1266759 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關於五氟乙烷之製造方法，使用該方法製 得之五氟乙烷製造六氟乙烷之方法，以及五氟乙烷之用途 〇 【先前技術】 五氟乙烷（即、CFgCHF2 〃）可用作例如，低溫冷 媒、蝕刻氣體，及作爲六氟乙烷（即、、CF3CF3 〃 ）之製 造原料。 五氟乙烷之製造方法，向來已知有下列，例如 (1 ) 四氯乙烯（即、、CC12 = CC12 〃 ）或其氟化物 以氟化氫氟化之方法（日本專利特開平8-26893 2號公報、 特表平9-511515號公報）， (2) 氯五氟乙烷（即〜CF3CF2C1 〃 ）之氫化分解 方法（專利第254〇4〇9號公報）， (3 ) 含鹵乙烯以氟氣反塵之方法（特開平I-3 8 〇3 4 號公報）等。 使用這些製造方法時，目標產物五氟乙烷中會含氟氯 化碳（CFC )類、氫氟氯化碳（HCFC )類、氫氟化碳（ HFC )類等之種種雜質。 爲製得高純度五氟乙烷，須盡可能去除此等雜質。這 些雜質之中，有關氟氯化碳類除高度純化之目的以外’基 於避免臭氧層之破壌，有種種純化方法之提議。尤以氯五 -6- (2) 1266759 氟乙烷因與五氟乙烷沸點接近，通常之蒸餾難以分離’而 有以下純化方法之提議，例如 (1) 萃取蒸餾法（特表平9-508626號公報）， (2) 氯五氟乙烷之氫化分解法（特開平8_3〇1801號 公報）， (3 ) 氯五氟乙烷以氟化氫（HF )氟化後去除之方 法（特開200 1 -48 8 1 6號公報）等。 相對於此，氫氟氯化碳類、氫氟化碳類雜質之分離而 純化之方法卻極少見有提議，僅例如特表平9-50S627號公 報之經萃取蒸餾純化之方法。氫氟氯化碳類、氫氟化碳類 中，二氟甲烷（即、、CH2F2 〃 ）及1,1，卜三氟乙烷（即 CF3CH3 〃 ）因已知與五氟乙烷形成共沸混合物，係非常 難以與五氟乙烷分離之化合物。 以包含氫化分解之方法製造五氟乙烷時，加氫脫鹵反 應過度之結果，形成副產物1，1，1 -三氟乙烷的可能性提高 ，於五氟乙烷中之含量相對較高。含於五氟乙烷1,1，1-三 氟乙烷之去除方法，已知有萃取蒸餾法。然而，該方法因 須多套蒸餾塔等昂貴設備，有設備成本膨大之問題。 〔發明所欲解決之課題〕 本發明在如此之背景下，其課題在提供，可用作低溫 冷媒、鈾刻氣體、或高純度六氟乙烷製造原料之高純度五 氟乙烷的工業上之有利製造方法，高純度五氟乙烷的工業 上之有利製造方法及使用該方法製得之五氟乙烷的六氟乙 (3) 1266759 烷製造方法，以及五氟乙烷之用途。 【發明內容】 〔用以解決課題之手段〕 本發明人等爲解決上述課題精心探討結果發現，利用 包含四氟乙烯氟化以得含雜質之粗五氟乙烷之過程（1) ’及觸媒存在下，使上述含雜質之粗五氟乙烷與氧及/或 含氧化合物接觸之過程（2)的五氟乙烷之製造方法，上 述課題即可解決，終於完成本發明。 本發明之五氟乙烷製造方法，其特徵爲：包含以下過 (1 ) 四氟乙烯之氟化以得粗五氟乙烷的過程 (2) 觸媒存在下，使上述粗五氟乙烷與氧及/或含 ------- 用於過程（2 )之粗五氟乙烷，係以經與氫接觸之過 程而得者爲佳。 過程（2 )之溫度以1 5 0至4 0 0 t：爲佳。 觸媒以主要成分係三價氧化鉻之載持型或塊狀型觸媒 爲佳。 觸媒以主要成分係選自鈀、鍺、釕、銶、鉑及金所成 群之至少一種金屬的載持型觸媒爲佳。 用於載持型觸媒之載體以氧化物鋁、氟化氧化鋁或沸 石爲佳。 粗五氟乙烷之主要成係五氟乙烷，可含雜質其係選自 -8- (4) 1266759 氟代甲烷、二氟甲烷、氟代乙烷、1，1-二氟乙烷、l52_二 氟乙烷、1，1，1-三氟乙烷及1，1，2_三氟乙烷所成群之至少一 種。 粗五氟乙烷中所含雜質總重以占2體積％以下爲佳。 本發明之五氟乙烷製造方法，其特徵爲：主要成分係 三價氧化鋁的觸媒之存在下，使粗五氟乙烷與氧及/或含 氧化合物於1 5 0至4 0 0 °C接觸，其次以蒸餾分離雜質。 又，本發明之五氟乙烷製造方法，其特徵爲：主要成 分係選自鈀、鍺、釕、銶、鉑及金所成群之至少一種金屬 的載持型觸媒之存在下，使粗五氟乙烷與氧及/或含氧化 合物於150至4〇0 °C接觸，其次蒸餾分離雜質。 粗五氟乙烷其雜質可至少包含三氟乙烷。 氧及/或含氧化合物之濃度以0.1至20體積％爲佳。 本發明係經上述任一製造方法所得，雜質總量占500 體積ppm以下之五氟乙烷。 五氟乙烷中所含雜質三氟乙烷其含量以100體積ppm 以下爲佳。 本發明係其特徵爲含五氟乙烷之冷媒。 本發明之六氟乙烷製造方法，其特徵爲：包含以下過 程。 (1 ) 四氯乙烯之氟化以得粗五氟乙烷之過程 (2) 觸媒存在下，使上述粗五氟乙烷與氧及/或含 氧化合物接觸以得五氟乙烷之過程 (3 ) 經過程（2 )而得之五氟乙烷與氟氣反應以得 -9 - (5) 1266759 六氟乙院之過程 用於過程（2 )之粗五氟乙烷，以經與氫接觸之過程 所得者爲佳。 【實施方式】 以下詳細說明本發明。 如上述，五氟乙烷可經四氯乙烯或其氟化物以氟化氫 (HF )氟化之方法，或，氯五氟乙烷之氫化分解方法等 製造。無論採用何種方法，經一般蒸餾操作等純化過程而 得之五氟乙烷中，含難與五氟乙烷分離之雜質氯五氟乙烷 。爲提高五氟乙烷之純度，氯五氟乙烷須予分離，而從防 止破壞臭氧層之觀點，有不含氯五氟乙烷之要求。 五氟乙烷中所含氯五氟乙烷之分離方法，如上述，有 氫化分解法、萃取蒸餾法、吸附法等之提議。這些方法當 中，考慮設備成本等時，可廉價製造五氟乙烷者乃氫化分 解法。在此，五氟乙烷之製造方法或純化方法，選擇包含 氫化分解過程之方法時，會有過度加氫反應之結果，產生 難以分離之1,1，1-三氟乙烷等氫氟化碳（HFC )類。尤以 二氟甲烷及1,1,1-三氟乙烷與五氟乙烷沸點非常接近，並 知可形成共沸混合物，係以蒸餾等一般純化方法難以分離 之物質。五氟乙烷中所含氫氟化碳（HCF )類之分離方法 雖有上述萃取蒸餾法之提議，但有需要多套蒸餾塔等昂貴 設備，而設備成本膨大之問題。 本發明之五氟乙烷製造方法，其特徵爲：包含（1) -10- (6) 1266759 四氯乙烯之氟化以得含雜質之粗五氟乙烷之過程，及（2 )觸媒存在下，使上述粗五氟乙烷與氧及/或含氧化合物 接觸之過程。過程（1 )之方法無特殊限制，可於觸媒之 存在下，用氟化氫（HF )將四氯乙烯二段氟化，得粗S 氟乙烷。 本發明係使五氟乙烷中所含，如氫氟化碳（HFC )之 雜質於接觸存在下，以氣相在150至4〇0 °C之高溫與氧及/ 或含氧化合物接觸，使所含雜質氫氟化碳類氧化，轉化爲 C〇2等。例如，五氟乙烷中所含之二氟甲烷及1，1，卜三氟 乙烷，推測係經氧如下述式（a )、式（b )進行氧化反應 CH2F2 + 02— C02 + 2HF 式（Ο CF3CH3 + 2〇2-> 2C〇2 + 3HF 式(b ) 主要氧化產物係C Ο 2，副產物係HF。 以該反應轉化爲C02之化合物有氟代甲烷、二氟甲院 、氟代乙烷、1，1-二氟乙烷、1,2-二氟乙烷、1,1，1-三氟乙 烷、1,1，2_三氟乙烷等。這些化合物用於包含氫化分解 '過 程之製造方法或純化方法時，於五氟乙烷中通常約占總纛 的數千ppm。這些雜質從五氟乙烷的高度純化之觀點須予 去除。 本發明的五氟乙烷之製造方法中，粗五氟乙烷所含氫 氟化碳（HFC )等雜質總量以2體積％以下又更佳’ 0.5體 積°/〇以下更佳，0.3體積％以下又更佳。氫氟化碳類等雜質 含量若超過2體積％，則反應溫度高，觸媒壽命短。 -11 - (7) 1266759 用於反應之觸媒係以（i)三價氧化鉻爲主要成分之 載持型或塊狀型觸媒，或（ii )主要成分係選自鈀、鍺、 釕、銶、鉑或金所成群之至少一種金屬的載持型觸媒。原 料可用這些金屬，其氧化物或鹽等。又，可用於載持型觸 媒之載體有氧化鋁、氟化氧化鋁或沸石。 主要成分係三價氧化鉻之觸媒（i )的調製方法可係 例如，以氨等鹼性物質滴入鉻金屬鹽水溶液中沈澱出氫氧 化鉻後，淸洗、過濾、乾燥後之氫氧化鉻於成形後，再於 氮等惰性氣體存在下加熱處理。而主要成分係鈀、鍺、釕 、鍊、鉑及/或金之載持型觸媒（ii )之調製方法可係例如 ，上述金屬鹽溶解於例如水、甲醇或丙酮等水溶性溶劑， 將載體浸入以吸附必要之元素。其次餾除溶劑，以氫等作 加熱還原處理。