5以 上時須負擔未反應氟氣之去除成本，故均不佳。又，氟氣 /2Η-七氟丙烷之莫耳比在1·5以上時，將步驟（2 )之出口氣體循環再使用作步驟（2 )之稀釋氣體時，循 環氣體（稀釋氣體）中氟濃度變高，會有爆炸等問題而不 佳。 經濟部智慧財產局員工消費合作社印製 以稀釋氣體稀釋成爲爆炸範圍以下之濃度的2 Η -七 氟丙烷及氟氣可於氣相反應。反應溫度可在2 5 0至 50CTC，以35〇至45CTC爲佳。反應溫度在25〇 °C以下時反應慢，在5 0 0 °C以上時目標物八氟化丙烷之 碳-碳鍵有斷裂之傾向而不佳。 該步驟（2 )之出口氣體主要係氟化氫，八氟丙烷， 本發明（I )可將該出口氣體之至少一部份循環，再使用 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） -14- 1242545 A7 __B7 五、發明説明（Θ (請先閲讀背面之注意事項再填寫本頁) 作爲步驟（2 )之稀釋氣體。而出口氣體中，因有時含未 反應之氟氣，檢測未反應氟氣濃度之方法，可用將出口氣 體一部份連續導入連續流動之含金屬碘化物之溶液，生成 碘，測定該溶液在特定波長範圍之可見光穿透度以連續定 量生成之碘，算出未反應氟氣濃度之方法。又，檢測氟化 合物以求出反應率之方法，可用以紅外分光法測定混合氣 體中所含之全赢化物’氣氧碳化物，赢化氣濃度之方法 ，而能作工業上安全條件下的連續操作。 經濟部智慧財產局員工消費合作社印製 又，步驟（2 )之出口氣體，除循環再使用作稀釋氣 體以外，含未反應氟氣時，係以例如取出與所供給之2 Η -七氟丙烷大約等量的反應出口氣體，導入去除未反應氟 氣之步驟，’與對過剩氟氣之化學當量比1 . 1倍莫耳之氫 氟碳化物接觸，去除氟氣爲佳。氟氣去除步驟之接觸溫度 隨氫氟碳化物之種類而異，但較佳者在2 5 0至5 0 0 °C ，更佳者在3 5 0至4 5 Ot。氟氣去除步驟後之出口氣 體中氟之濃度通常在5 0 p p m以下，依條件可爲1〇 p p m以下。與過剩氟氣反應之氫氟碳化物，可用三氟甲 烷，四氟乙烷，五氟乙烷，2H -七氟丙烷。 步驟（2 )之出口氣體除一部份循環再使用作步驟（ 2 )之稀釋氣體外，有氟氣殘留時經氟去除步驟後導入分 餾步驟。氣體之主要成分係氟化氫及八氟化丙烷。於分餾 步驟以冷卻分離出氟化氫液體，及主要爲八氟化丙烷之氣 體。經分離之氟化氫送返氟化步驟（1 )及/或直接氟化 步驟（2 )，可循再利用。分離出之氣體，主要含八氟化 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）~' ~ -15- 1242545 A7 B7 五、發明説明（ 丙院，經脫水步驟，以壓縮機升壓導入蒸衝塔。 r— (請先閱讀背面之注意事項再填寫本頁) 導入蒸餾塔，主要含八氟化丙烷之氣體，於例如第一 蒸餾塔以低沸分自塔頂取出。低沸分乃係惰性氣體，四氟 甲烷，六氟乙烷等，可利用作直接氟化步驟（2)之稀釋 氣體。另一方面，由底部取出之以八氟化丙院爲主要成分 之氣體則導入第二蒸餾塔，八氟化丙烷係以低沸分由第二 蒸餾塔之塔頂取出，導入產品步驟。由第二蒸餾塔底部取 出之高沸分，可以送返步驟（Z)用作稀釋氣體，而依情 況用除害劑等加以分解處理亦可。 經濟部智慧財產局員工消費合作社印製 導入產品步驟之目標物八氟化丙烷，必要時予以純化 ，依情況或經脫水步驟導入產品桶。導入產品桶之八氟化 丙烷可用（1)氣相層析法（GC)之TCD法，F ID 法及E C D法，（2 )氣相層析一質譜儀（G C - M S ) 等分析方法求出純度。本發明（I I )係用本發明（I ) 之製造方法所得，純度9 9 _ 9 9 5體積％以上之高純度 八氟化丙烷，其所含雜質分子由含氯原子之化合物及環狀 化合物，總量在5 0體積p p m以下，亦可將該雜質總量 降到1 0體積P P m以下。 其次說明本發明（I I I )及（I V )，用本發明（ I )之製造方法所得高純度八氟化丙烷之用途。 本發明（I I )之高純度八氟化丙烷，可用作半導體 裝置製程中鈾刻步驟的鈾刻氣體。又，亦用作半導體裝置 製程中洗淨步驟之洗淨氣體。L I S，T F T等半導體裝 置之製程中，係用C V D法，濺鍍法或蒸鍍法形成薄膜， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 1242545 A7 B7 五、發明説明（你 表3 化合物名稱 化學式 組成（V 0 1 % ) 六氟丙烯 CF3CF = CF2 99.9685 四氟乙烯 CF2 = CF2 0.0033 氯三氟乙烯 CF2 = CC1F 0.0008 二氯四氟乙院 CF3CC12F 0.0011 氯五氟乙院 CF3CC1F2 0.0192 五氟乙烷 CF3CHF2 0.0028 氯三氟乙院 CF3CH2C1 0.0004 氯二氟甲院 CHC1F2 0.0039 (請先閲讀背面之注意事項再填寫本頁) 〔原料例2〕 市售六氟丙烯加以分析，具表4之組成。 經濟部智慧財產局員工消費合作社印製 表4 化合物名稱 化學式 組成（V 0 1 % ) 六氟丙烯 CF3CF = CF2 99.9196 四氟乙烯 CF2 = CF2 0.0008 氯三氟乙烯 cf2=ccif 0.0004 氯五氟乙院 CF3CC1F2 0.00414 二氯二氟甲院 CC12F2 0.0248 氯二氟曱院 CHC1F2 0.0069 氯二氟乙烷 CF2 = CHC1 0.0042 四氟乙院 CF3CH2F 0.0019 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐） -18- 1242545 A7 B7 五、發明説明（1$ [氟化觸媒之製造] (請先閲讀背面之注意事項再填寫本頁) 內有純水0 · 6公升之1 0公升容器，以4 5 2公克 之Cr (Ν〇3)3·9Η2〇及42公克之 I η ( Ν〇3 ) 3 · η Η 2〇（η約爲5 )溶解於1 · 2公 升純水之溶液，及0 . 3 1公升之2 8 %氨水，一面攪拌 一面*保持反應液之pH於7.5至8.5之範圍內，以 約1小時滴入。過濾所得氫氧化物之漿液，以純水詳加洗 淨後，於1 2 0 t經1 2小時乾燥。將所得固體粉碎後與 石墨混合’以打旋成形器粒料化。在氮氣流下，將該粒料 於4 0 0 °C煅燒4小時，得觸媒前驅物。將觸媒前驅物充 塡於Inconel製之反應器，於常壓3 5 〇。(：，在氮稀釋之 H F氣流下，再於1 〇 〇 % H F氣流下進行氟化處理（觸 媒之活化處理），調製觸媒。 (實施例1 ) 經濟部智慧財產局員工消費合作社印製 以上述〔氟化觸媒之製造〕之方法調製之觸媒1 〇〇 毫升，充塡於內徑1英吋，長1米之Inconel 600反應器，一 面通熱热一*面日13溫爲4 0 0 C。以6 · 3 2標準公升/小 時供給氟化氫，其次以3 · 2 4標準公升/小時供給〔原 料例1〕之六氟丙烯爲主要成分之氣體。停止氮氣之供給 開始反應。2小時後，排氣以氫氧化鈉水溶液洗淨去除酸 分後’以氣相層析法分析氣體組成，得表5之組成。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19- 1242545 A7 B7 五、發明説明（1> 表5 化合物名稱 化學式 組成（v 0 1 % ) 2 Η -七氟丙院 CF3CHFCF3 99.9611 三氟甲烷 CHF3 0.0053 六氟乙焼 CF3CF3 0.0192 五氟乙院 CF3CHF2 0.0071 八氟化丙烷 CF3CF2CF3 0.0004 六氟丙烯 CF3CF = CF2 0.0052 氯五氟乙烷 CF3CCIF2 0.0008 四氟乙烷 CF3CH2F 0.0008 氯三氟乙烷 CF3CH2CI 0.0001 (請先閱讀背面之注意事項再填寫本頁) 酸分去除後之氣體用筒狀容器冷卻捕集，以習知方法 蒸餾純化分爲低沸分及高沸分。蒸餾純化後之組成物以氣 相層析法分析，得表6之組成。 經濟部智慧財產局員工消費合作社印製 表6 化合物名稱 化學式 組成（v 0 1 % ) 2 Η -七氟丙烷 CF3CHFCF3 99.9965 五氟乙烷 CF3CHF2 0.0003 八氟化丙焼 CF3CF2CF3 0.0001 六氟丙烯 CF3CF = CF2 0.0019 氯五氟乙烷 CF3CC1F2 0.0007 四氟乙烷 CF3CH2F 0.0005 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -20 - 1242545 Α7 Β7 五、發明説明（ 由表6之結果可知，2 Η -七氯丙院中所含雑質氯化合 物，藉蒸餾可減至0 . 〇 1體積％以下。 (實施例2 ) 用實施例1所得之蒸餾後以2 Η -七氟丙烷爲主要成 分之氣體，與氟氣進行直接氟化反應。 內徑2 0 . 6毫米0，長5 0 0毫米之鎳製反應器（ 電熱器加熱：反應器係以氟氣於溫度5 0 0 °C施行鈍態化 處理）以2 0標準公升/小時供給氮氣，一面升溫至 4 0 0 〇C。 其次，以氟化氫（稀釋氣體）於6 0標準公升/小時 分二支供給，於其一以3 · 2 4標準公升/小時供給上述 2 Η -七氟丙院爲主要成分之氣體。之後於另一氟化氫氣 流以3 . 5 5標準公升/小時供給氟氣，停止氮氣之供給 進行直接氟化反應。3小時後，用氫氧化鈉水溶液及碘化 鉀水溶液洗淨反應產生之氣體，分析氟化氫及未反應氟氣 ，其次於這些酸分去除後以氣相層析法分析，得有機物氣 體組成如表7。 (請先閲讀背面之注意事項再填寫本頁) 衣· 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） '21 - 1242545 B7 五、發明説明（1令 表7 化合物名稱 化學式 組成（v 0 1 % ) 八氟化丙烷 CF3CF2CF3 99.1042 四氟甲烷 CF4 0.0011 六氟乙烷 CF3CF3 0.0017 2 Η -七氟丙烷 CFsCHFCFs 0.8762 氯五氟乙烷 CF3CC1F2 0.0006 全氟己院 C6Fl4 0.0162 (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 另一方面，反應出□氣體中未反應氟氣量爲〇 · 2 6 標準公升/小時。 酸分去除後之氣體以筒狀容器冷卻捕集，用已知方法 進行蒸餾純化分出低沸分及高沸分。蒸餾純化後所得之組 成物以氣相層析法分析，得表8之組成。 表8 化合物名稱 化學式 組成（ν ο 1 % ) 八氟化丙院 CF3CF2CF3 99.9992 2 Η -七氟丙院 CF3CHFCF3 0.0002 氯五氟乙烷 CF3CCIF2 0.0006 由表8之結果可知，所得八氟化丙烷之純度在 9 9 . 9 9 9體積％以上。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -22- 1242545 A7 B7 五、發明説明（20 C實施例3 ) (請先閲讀背面之注意事項再填寫本頁) 將實施例2所得之含未反應氟氣的直接氟化反應之出 口氣體，導入內徑20 · 6毫米0 ’長500毫米之鎳製 反應器。氣體組成爲氟化氫6 2 . 8 2標準公升/小時’ 有機物3 . 1 6標準公升/小時’未反應氟氣約〇 . 2 6 標準公升/小時，將反應器升溫至3 9 0 °C，從反應器入 口部，以約0 . 2 8 6標準公升/小時供給氫氟碳化物三 氟甲烷，未反應氟及有機物組成物各以滴定及氣相層析法 分析。與三氟甲烷反應後的出口氣體中之未反應氟氣量在 5 0 ρ p m以下，該氣體組成如表9所不。 表9 化合物名稱 化學式 組成（v 0 1 % ) 八氟化丙烷 CF3CF2CF3 91.6849 四氟曱烷 CF4 5.2707 三氟甲烷 CHF3 3.0232 六氟乙烷 CF3CF3 0.0028 2 Η -七氟丙烷 CF3CHFCF3 0.0029 氯五氟乙烷 CF3CCIF2 0.0006 全氟己烷 CeF 14 0.0149 經濟部智慧財產局員工消費合作社印製 其次，殘餘氟氣已去除之出口氣體用氫氧化鉀水溶液 洗淨，去除氟化氫。酸分去除後之氣體用筒狀容器冷卻捕 集，用已知方法進行蒸餾純化分出低沸分及高沸分。蒸餾 純化後之氣體以氣相層析法分析，得表1 0之組成。