1266759 (1) Description of the Invention [Technical Field] The present invention relates to a process for producing pentafluoroethane, a process for producing hexafluoroethane from pentafluoroethane produced by the process, and pentafluoroethane Use of alkane [Prior Art] Pentafluoroethane (i.e., CFgCHF2®) can be used, for example, as a low-temperature refrigerant, an etching gas, and as a raw material for the production of hexafluoroethane (i.e., CF3CF3®). As a method for producing pentafluoroethane, the following are known, for example, (1) tetrachloroethylene (ie, CC12 = CC12 〃) or a method in which a fluoride thereof is fluorinated with hydrogen fluoride (Japanese Patent Laid-Open No. Hei 8-26893 No. 2) (2) Hydrogenation decomposition method of chloropentafluoroethane (that is, ~CF3CF2C1 〃) (Patent No. 254〇4〇9), (3) Halogen-containing vinyl fluoride Gas dusting method (Special Kaiping I-3 8 〇3 4 bulletin) and the like. When these production methods are used, the target product pentafluoroethane contains various impurities such as fluorine-containing chlorocarbon (CFC), hydrochlorofluorocarbon (HCFC), and hydrofluorocarbon (HFC). In order to produce high purity pentafluoroethane, such impurities must be removed as much as possible. Among these impurities, there are various proposals for purification methods based on the purpose of avoiding the destruction of the ozone layer in addition to the purpose of high-purification of CFCs. In particular, chloropenta-6-(2) 1266759 fluoroethane is close to the boiling point of pentafluoroethane, and it is usually difficult to separate by distillation, and there are proposals for the following purification methods, such as (1) extractive distillation method (special table 9- (No. 508626), (2) Hydrogenation decomposition method of chloropentafluoroethane (JP-A-8-31801), (3) Method of removing chloropentafluoroethane by fluorination of hydrogen fluoride (HF) (Special opening 200) 1 - 48 8 1 6 bulletin) and so on. On the other hand, there are few proposals for the separation and purification of hydrofluorocarbons and hydrofluorocarbons, and only the method of extractive distillation purification is disclosed in, for example, JP-A-9-50S627. Among hydrofluorocarbons and hydrofluorocarbons, difluoromethane (ie, CH2F2 〃) and 1,1, trifluoroethane (ie CF3CH3 〃) are known to form azeotrope with pentafluoroethane. The mixture is a compound which is very difficult to separate from pentafluoroethane. When pentafluoroethane is produced by a method including hydrogenation decomposition, as a result of excessive hydrodehalogenation, the possibility of forming by-product 1,1,1-trifluoroethane is increased, and the content in pentafluoroethane is relatively high. high. An extraction distillation method is known as a method for removing pentafluoroethane 1,1,1-trifluoroethane. However, this method has a problem of an increase in equipment cost due to the necessity of expensive equipment such as a plurality of distillation towers. [Problems to be Solved by the Invention] Under the circumstances, the present invention provides an industrial high-purity pentafluoroethane which can be used as a raw material for producing low-temperature refrigerant, uranium engraving gas or high-purity hexafluoroethane. An advantageous manufacturing method, an industrially advantageous manufacturing method of high-purity pentafluoroethane, a method for producing hexafluoroethane (3) 1266759 by using the method, and a use of pentafluoroethane. [Means for Solving the Problem] The inventors of the present invention have carefully studied the above-mentioned problems and found that the process of using fluorochemical tetrafluoroethylene to obtain crude pentafluoroethane containing impurities (1) ' In the presence of a medium, the method for producing pentafluoroethane in the process (2) of contacting the above-mentioned impurity-containing crude pentafluoroethane with oxygen and/or an oxygen-containing compound can solve the above problems, and finally the present invention has been completed. The process for producing pentafluoroethane of the present invention is characterized by comprising the following process of fluorinating tetrafluoroethylene to obtain crude pentafluoroethane (2) in the presence of a catalyst to make the above crude pentafluoroethane It is preferred that the oxygen and/or the crude pentafluoroethane used in the process (2) be in contact with hydrogen. The temperature of the process (2) is preferably from 150 to 4,000 t:. The catalyst is preferably a carrier type or a block type catalyst in which the main component is trivalent chromium oxide. The catalyst is preferably a supported catalyst in which the main component is at least one metal selected from the group consisting of palladium, rhodium, ruthenium, iridium, platinum, and gold. The carrier for the carrier-type catalyst is preferably aluminum oxide, aluminum fluoride or zeolite. The main constituent of crude pentafluoroethane is pentafluoroethane, which may contain impurities selected from -8-(4) 1266759 fluoromethane, difluoromethane, fluoroethane, 1,1-difluoroethane, At least one of l52_difluoroethane, 1,1,1-trifluoroethane and 1,1,2-trifluoroethane. The total weight of impurities contained in the crude pentafluoroethane is preferably 2% by volume or less. The method for producing pentafluoroethane according to the present invention is characterized in that: in the presence of a catalyst containing trivalent alumina as a main component, crude pentafluoroethane and oxygen and/or an oxygen compound are present at 150 to 400. Contact at °C, followed by separation of impurities by distillation. Further, the method for producing pentafluoroethane according to the present invention is characterized in that the main component is selected from the group consisting of a supported catalyst of at least one metal selected from the group consisting of palladium, rhodium, ruthenium, iridium, platinum, and gold, and The crude pentafluoroethane is contacted with oxygen and/or an oxygenate at 150 to 4 ° C, and the impurities are separated by distillation. The crude pentafluoroethane may contain at least trifluoroethane as an impurity thereof. The concentration of oxygen and/or oxygenate is preferably from 0.1 to 20% by volume. The present invention is obtained by any of the above production methods, and the total amount of impurities is 500 ppm by volume or less of pentafluoroethane. The content of the impurity trifluoroethane contained in the pentafluoroethane is preferably 100 ppm by volume or less. The present invention is characterized by a refrigerant containing pentafluoroethane. The method for producing hexafluoroethane of the present invention is characterized by comprising the following process. (1) The process of fluorination of tetrachloroethylene to obtain crude pentafluoroethane (2) The process of contacting the above crude pentafluoroethane with oxygen and/or oxygenate to obtain pentafluoroethane in the presence of a catalyst (3) The pentafluoroethane obtained by the process (2) is reacted with fluorine gas to obtain the process of -9 - (5) 1266759 hexafluoride, which is used for the crude pentafluoroethane of the process (2). The process of hydrogen contact is preferred. [Embodiment] Hereinafter, the present invention will be described in detail. As described above, pentafluoroethane can be produced by a method in which