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23 - 1242545 A7 B7 五、發明説明（2) 表1 0 丄匕合物名稱 化學式 組成（ν 〇 1 % ) 八氟化丙烷 CF3CF2CF3 99.9993 2 Η -七氟丙烷 CF3CHFCF3 0.0001 氯五氟乙烷 CF3CCIF2 0.0006 (比較例1 ) 以六氟丙烯與氟氣反應進行直接氟化反應。內徑 2 0 . 6毫米0，長5 0 0毫米之鎳製反應器（電熱器加 熱：反應器以氟氣於5 0 0 °C施行鈍態化處理）以氮氣 6〇標準公升/小時分二支供給，一面§周溫爲5 〇 〇。 於一氮氣流以3 . 2 4標準公升/小時供給〔原料例1 ] 之以六氟丙烯爲主要成分之氣體，其次於另一氮氣流以 3 . 5 5標準公升/小時供給氟氣，進行直接氟化反應。 2小時後，反應產生之氣體用氫氧化鉀水溶液及碘化鉀水 溶液洗淨，去除未反應氟氣，以氣相層析法分析，氣體組 成如表1 1所示。 (請先閱讀背面之注意事項再填寫本頁) 、11Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 122545 A7 B7 V. Description of the invention (5) Table 1 Compound name Structural formula Boiling point chlorodifluoromethane CHC1F2 -4 1 ° C Chloropentafluoroethane CF3CCIF2 ~ 3 9 .3 ° C Propane octafluoride CF3CF2CF3-3 6 · 7 t: Dichlorodifluoromethane CCI2F2 -2 9. 2 ° C hexafluoropropylene CF3CF = CF2 -2 9 ° C chlorotrifluoroethylene cf2 = ccif -2 7. 9 ° C 2 Η-Heptafluoropropane CF.3 CHFCF3 -1 5. 2 ° C Chlorotetrafluoroethane CF3CHCIF -1 2 t: (Please read the precautions on the back before filling this page) The boiling points shown in Table 1 It can be seen that the compounds contained in the starting material hexafluoropropylene and having a chlorine atom in the molecule have a boiling point close to the boiling point of the propylene fluoride octafluoride compound, which is difficult to separate by distillation alone. To this end, the method for producing (I) propane octafluoride according to the present invention is carried out by reacting hexafluoropropylene with hydrogen fluoride in the gas phase at 150 ° to 450 ° C in the presence of a fluorination catalyst to obtain 2 Η-Step (i) of heptafluoropropane. Step (1) has the following two points. That is, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [1] When hexafluoropropylene is directly fluorinated with fluorine gas, or when it is directly fluorinated with fluorine gas in the presence of catalysts, advanced metal fluorides, etc. Through the carbon-carbon bond cleavage reaction, free radical addition reaction, cyclization addition reaction, etc., various by-products are generated. Therefore, not only the yield but the selectivity is low, it is difficult to obtain high-purity propane octafluoride. The present invention is based on the addition of hydrogen fluoride to hexafluoropropene in the presence of a catalyst, and the intermediate 2Η-heptafluoropropane with good yield and selectivity can be used to suppress the production of by-products by its reaction. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -8- 1242545 A7 B7 V. Description of invention (6) (Please read the precautions on the back before filling this page) 〔2〕 Nitrogen and propylene mostly contain compounds such as scallops with chlorine atoms in the molecule, which makes it difficult to separate these compounds by distillation. In the present invention, hydrogen fluoride is added to / and fluoropropene to obtain the intermediate 2H-heptafluoropropane. At the same time, the compound containing chlorine atom in the molecule is fluorinated with ammonia chloride, which can be converted into a compound that can be easily separated by distillation. The reaction of hexachloropropene with hydrogen fluoride is carried out in the presence of a fluorinated catalyst in accordance with the following formula (1). CF3CF = CF2 + HF- > CF3CHFCF3 (1) The fluorinated catalyst can be a commonly used chromium catalyst. Hexafluoropropene containing chlorine-based impurities' When this chlorine-based impurity is fluorinated to other compounds, the catalyst with high reaction temperature, high activity (performance) and stability (lifetime) is an oxide whose main component is chromium. A bulk catalyst containing at least one of indium, zinc and nickel is preferred. Supported catalysts (such as alumina carriers) are also acceptable, but block catalysts are still preferred for stability based on activity. Before these catalysts are used in the reaction, they can be activated by hydrogen fluoride as a fluorination treatment and then used in the reaction. In step (1), although it varies with the type and content of impurities in hexafluoropropylene, the reaction temperature is in the range of 150 to 4 5 CTC, and it is printed from 2000 to the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 3 50 ° C is better. When hexafluoropropylene contains CFC-1 115 as an impurity, the reaction temperature should be in the range of 350 to 450 ° C, and more preferably 35 to 400 / C. When the reaction temperature is above 450 ° C, the stability of the catalyst tends to decrease and is not good. If it is below 150 ° C, the conversion rate of the target reaction is low, and the fluorination reaction of the impurity compound is slow and not good. In addition, the molar ratio (HF / FC-1216) of hydrogen fluoride and hexafluoropropylene (FC-12 16) is preferably from 0.8 to 3.0. This paper applies Chinese national standards. (See Grid ^ Tear male thin) -9-1242545 A7 B7 V. Description of the invention (7) 1.0 to 2 _ 0 is better. The molar ratio of hydrogen fluoride and hexafluoropropylene is (please read the precautions on the back before filling this page). 