tetrachloroethylene or a fluoride thereof is fluorinated with hydrogen fluoride (HF), or a hydrogenation decomposition method of chloropentafluoroethane. Regardless of the method used, the pentafluoroethane obtained by a purification process such as a general distillation operation contains an impurity chloropentafluoroethane which is difficult to separate from pentafluoroethane. In order to improve the purity of pentafluoroethane, chloropentafluoroethane must be separated, and from the viewpoint of preventing the destruction of the ozone layer, there is no requirement for chloropentafluoroethane. The separation method of chloropentafluoroethane contained in pentafluoroethane, as described above, is proposed by a hydrogenation decomposition method, an extractive distillation method, an adsorption method, and the like. Among these methods, when the equipment cost and the like are considered, it is possible to inexpensively produce pentafluoroethane as a hydrogenation decomposition method. Here, in the method for producing or purifying pentafluoroethane, when a method including a hydrogenation decomposition process is selected, there is excessive hydrogenation reaction, and hydrogen fluoride which is difficult to separate, 1, 1, 1-trifluoroethane or the like is generated. Carbon (HFC) class. In particular, difluoromethane and 1,1,1-trifluoroethane have very close boiling points with pentafluoroethane, and it is known that an azeotropic mixture can be formed, which is difficult to separate by a general purification method such as distillation. Separation method of hydrofluorocarbon (HCF) contained in pentafluoroethane Although there is a proposal for the above-described extractive distillation method, there are many problems such as requiring expensive sets of distillation towers and the like, and the cost of the equipment is increased. The process for producing pentafluoroethane of the present invention is characterized by comprising: (1) -10- (6) 1266759 fluorination of tetrachloroethylene to obtain crude pentafluoroethane containing impurities, and (2) catalyst The process of bringing the above crude pentafluoroethane into contact with oxygen and/or an oxygen-containing compound in the presence of the above. The method of the process (1) is not particularly limited, and the second stage of tetrachloroethylene can be fluorinated with hydrogen fluoride (HF) in the presence of a catalyst to obtain crude S fluoroethane. The present invention is such that impurities such as hydrofluorocarbon (HFC) contained in pentafluoroethane are contacted with oxygen and/or an oxygen compound in a gas phase at a high temperature of 150 to 4 ° C in the presence of a contact. The impurity-containing hydrofluorocarbons are oxidized and converted into C〇2 or the like. For example, difluoromethane and 1,1,trifluoroethane contained in pentafluoroethane are presumed to be oxidized by the following formula (a) and formula (b). CH2F2 + 02 - C02 + 2HF (Ο CF3CH3 + 2〇2-> 2C〇2 + 3HF Formula (b) The main oxidation product is C Ο 2, and the by-product is HF. The compound converted to CO 2 by this reaction is fluoromethane, difluoromethyl, Fluorine, 1,1-difluoroethane, 1,2-difluoroethane, 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, etc. These compounds are used for In the case of a production method or a purification method comprising a hydrogenation decomposition process, it usually accounts for several thousand ppm of total ruthenium in pentafluoroethane. These impurities must be removed from the viewpoint of high purification of pentafluoroethane. In the method for producing ethane, the total amount of impurities such as