〇8 or lower, the conversion rate of hexafluoropropylene is low, and there is a recovery equipment for unreacted HF above 3.0. Waiting for cost demand is not good. As mentioned above, the raw material hexafluoropropylene may contain impurities, and compounds having a chlorine atom in the molecule. These impurities are usually difficult to separate by distillation. The compounds containing chlorine atoms in the molecule include chlorodifluoromethane, chloropentafluoroethane, dichlorodifluoromethane, chlorotrifluoroethylene, chlorotetrafluoroethane and the like. In the present invention (I), in the presence of a fluorination catalyst, these chlorine-containing compounds are converted into other fluorine-containing compounds that are easily distilled and separated by a step of mainly reacting hexafluoropropene with hydrogen fluoride to obtain 2Η-heptafluoropropane. For example, 'can convert a chlorine compound into another fluorine-containing compound by a reaction of the following formulae (2) to (5). CHC1 F2 + HF- > C Η F a + Η C 1 (2) CF2 = CC 1 F + HF ^ CFaCHC 1 F (3) CF3CHC 1 F + HF ~ ^ CF3CHF2 + HC 1 (4) CF3CC 1 F2 + HF- > CF3CF3 + HC 1 (5) The boiling points of the compounds and intermediates 2 H-Heptafluoropropane Institute printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs are shown in Table 2. This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -10- 1242545 Α7 Β7 V. Description of invention (8) Table 2 Chemical name σ Structure name Boiling point Tetrafluoromethane institute CF4 -1 2 8 ° C trifluoromethane CHF3 -8 4 _ 4 ° C chlorotrifluoromethane CC1F3-8 1 • 4 ° c Γ. /, Fluoroethane CF3CF3-7 8 1 ° c pentafluoroethane CFsCHFi -4 8 • 5 ° c 2 Η — Heptafluoropropane CF3CHFCF3 -1 5 _ 2 ° c (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, as shown in Table 2, Intermediate 2 Η-Heptafluoropropane and The difference in boiling point of the compound fluorinated by the above reaction is greatly increased, and it can be easily separated by distillation. Next, from step (1), a gas' containing 2Η-heptafluoropropane as its main component is a deacidification step in which hydrogen fluoride is separated from unreacted hydrogen fluoride. Hydrogen fluoride and hydrogen fluoride are separated by distillation and neutralized with an alkaline aqueous solution as hydrogen chloride. In addition, hydrogen fluoride can be returned to the fluorination step of hexafluoropropylene, and an alkaline aqueous solution can also be used for neutralization treatment. After the separation of hydrogen chloride and hydrogen fluoride in the deacidification step, the gas containing 2 Η-heptafluoropropane as the main component is followed by step (2), but it is better to introduce the distillation column to remove impurities contained in 2 Η-heptafluoropropane. Impurities contained in 2 七-heptafluoropropane include tetrafluoromethane, trifluoromethane, chlorotrifluoromethane, hexafluoropropylene, pentafluoroethane, etc. These impurities are preferably removed by distillation. In the distillation column, there are low-boiling tetrafluoromethane institute, trifluoromethane institute, chlorotrifluoromethane, hexafluoroethane, and pentafluoroethane are taken out from the top of the tower, and 2Η-heptafluoropropane is taken out from the bottom of the tower. Gas containing 2 Η-heptafluoropropane as the main component. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 meals) -11-1242545 A7 B7 5. Description of the invention (9) The body can be used for direct fluorination with fluorine gas The raw materials for the reaction, but no matter whether the deacidification step is distilled or not, the impurities of chlorinated compounds in 2 七-heptafluoropropane are present (please read the precautions on the back before filling this page) 0 · 01% by volume is preferred, 0.005 It is more preferably 0% by volume or less. Next, the step (2) will be described. Step (2) is the reaction of 2 七 -heptafluoropropane obtained from the fluorination step of the above step (1) with fluorine gas without a catalyst at a gas-phase reaction temperature of 250 to 500 ° C to obtain octafluoro The direct fluorination reaction step of propane has the following three points. That is, [1] When a perfluorocarbon is produced by reacting a hydrofluorocarbon with a fluorine gas, a very large heat of reaction is accompanied. The heat of reaction is directly proportional to the mole number of fluorine reacted per molecule. The more the amount of fluorine, the larger the heat of reaction, which is likely to cause carbon-carbon bond cleavage, polymerization, cyclization addition, and sometimes even an explosion, and the yield decreases. It becomes a problem in industrial manufacturing and operation. Therefore, methods for suppressing the intense generation of reaction heat in the direct fluorination method include a method of diluting fluorine with other inert gases (such as nitrogen, chlorine, etc.), and a method of diluting the organic matter using a matrix. Nitrogen, helium, and other inert gases are separated from the target perfluorocarbons by distillation, purification, and cost considerations. This is not an advantageous method. The present invention (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs1) is selected from hydrogen fluoride. At least one of the four fluorine hospitals, six fluorine B hospitals, and eight fluorine C hospitals can be used as diluent gases to solve the above problems. [2] In the present invention (I), the reaction is carried out by adjusting the concentration of the reactor inlet of the reaction matrix 2H-sevofluropropane with the diluent gas below the explosion range, specifically, the reaction is performed at 8 mol% or less. As mentioned above, the direct fluorination reaction using fluorine gas, because the highly reactive fluorine gas is used, the matrix organic compounds (especially hydrogen-containing compounds) have the danger of burning or exploding because of the fluorine gas. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 1242545 A7 ____B7 V. Description of the invention ((Please read the precautions on the back before filling this page) Step 2 contains hydrogen. Atomium 2Η-Heptafluoropropane is used as a substrate to prevent the explosion of 2Η-Heptafluoropropane and fluorine gas. In order to prevent the explosion, the composition of the mixed gas must be outside the explosion range. It is learned that the lower limit of the explosion range of 22-sevofluropropane is below 8 mol%, and the reactor inlet concentration of 2Η-sevofluoropropane can be set within a safe range. [3] 2〕 -sevofluropropane reacts with fluorine gas The direct fluorination reaction, although using 2 Η-heptafluoropropane in excess of fluorine gas, does not require a step of removing fluorine gas, but it brings great difficulties for subsequent separation and purification. Step (2) of the present invention (I) ), In order to improve the reaction efficiency, compared with 2 七-heptafluoropropane, an excessive mole of fluorine gas is used, and when an excessive mole of fluorine gas is used, the reaction product gas flowing out of the reaction step mainly contains perfluoro Carbides and excess fluorine gas other than hydrogen fluoride. The method of treating the remaining fluorine gas is known as a method of reacting with inorganic oxides such as alumina, soda lime, etc. This method causes corrosion of device materials due to water generated during the reaction. The reason is not good. In the present invention (I), the excess fluorine gas can be removed by contacting the hydrofluorocarbon with a chemical equivalent ratio of 1.1 times mole. The excess fluorine gas can be removed. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs The direct fluorination reaction of 2 反应 -Heptafluoropropane with fluorine gas printed by the cooperative is carried out according to the following formula (6): CF3CHFCF3 + F2— CF3CF2CF3 + HF (6) This reaction can be performed with a catalyst, but it can also be performed without a catalyst. Also, as mentioned above, the direct fluorination reaction of the reaction of hydrofluorocarbons with fluorine gas has a large reaction heat, and the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied to this paper scale -13-1242545 A7 B7 V. Description of the invention (1) It is better to carry out the reaction in the presence of a diluent gas. The diluent gas can be at least one selected from the group consisting of hydrogen fluoride, tetrafluoromethane, hexafluoroethane, and octafluoropropane, and fluorine (please read the note on the back first) Refill This page) Hydrogen hydride and / or propane fluorofluoride are more preferred, and hydrogen fluoride-rich gas is more preferred. The method for introducing diluent gas is to introduce 2 Η-heptafluoropropane and fluorine gas into the reactor. One or both of them are first diluted with a diluent gas and then introduced into the reactor. The concentration of the reactor inlet of the substrate 2 Η-sevofluropropane is preferably 8 mol% or less below the explosion range, and more preferably 6% or less. The fluorine gas reactor The inlet concentration is based on a concentration of fluorine gas / 2 Η-heptafluoropropane mole ratio in the range of 0-9 to 1.5, and more preferably in the range of 0.9 to 1.2. The fluorine gas concentration of fluorine gas at 2 Η-heptafluoropropane mole ratio below 0.9 is not good because the conversion rate of 2 七-heptafluoropropane is low, and the removal cost of unreacted fluorine gas is borne by 1.5 or more, which is not good. When the molar ratio of fluorine gas / 2Η-sevofluropropane is 1.5 or more, when the outlet gas in step (2) is recycled and used as the dilution gas in step (2), the fluorine concentration in the circulating gas (diluent gas) changes. High, there will be problems such as explosion. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 2Η-Heptafluoropropane and fluorine gas diluted with diluent gas to a concentration below the explosion range can react in the gas phase. The reaction temperature may be from 250 to 50 CTC, and preferably from 35 to 45 CTC. When the reaction temperature is below 25 ° C, the reaction is slow, and above 500 ° C, the target carbon-carbon bond of propane octafluorofluoride tends to be broken, which is not good. The outlet gas in this step (2) is mainly hydrogen fluoride and octafluoropropane. The present invention (I) can recycle at least a part of the outlet gas, and then use this paper size to apply the Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) -14- 1242545 A7 __B7 V. Description of the invention (Θ (please read the precautions on the back before filling out this page) as the diluent gas in step (2). And there may be some reasons for the outlet gas. The method of detecting unreacted fluorine gas containing unreacted fluorine gas can be used to continuously introduce a part of the outlet gas into a continuously flowing solution containing metal iodide to generate iodine, and measure the visible light transmittance of the solution in a specific wavelength range. The method of continuously quantifying the generated iodine to calculate the concentration of unreacted fluorine gas. In addition, the method of detecting the fluorine compound to determine the reaction rate can be determined by infrared spectrometry with all the compounds 'gas oxygen carbides' contained in the mixed gas, The method of reducing the gas concentration can be used for continuous operation under industrial safety conditions. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the outlet gas of step (2), except the circulation When it is used as a diluent gas and contains unreacted fluorine gas, it is necessary to take out a reaction outlet gas approximately equal to the supplied 2 Η-heptafluoropropane, and introduce a step of removing the unreacted fluorine gas. The equivalent ratio is 1.1 times the mole of hydrofluorocarbon to contact, and it is better to remove fluorine gas. The contact temperature of the fluorine gas removal step varies depending on the type of hydrofluorocarbon, but the preferred range is from 250 to 500. ° C, more preferably between 350 and 4 5 Ot. The concentration of fluorine in the outlet gas after the fluorine gas removal step is usually below 50 ppm, depending on the conditions, it may be below 10 ppm. Hydrogen that reacts with excess fluorine gas As the fluorocarbon, trifluoromethane, tetrafluoroethane, pentafluoroethane, and 2H-heptafluoropropane can be used. Except that a part of the outlet gas in step (2) is recycled and used as the diluent gas in step (2), there is fluorine gas. When the residue is left, it is introduced into the fractionation step after the fluorine removal step. The main components of the gas are hydrogen fluoride and propane octafluoride. In the fractionation step, the hydrogen fluoride liquid and the gas mainly composed of propane octafluoride are separated by cooling. The separated hydrogen fluoride is returned to fluorine. Step (1) and / or After the fluorination step (2), it can be reused. The separated gas mainly contains octafluoride. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) ~ '~ -15-1242545 A7 B7 5 2. Description of the invention (Cangyuan Institute, after dehydration step, the pressure of the compressor is introduced into the distillation tower. R— (Please read the precautions on the back before filling this page). Introduction of the distillation tower, which mainly contains propane octafluoride gas. For example, the first distillation column is taken out from the top of the column with a low boiling point. The low boiling point is an inert gas, tetrafluoromethane, hexafluoroethane, etc., which can be used as a diluent gas for the direct fluorination step (2). On the other hand, The gas with the main component of propylene fluoride as the main component taken out from the bottom is introduced into the second distillation column, and the propane fluorofluoride is taken out from the top of the second distillation column with a low boiling point and introduced into the product step. The high boiling point taken from the bottom of the second distillation column may be returned to step (Z) for use as a diluent gas, or may be decomposed and treated with a pesticide or the like as appropriate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Propane octafluoride, which is the target of the product introduction step, is purified if necessary, and is introduced into the product barrel according to circumstances or through the dehydration step. Propane octafluoride introduced into product barrels can be obtained by (1) gas chromatography (GC) TCD method, F ID method and ECD method, (2) gas chromatography-mass spectrometer (GC-MS) and other analytical methods. Out of purity. The present invention (II) is obtained by the production method of the present invention (I), and the purity of the high-purity propane octafluoride of 9 9 to 99 5 vol% or more, and the impurity molecules thereof include a chlorine atom-containing compound and a cyclic compound. , The total amount is 50 volume ppm or less, the total amount of impurities can also be reduced to 10 volume PP m or less. Next, the use of the present invention (I I I) and (I V) and the high-purity propane octafluoride obtained by the production method of the present invention (I) will be described. The high-purity propane octafluoride of the present invention (I I) can be used as a uranium-etching gas in a uranium-etching step in a semiconductor device manufacturing process. It is also used as a purge gas in a purge step in a semiconductor device manufacturing process. In the manufacturing process of semiconductor devices such as LIS and TFT, thin films are formed by CVD method, sputtering method or evaporation method. The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -16-1242545 A7 B7 V. Description of the invention (Your Table 3 Compound name Chemical formula Composition (V 0 1%) Hexafluoropropylene CF3CF = CF2 99.9685 Tetrafluoroethylene CF2 = CF2 0.0033 Chlorotrifluoroethylene CF2 = CC1F 0.0008 Dichlorotetrafluoroethane institute CF3CC12F 0.0011 Chloropentafluoroethyl Hospital CF3CC1F2 0.0192 Pentafluoroethane CF3CHF2 0.0028 Chlorotrifluoroethane CF3CH2C1 0.0004 Chlorodifluoromethane CHC1F2 0.0039 (Please read the precautions on the back before filling this page) [Raw material example 2] Commercially available hexafluoropropylene is analyzed and Composition of Table 4. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 4 Chemical composition of compound names (V 0 1%) Hexafluoropropylene CF3CF = CF2 99.9196 Tetrafluoroethylene CF2 = CF2 0.0008 Chlorotrifluoroethylene cf2 = ccif 0.0004 Chlorine Pentafluoromethane CF3CC1F2 0.00414 Dichlorodifluoromethane CC12F2 0.0248 Chlorodifluoromethane CHC1F2 0.0069 Chlorodifluoroethane CF2 = CHC1 0.0042 Tetrafluoro Yiyuan CF3CH2F 0.0019 This paper size applies to Chinese National Standard (CNS) A4 specification (21 OX 297 mm) -18- 1242545 A7 B7 V. Description of the invention (1 $ [Manufacture of fluorinated catalyst] (Please read the Note: Please fill in this page again.) There is a 10 litre container of 0. 6 litres of pure water, with 4 5 2 g of Cr (N〇3) 3. 9Η20 and 42 g of I η (N〇3) 3 · η Η 20 (η is about 5) dissolved in 1.2 liters of pure water, and 0.31 liters of 28% ammonia water, while stirring while maintaining the pH of the reaction solution in the range of 7.5 to 8.5, Drop in for about 1 hour. Filter the obtained hydroxide slurry, wash it with pure water, and dry it at 120 t for 12 hours. Crush the obtained solid with graphite to spin the shaper pellets The pellets were calcined under a stream of nitrogen at 400 ° C for 4 hours to obtain a catalyst precursor. The catalyst precursor was charged into a reactor made by Inconel, and the atmospheric pressure was 3 5 0. (: In a nitrogen-diluted HF gas stream, a fluorination treatment (catalyst activation treatment) was performed under a 100% HF gas stream to prepare a catalyst. (Example 1) The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 100 ml of the catalyst prepared by the above-mentioned [manufacturing of fluorinated catalyst], filled with 1 inch inner diameter and 1 meter long Inconel 600 reactor, one side of the heat and one side * 13 days at 4 0 C. The hydrogen fluoride was supplied at 6.32 liters / hour, and the gas containing hexafluoropropylene in [Raw Material 1] as the main component was supplied at 3.24 liters / hour. The nitrogen supply was stopped and the reaction was started. After 2 hours, the exhaust gas was washed with an aqueous sodium hydroxide solution to remove the acid, and the gas composition was analyzed by gas chromatography to obtain the composition shown in Table 5. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -19- 1242545 A7 B7 V. Description of the invention (1 > Table 5 Compound name chemical formula composition (v 0 1%) 2 Η-Heptafluoropropane compound CF3CHFCF3 99.9611 trifluoromethane CHF3 0.0053 hexafluoroethane CF3CF3 0.0192 pentafluoroethane CF3CHF2 0.0071 hexafluoropropane CF3CF2CF3 0.0004 hexafluoropropylene CF3CF = CF2 0.0052 chloropentafluoroethane CF3CCIF2 0.0008 tetrafluoroethane CF3CH2F 0.0008 chlorotrifluoroethane CF3CH2CI 0.0001 (Please read the precautions on the back before filling this page) The gas after the acid content is removed is cooled and collected in a cylindrical container, and distilled and purified by conventional methods. It is divided into low boiling point and high boiling point. Analysis by gas chromatography revealed the composition of Table 6. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 6 Compound name Chemical formula composition (v 0 1%) 2 Η -Heptafluoropropane CF3CHFCF3 99.9965 Pentafluoroethane CF3CHF2 0.0003 Octafluoro CF3CF2CF3 0.0001 hexafluoropropylene CF3CF = CF2 0.0019 chloropentafluoroethane CF3CC1F2 0.0007 tetrafluoroethane CF3CH2F 0.0005 this Zhang scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -20-1242545 Α7 Β7 V. Description of the invention (According to the results in Table 6, it can be seen that the ammonium chloride compounds contained in 2 Η-heptachloropropane hospital, Distillation can be reduced to less than 0.01% by volume. (Example 2) Directly fluorinated with fluorine gas using 2Η-heptafluoropropane as the main component after the distillation obtained in Example 1 was used. Inner diameter 2 0 6 mm 0, 500 mm long nickel reactor (heated by electric heater: the reactor is passivated with fluorine gas at a temperature of 50 ° C). Nitrogen is supplied at 20 standard liters / hour. The temperature was raised to 400 ° C. Next, hydrogen fluoride (diluent gas) was supplied at 60 standard liters / hour in two pieces, and one of them was supplied at 3.24 standard liters / hour. The gas of main component. Then supply fluorine gas at 3.55 standard liters / hour in another hydrogen fluoride flow, and stop the nitrogen supply for direct fluorination reaction. After 3 hours, the reaction is washed with sodium hydroxide aqueous solution and potassium iodide aqueous solution. Gas, analysis of hydrogen fluoride and unreacted Gas, followed by the partial removal of these acids in the gas chromatography analysis to obtain the organic gas composition as shown in Table 7. (Please read the precautions on the back before filling in this page) Clothing · Order 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) A4 (210X297 mm) '21-1242545 B7 V. Description of the invention (1 order Table 7 Compound name Chemical formula Composition (v 0 1%) Propane octafluoro CF3CF2CF3 99.1042 Tetrafluoromethane CF4 0.0011 