hydrofluorocarbon (HFC) contained in crude pentafluoroethane is preferably 2% by volume or less and more preferably 0.5% by volume or less, more preferably 0.3% by volume or less. When the content of impurities such as hydrofluorocarbons exceeds 2% by volume, the reaction temperature is high and the catalyst life is short. -11 - (7) 1266759 The catalyst used for the reaction is (i) trivalent chromium oxide a carrier-type or block-type catalyst of the component, or (ii) a carrier-type catalyst of at least one metal selected from the group consisting of palladium, rhodium, ruthenium, iridium, platinum or gold. And an oxide or a salt thereof, etc. Further, the carrier which can be used for the carrier-type catalyst is alumina, fluorided alumina or zeolite. The preparation method of the catalyst (i) whose main component is trivalent chromium oxide can be, for example, After the alkaline substance such as ammonia is dropped into the chromium metal salt aqueous solution to precipitate chromium hydroxide, the chromium hydroxide after washing, filtering and drying is formed, and then heat-treated in the presence of an inert gas such as nitrogen. The method for preparing a supported catalyst (ii) of palladium, rhodium, iridium, a chain, platinum, and/or gold may be, for example, the above metal salt is dissolved in a water-soluble solvent such as water, methanol or acetone, and the carrier is immersed for adsorption. The necessary elements are followed by distillation of the solvent, and hydrogen or the like as a heating reduction treatment.
過程（2 )之溫度以150至400 °C爲佳，180至3 70 °C 更佳。反應溫度若高於400 °C則觸媒壽命傾向偏短，非 出自主要反應之副產物種類、量增加。 反應基質氣體中所含氧及/或含氧化合物之濃度以0.1 至20體積％爲佳。氧可用高純度氧或空氣，以用高純度 氧爲佳。氧濃度不及0.1體積％時，雖隨五氟乙烷中所含 雜質氫氟化碳類之種類、量而異，但氧不及反應所需，轉 化率低而不佳。又若氧濃度高於20體積％，則過度反應 ，反應基質氣體主要成分五氟乙烷起分解反應，五氟乙烷 之耗損量增大於經濟上不佳。又，含氧化合物可用一氧化 氮（NO )、一氧化二氮（N20 )、二氧化氮（N〇2 )或臭 (8) 1266759 氧（〇3 )。 本發明之五氟乙烷之製造方法，可於如上之反應條件 下實施，但因反應產物除五氟乙烷以外，含co2、非主反 應所致氫氟化碳類等副產物、HF等酸分，故以將C02、酸 分去除爲佳。 酸分之去除可用例如，與純化劑接觸之方法，與水、 鹼水溶液等接觸之方法等。酸分經去除之氣體以用例如沸 石等脫水劑脫水，然後蒸餾去除C02爲佳，與此同時去除 上述非主反應所致副產物爲佳。 又本發明係，其特徵爲：主要成分係三價氧化鉻之觸 媒存在下，使粗五氟乙烷與氧及/或含氧化合物於150至 40 0 °C接觸，其次以蒸餾分離雜質之五氟乙烷製造方法 〇 又，本發明係其特徵爲：主要成分係選自鈀、铑、釕 、鍊、鉑及金所成群之至少一種金屬的載持型觸媒之存在 下，使粗五氟乙烷與氧及/或含氧化合物於150至400 °C接 觸，其次以蒸餾分離雜質之五氟乙烷製造方法。 反應後，純化方法無特殊限制，可經一般所用之蒸餾 純化。蒸餾可用例如以下之方法。 反應器中於150至4〇0 °C接觸之粗五氟乙烷與氧及/或 含氧化合物氣體導入蒸餾塔。蒸餾塔內壓力以在大氣壓至 2百萬帕之範圍內爲佳。低於大氣壓則須減壓系之設備， 若超過2百萬帕則須高壓系之設備而不佳。例如用氧進行 上述之接觸反應時，含氧之低沸分自蒸餾塔頂抽出，高沸 -13- (9) 1266759 分自蒸餾塔底抽出。此時，自塔頂及塔底抽出之成分中’ 包含目標成分五氟乙烷，可各導入蒸餾塔純化回收五氟乙 烷。分離成分係五氟乙烷之製造中間體時可送返反應過程 再利用。 經如此之純化，可得高純度五氟乙烷。雜質含量在 5 00體積ppm以下。純度99.9 5體積％以上的五氟乙烷之 分析方法有，氣相層析（GC )法之TCD、FID法、或氣相 層析-質譜分析（GC-MS )法等。 其次說明利用本發明製造方法所得之五氟乙烷之用途 〇 高純度之五氟乙烷可用作目前作爲低溫冷凍機作動流 體之氯二氟甲烷（CHF2C1 )之替代品。亦可用作氯二氟 甲烷之其它替代品二氟甲烷/五氟乙烷/1,1，1,2-四氟乙烯、 二氟甲烷/五氟乙烷等混合冷媒之原料。 又，高純度五氟乙烷亦可用作高純度六氟乙烷之製造 原料。尤以五氟乙烷與氟氣（F2)反應製造六氟乙烷之製 造方法中，因使用高純度五氟乙烷作原料，難與六氟乙烷 分離之雜質的產生受到抑制，氟化反應條件範圍擴大，可 穩定控制，純化過程簡化。 因此本發明係其特徵爲：包含（1 )四氯乙烯之氟化 以得含雜質之粗五氟乙烷的過程，（2)觸媒存在下，使 上述粗五氟乙烷與氧及/或含氧化合物接觸之過程，以及 (3 )經過程（2 )所得五氟乙院與氟氣反應之過程的六氟^ 乙烷之製造方法。 -14- (10) 1266759 過程（2 )之粗五氟乙烷，以係經與氫接觸之過程而 得者爲佳。 又，高純度五氟乙烷，或與He、N2、At*等惰性氣體 ，HC1、〇2、H2等之混合氣體，可用作半導體裝置之製程 中，鈾刻過程之蝕刻氣體。LSI、TFT、有機EL等半導體 裝置之製程中，係用CVD法、濺鍍法或蒸鍍法等形成薄膜 、厚膜，爲形成電路圖型進行鈾刻時，含上述五氟乙烷之 混合氣體可用作蝕刻氣體。使用五氟乙烷之鈾刻方法，可 於電漿蝕刻、微波鈾刻等各種乾式蝕刻條件下實施。 【實施方式】 以下藉實施例更詳細說明本發明，惟本發明並非僅限 於此等實施例。 (五氟乙烷之原料例） 於充塡有觸媒之第一反應器導入四氯乙烯及氟化氫， 產生主要成分係中間體1，1，1_三氟-2,2-二氯乙烷及1，1,1,2-四氟-2-氯乙烷之氣體，連同HF導入第二反應器製造五氟 乙烷。蒸餾該五氟乙烷，得含雜質氯五氟乙烷0.5 %之五氟 乙烷。 上述五氟乙烷於市售氫化觸媒之存在下，與氫反應（ 反應壓力0.3 5百萬帕，反應器溫度280 °C，H2/氯五氟乙 烷莫耳比=5 )。用已知方法從所得混合氣體去除酸分後， 蒸餾純化得主要成分係五氟乙烷之餾出物。該餾出物以氣 -15- (11) (11)1266759 相層析分析，知係組成如表1之混合氣體。 表1 成分 濃度（體積％) CF3CHF2 99.7171 CF3CF2C1 0.0005 CF3CH2F 0.0201 CF3CH3 0.2621 CHF3 0.0002 (觸媒之製造例） （觸媒1 ) 溶解硝酸鉻9水合物於水，攪拌下混合2 8重量％之氨 水，得氫氧化鉻漿體。