Hexafluoroethane CF3CF3 0.0017 2 Η-Heptafluoropropane CFsCHFCFs 0.8762 Chloropentafluoroethane CF3CC1F2 0.0006 Perfluorohexyl Hospital C6Fl4 0.0162 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs On the other hand, the amount of unreacted fluorine in the reaction gas is 0.26 standard liters / hour. The removed gas was collected by cooling in a cylindrical container, and the low-boiling and high-boiling components were separated by distillation and purification by a known method. The composition obtained after the distillation and purification was analyzed by gas chromatography to obtain the composition in Table 8. Table 8 Compound name Chemical formula Composition (ν ο 1%) CF3CF2CF3 CF3CF2CF3 99.9992 2 Η -Heptafluoropropane CF3CHFCF3 0.0002 Chloropentafluoroethane CF3CCIF2 0.0006 From the results in Table 8, it can be known that the purity of the propane octafluoride obtained is more than 99.9% by volume. The paper size is applicable to China National Standard (CNS) A4 (210X 297mm) -22-1242545 A7 B7 V. Description of the invention (Example 3 of 20 C) (Please read the precautions on the back before filling out this page) Introduce the outlet gas of the direct fluorination reaction containing unreacted fluorine gas obtained in Example 2 into the inner diameter of 20 · 6 mm 0 '500 mm long nickel reactor. The gas composition is hydrogen fluoride 6 2. 8 2 standard liters / hour' organic matter 3. 16 standard liters / hour 'unreacted fluorine gas about 0.2 6 standard liters / hour The reactor was heated to 390 ° C, and the hydrofluorocarbon trifluoromethane was supplied from the reactor inlet at about 0.286 liters / hour. The unreacted fluorine and organic compounds were each titrated and gas Analysis by phase chromatography. The amount of unreacted fluorine in the outlet gas after reacting with trifluoromethane is below 50 ρ pm, and the composition of the gas is shown in Table 9. Table 9 Chemical formula of the compound name (v 0 1%) CF3CF2CF3 91.6849 Tetrafluoromethane CF4 5.2707 Trifluoromethane CHF3 3.0232 Hexafluoroethane CF3CF3 0.0028 2 Η-Heptafluoropropane CF3CHFCF3 0.0029 Chloropentafluoroethane CF3CCIF2 0.0006 Perfluorohexane CeF 14 0.0149 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the residual fluorine gas has been removed The outlet gas was washed with an aqueous potassium hydroxide solution to remove hydrogen fluoride. The acid-removed gas is cooled and captured in a cylindrical container, and distilled and purified by a known method to separate low-boiling and high-boiling. Distillation The purified gas was analyzed by gas chromatography to obtain the composition of Table 10. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -23-1242545 A7 B7 V. Description of the invention (2) Table 1 0 Chemical composition of the compound name (ν 〇1%) Propane octafluoride CF3CF2CF3 99.9993 2 Thallium-Heptafluoropropane CF3CHFCF3 0.0001 Chloropentafluoroethane CF3CCIF2 0.0006 (Comparative Example 1) A direct fluorination reaction was performed by reacting hexafluoropropylene with fluorine gas. Nickel reactor with an inner diameter of 2.0 mm and a length of 500 mm (electric heater heating: the reactor is passivated with fluorine gas at 500 ° C) and nitrogen at 60 standard liters / hour Two supplies, one side § weekly temperature is 500. Supply hexafluoropropylene as the main component of [raw material example 1] at 3.24 standard liters / hour in a nitrogen flow, and supply fluorine gas at 3.55 standard liters / hour in another nitrogen flow. Direct fluorination. After 2 hours, the gas produced by the reaction was washed with an aqueous potassium hydroxide solution and an aqueous potassium iodide solution to remove unreacted fluorine gas, and analyzed by gas chromatography. The gas composition is shown in Table 11-1. (Please read the precautions on the back before filling this page), 11
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） -24 - 1242545 A7 _ _ B7 五、發明説明（2会 表1 1 化合物名稱 ------ 化學甘 組成（V 0 1 % ) 八氟化丙烷 ---------- —CF3CF2CF3 93.3515 六氟乙烷 CF3CF, 0.0063 氯三氟甲烷 ------- CC1F, 0.0039 氯五氟乙烷 _ cf3CC1F2 0.0204 二氯四氟乙烷 ChccuF 0.0011 全氟己烷 CM 6.6122 八氟環丁烷 ~—----^ C4F, 0.0046 (請先閲讀背面之注意事項再填寫本頁) 衣· 如由表1 1之結果可知，六氟丙烯與氟氣直接氟化反 應製造八氟化丙烷之方法’會有聚合，環化加成等發生， 收率低。 其次，酸分去除後之氣體用筒狀容器冷卻捕集，用已 知方法進行蒸餾純化分爲低沸分丹离她^ 〃 力及问沸分。蒸餾純化後之 組成物以氣相層析法分析，得表i 2之組成。 表1 2 化合物名稱 ~~--—^ 化學式 —組成（v 0 1 % ) 八氟化丙烷 CF3CF2CF3 一99.9768 氯五氟乙烷 —----- CF3CC1F2 0 02 1 8 八氟環丁烷 C4F8 —---J 0.0022 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 訂The paper size printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -24-1242545 A7 _ _ B7 V. Description of the invention (2 sessions Table 1 1 Compound name --- --- Chemical composition (V 0 1%) Propane octafluoride ---------- --CF3CF2CF3 93.3515 Hexafluoroethane CF3CF, 0.0063 Chlorotrifluoromethane ------- CC1F, 0.0039 Chloropentafluoroethane_ cf3CC1F2 0.0204 Dichlorotetrafluoroethane ChccuF 0.0011 Perfluorohexane CM 6.6122 Octafluorocyclobutane ~ -------- C4F, 0.0046 (Please read the precautions on the back before filling this page) As can be seen from the results in Table 11, the method of producing hexafluoropropane by direct fluorination of hexafluoropropylene and fluorine gas will cause polymerization, cyclization, etc., and the yield will be low. Second, after the acid content is removed The gas was cooled and collected in a cylindrical container, and purified by a known method. Distillation was divided into a low boiling point and a boiling point. The composition after distillation was analyzed by gas chromatography to obtain Table i. Composition of 2. Table 1 2 Compound name ~~ --— ^ Chemical formula—Composition (v 0 1%) Propyl octafluoride CF3CF2CF3-99.9768 chloropentafluoroethane ------- CF3CC1F2 0 02 1 8 octafluorocyclobutane C4F8 ----- J 0.0022 This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) Order