將之過濾，以水仔細淸洗後，於 12〇 °c乾燥。所得固體予以粉碎，混合以石墨，用打錠 成形機粒料化。該粒料在N2氣流下於400 °c煅燒4小時· ，得主要成分係三價氧化鉻之觸媒1。 (觸媒之製造粒） （觸媒2 ) 將氯化鉑酸溶解於水，將3毫米0之球狀氧化鋁載 體浸入以吸附鉑鹽。然後於1 00 °C餾去溶劑，在3 00 °C 空氣中煅燒後，於3 5 0 °C進行氫還原。所得鉑觸媒2之鉑 載持率爲0.2 5 %。 (實施例1 ) 內徑1英吋，長1米之因科鎳600反應器內充塡以觸 -16- (12) 1266759The temperature of the process (2) is preferably 150 to 400 ° C, and more preferably 180 to 3 70 ° C. When the reaction temperature is higher than 400 °C, the catalyst life tends to be short, and the type and amount of by-products which are not caused by the main reaction increase. The concentration of oxygen and/or oxygen-containing compound contained in the reaction substrate gas is preferably from 0.1 to 20% by volume. Oxygen may be used in high purity oxygen or air to preferably use high purity oxygen. When the oxygen concentration is less than 0.1% by volume, the type and amount of the hydrofluorocarbons contained in the pentafluoroethane vary, but oxygen is not required for the reaction, and the conversion rate is low. Further, if the oxygen concentration is higher than 20% by volume, the reaction is excessively reacted, and the main component of the reaction matrix gas, decafluoroethane, is decomposed, and the amount of depletion of pentafluoroethane is increased to be economically unsatisfactory. Further, the oxygen-containing compound may be nitrogen monoxide (NO), nitrous oxide (N20), nitrogen dioxide (N〇2) or odor (8) 1266759 oxygen (〇3). The method for producing pentafluoroethane of the present invention can be carried out under the above reaction conditions, but the reaction product contains, in addition to pentafluoroethane, by-products such as co2, hydrofluorinated carbons due to non-main reaction, HF, and the like. Acid, so it is better to remove CO 2 and acid. The removal of the acid can be, for example, a method of contacting with a purifying agent, a method of contacting with water, an aqueous alkali solution or the like. The acid-removed gas is dehydrated with a dehydrating agent such as a zeolite, and then CO 2 is preferably distilled off, and at the same time, it is preferable to remove the by-products caused by the above non-main reaction. Further, the present invention is characterized in that: in the presence of a catalyst containing trivalent chromium oxide as a main component, the crude pentafluoroethane is contacted with oxygen and/or an oxygen compound at 150 to 40 ° C, and secondly, impurities are separated by distillation. Process for producing pentafluoroethane, and the present invention is characterized in that the main component is selected from the group consisting of a supported catalyst of at least one metal selected from the group consisting of palladium, rhodium, ruthenium, chain, platinum, and gold, A method in which crude pentafluoroethane is contacted with oxygen and/or an oxygen-containing compound at 150 to 400 ° C, followed by distillation to separate impurities of pentafluoroethane. After the reaction, the purification method is not particularly limited and can be purified by distillation generally used. Distillation can be carried out, for example, in the following manner. The crude pentafluoroethane and oxygen and/or oxygen-containing gas which are contacted at 150 to 4 °C in the reactor are introduced into the distillation column. The pressure in the distillation column is preferably in the range of from atmospheric pressure to 2 MPa. Equipment that is depressurized below atmospheric pressure, if it exceeds 2 million Pa, the equipment of high pressure system is not good. For example, when the above contact reaction is carried out with oxygen, the low oxygen-containing