經濟部智慧財產局員工消費合作社印製 -25 - 1242545 A7 B7 五、發明説明（2$ 如由表1 2之結果可知，八氟化丙烷與氯化合物氯五 氟乙烷及環狀化合物八氟環丁烷難以分離而高度純化。 (實施例4 ) 除六氟丙烯原料改用〔原料例2〕以外，如同（寶施 例1 )反應，酸分去除後之氣體分析後得表i 3之組成。 表1 化合物名稱 化學式 組成（v 0 1 2 Η -七氟丙烷 CF3CHFCF3 99.9079 三氟甲烷 CHF3 0.0098 六氟乙烷 CF3CF3 0.0414 五氟乙烷 CF3CHF2 0.0028 氯三氟甲院 CCIFs 0.0236 八氟化丙烷 CF3CF2CF3 0.005 六氟化丙烷 CF3CF-CF2 0.0049 氯五氟乙院 CF3CCIF2 0.0004 四氯乙院 CF3CH2F 0.0029 二氯二氟甲烷 CChFa 0.0012 氯四氟乙烷 CF3CHC1F 0.0005 氯三氟乙院 CF3CH2C1 0.0041 經濟部智慧財產局員工消費合作社印製 酸分去除後之氣體用筒狀容器冷卻捕集，用已知方法 進行蒸餾純化分爲低沸分及高沸分，蒸餾純化物之組成物 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） -26- 1242545 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（2) 以氣相層析法分析，得表1 4之組成。 表1 4 化合物名稱 化學式 組成（V 0 1 % ) 2. Η -七氟丙院 CF3CHFCF3 99.9925 五氟乙烷 CF3CHF2 ----- 0.0009 八氟化丙烷 CF3CF2CF3 0.0002 六氟丙烯 CF3CF = CF2 0.0016 氯五氟乙烷 CF3CC1F2 -- —---- 0.0014 四氟乙烷 CF3CH2F 0.0025 二氯二氟甲烷 CC12F2 0.0009 由表1 4之結果可知，2H -七氟丙烷中所含之雜質 氯化合物，以蒸餾可降至〇 · 0 1體積％以下。 (實施例5 ) 除2 Η -七氟丙院改用（實施例4 )之蒸餾純化物以 外，如同（實施例2 )反應，酸分去除後之氣體冷卻捕集 於鋼瓶，用已知方法蒸餾純化分爲高沸分及低沸分，所得 組成物以氣相層析法分析，知具表1 5之組成。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ,------訂------— (請先閲讀背面之注意事項再填寫本頁) -27- 1242545 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（2令 表1 5 化合物名稱 化學式 組成（v 〇 1 % ) 八氟化丙烷 CF3CF2CF3 99.9979 氯五氟乙烷 CF3CC1F2 0.0015 二氯二氟甲焼 CC12F2 0.0006 如由表1 5之結果可知，可得純度9 9 . 9 9 5體積 %以上之八氟化丙烷。 發明之效果 如以上說明，用本發明之方法時，使用或含氯系雜質 之六氟丙烯，可製造高純度之八氟化丙烷；用本發明製造 之高純度八氟化丙烷，可以用作半導體裝置之製程中之鈾 刻氣體或洗淨氣體。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -25-1242545 A7 B7 V. Description of the invention (2 $ As can be seen from the results in Table 12, propane fluorofluoride, chloropentafluoroethane, and cyclic octafluoro Cyclobutane is difficult to separate and highly purified. (Example 4) Except that the hexafluoropropylene raw material was changed to [raw material example 2], the reaction was the same as in (Boshi Example 1). Composition. Table 1 Compound name Chemical formula Composition (v 0 1 2 Η-heptafluoropropane CF3CHFCF3 99.9079 trifluoromethane CHF3 0.0098 hexafluoroethane CF3CF3 0.0414 pentafluoroethane CF3CHF2 0.0028 chlorotrifluoromethane CCIFs 0.0236 octafluoropropane CF3CF2CF3 0.005 hexafluoropropane Propane CF3CF-CF2 0.0049 Chloropentafluoroethane House CF3CCIF2 0.0004 Tetrachloroethane House CF3CH2F 0.0029 Dichlorodifluoromethane CChFa 0.0012 Chlorotetrafluoroethane CF3CHC1F 0.0005 Chlorotrifluoroethane House CF3CH2C1 0.0041 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economy The acid-removed gas is collected by cooling in a cylindrical container, and purified by a known method. Distillation is divided into low boiling point and high boiling point. The composition of this paper is in accordance with Chinese National Standard (CNS) A4 specification (21〇 < 297 mm) -26- 1242545 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (2) Gas Analysis by phase chromatography, the composition of Table 14 is obtained. Table 14 Composition of the chemical formula of the compound name (V 0 1%) 2. Η-Heptafluoropropane CF3CHFCF3 99.9925 pentafluoroethane CF3CHF2 ----- 0.0009 octafluoride Propane CF3CF2CF3 0.0002 Hexafluoropropene CF3CF = CF2 0.0016 Chloropentafluoroethane CF3CC1F2------- 0.0014 Tetrafluoroethane CF3CH2F 0.0025 Dichlorodifluoromethane CC12F2 0.0009 From the results in Table 1, we can see that 2H-Heptafluoropropane The impurities contained in the chlorine compound can be reduced to 0.01% by volume or less by distillation. (Example 5) Except for the distilled purified product which was replaced by 2Η-Heptafluoropropane (Example 4), it is the same as (Example 2) ) Reaction, the gas after acid removal is cooled and trapped in a steel cylinder, and distilled and purified by a known method into high boiling point and low boiling point. The obtained composition is analyzed by gas chromatography, and the composition shown in Table 15 is known. This paper size applies to Chinese National Standard (CNS) Α4 Specifications (210 × 297 mm), ------ Order -------- (Please read the precautions on the back before filling out this page) -27- 1242545 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2 Orders Table 1 5 Compound name chemical formula composition (v 〇1%) propane octafluoride CF3CF2CF3 99.9979 chloropentafluoroethane CF3CC1F2 0.0015 dichlorodifluoromethane CC12F2 0.0006 As can be seen from the results of Table 1 5 To obtain propane octafluoride with a purity of 99.95% by volume. Effects of the Invention As described above, when using the method of the present invention, hexafluoropropylene containing or containing chlorine-based impurities can be used to produce high-purity octafluoropropane; the high-purity octafluoropropane produced by the present invention can be used as Uranium-etched gas or purge gas in the manufacturing process of semiconductor devices. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)
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