boiling point is withdrawn from the top of the distillation column, and the high boiling -13-(9) 1266759 points are withdrawn from the bottom of the distillation column. At this time, the component extracted from the top of the column and the bottom of the column contains the target component pentafluoroethane, and each of them can be introduced into a distillation column to purify and recover pentafluoroethane. When the separation component is a manufacturing intermediate of pentafluoroethane, it can be returned to the reaction process for reuse. After purification in this way, high purity pentafluoroethane can be obtained. The impurity content is below 500 ppm by volume. The analysis method of pentafluoroethane having a purity of 99.9 5% by volume or more includes a TCD, FID method, or a gas chromatography-mass spectrometry (GC-MS) method using a gas chromatography (GC) method. Next, the use of the pentafluoroethane obtained by the production method of the present invention will be described. 〇 High-purity pentafluoroethane can be used as a substitute for chlorodifluoromethane (CHF2C1) which is currently used as a moving fluid for a cryogenic refrigerator. It can also be used as a raw material for mixed refrigerants such as difluoromethane/pentafluoroethane/1,1,1,2-tetrafluoroethylene and difluoromethane/pentafluoroethane as alternatives to chlorodifluoromethane. Further, high-purity pentafluoroethane can also be used as a raw material for the production of high-purity hexafluoroethane. In the method for producing hexafluoroethane by reacting pentafluoroethane with fluorine gas (F2), the use of high-purity pentafluoroethane as a raw material suppresses the generation of impurities which are difficult to separate from hexafluoroethane, and fluorinates. The range of reaction conditions is expanded, the control is stable, and the purification process is simplified. Therefore, the present invention is characterized in that it comprises (1) a process of fluorination of tetrachloroethylene to obtain crude pentafluoroethane containing impurities, and (2) in the presence of a catalyst, the above crude pentafluoroethane and oxygen and/or Or a process of contacting an oxygenate, and (3) a process for producing hexafluoroethane by a process in which the pentafluoroethane obtained by the process (2) is reacted with fluorine gas. -14- (10) 1266759 The crude pentafluoroethane of process (2) is preferred to be in contact with hydrogen. Further, high-purity pentafluoroethane or a mixed gas of He, N2, At*, or the like, HC1, cesium 2, H2, or the like can be used as an etching gas for the uranium engraving process in the process of a semiconductor device. In a process of a semiconductor device such as an LSI, a TFT, or an organic EL, a thin film or a thick film is formed by a CVD method, a sputtering method, a vapor deposition method, or the like, and a mixed gas containing the above-described pentafluoroethane is formed for uranium engraving when forming a circuit pattern. Can be used as an etching gas. The uranium engraving method using pentafluoroethane can be carried out under various dry etching conditions such as plasma etching and microwave uranium engraving. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. (Example of raw materials of pentafluoroethane) Introducing tetrachloroethylene and hydrogen fluoride in a first reactor charged with a catalyst to produce a main component intermediate 1,1,1_trifluoro-2,2-dichloroethane And a gas of 1,1,1,2-tetrafluoro-2-chloroethane, together with HF, is introduced into the second reactor to produce pentafluoroethane. The pentafluoroethane was distilled to obtain 0.5% of pentafluoroethane containing an impurity of chloropentafluoroethane. The above pentafluoroethane is reacted with hydrogen in the presence of a commercially available hydrogenation catalyst (reaction pressure: 0.35 MPa, reactor temperature: 280 °C, H2/chloropentafluoroethene molar ratio = 5). After removing the acid component from the obtained mixed gas by a known method, the main component is a distillate of pentafluoroethane. The distillate was analyzed by gas chromatography on gas -15-(11) (11) 1266759, and it was known that the mixed gas of the composition shown in Table 1. Table 1 Component concentration (% by volume) CF3CHF2 99.7171 CF3CF2C1 0.0005 CF3CH2F 0.0201 CF3CH3 0.2621 CHF3 0.0002 (Production Example of Catalyst) (Catalyst 1) Dissolve chromium nitrate 9 hydrate in water and mix with 28% by weight of ammonia water with stirring. A chromium hydroxide slurry. It was filtered, washed carefully with water and dried at 12 ° C. The obtained solid was pulverized, mixed with graphite, and pelletized by a tableting machine. The pellet was calcined at 400 ° C for 4 hours under a stream of N 2 to obtain a catalyst 1 in which the main component was trivalent chromium oxide. (Manufacture of catalyst) (Catalyst 2) Chlorinated platinum acid was dissolved in water, and a 3 mm 0 spherical alumina carrier was immersed to adsorb the platinum salt. Then, the solvent was distilled off at 100 ° C, and after calcination in air at 300 ° C, hydrogen reduction was carried out at 350 ° C. The platinum catalyst 2 obtained had a platinum loading ratio of 0.25%. (Example 1) An Inco Nickel 600 reactor having an inner diameter of 1 inch and a length of 1 meter is filled with a tap -16- (12) 1266759
媒（觸媒1 ) 100毫升，氮氣流通下保持溫度於3 00 °C。 其次以2.0標準升/小時之流速供給氧，以38.0標準升/小時 之流速供給組成如表1之氣體，然後停止氮氣之供給開始 反應。2小時後出自反應器之氣體用氫氧化鉀水溶液淸 洗去除酸分後，與分子篩3 A ( UNION昭和（股）製）接 觸乾燥。冷卻捕集該乾燥之主要成分係五氟乙烷之氣體， 以蒸禮純化。純化後之氣體以氣相層析分析，知係組成如 表2之氣體。 表2 成分 濃度（體積％) CF3CHF2 99.9665 CF3CF2C1 0.0004 cf3ch2f 0.0126 CF3CH3 0.0204 chf3 0.0001Medium (catalyst 1) 100 ml, kept at a temperature of 300 ° C under nitrogen flow. Next, oxygen was supplied at a flow rate of 2.0 standard liters/hour, and a gas having a composition as shown in Table 1 was supplied at a flow rate of 38.0 liters/hour, and then the supply of nitrogen gas was stopped to start the reaction. After 2 hours, the gas from the reactor was washed with an aqueous solution of potassium hydroxide to remove the acid, and then contacted with molecular sieve 3 A (manufactured by UNION Showa Co., Ltd.) to dry. The gas which is the main component of the drying, which is pentafluoroethane, is cooled and purified by steaming. The purified gas was analyzed by gas chromatography, and it was known to constitute a gas as shown in Table 2. Table 2 Ingredient Concentration (% by volume) CF3CHF2 99.9665 CF3CF2C1 0.0004 cf3ch2f 0.0126 CF3CH3 0.0204 chf3 0.0001
(實施例2 ) 除使用觸媒2以外，如同實施例1，得五氟乙院。純化 後之氣體以氣相層析分析，知其組成如表3。 -17- (13) (13)1266759 成分 濃度（體積％) cf3chf2 99.9840 cf3cf2ci 0.0004 cf3ch2f 0.0101 CF3CH3 0.0054 chf3 0.0001(Example 2) Except that the catalyst 2 was used, as in Example 1, a pentacene fluorene was obtained. The purified gas was analyzed by gas chromatography, and its composition was as shown in Table 3. -17- (13) (13)1266759 Component Concentration (% by volume) cf3chf2 99.9840 cf3cf2ci 0.0004 cf3ch2f 0.0101 CF3CH3 0.0054 chf3 0.0001
(實施例3 ) 於內徑1英吋，長50公分之鎳製反應器（電熱器加熱 ，反應器經5 00 t之氟氣作非動態化處理），由二氣體 導入口供給共計3 0標準升/小時流速之氮氣，保持反應器 溫度於42〇 °C。其次，由上述二氣體導入口流入共計50 標準升/小時流速之HF，由其一氣體導入口導入流速3. 5標 準升/小時之主要成分係五氟乙烷之混合氣體。並由另一 氣體導入口導入3. 8 5標準升/小時流速之氟氣進行反應。3 小時後，出自反應器之氣體與氫氧化鉀水溶液及碘化鉀水 溶液接觸，去除HF及未反應之氟氣。其次與脫水劑接觸 乾燥，冷卻捕集乾燥氣體後蒸餾純化。純化後之氣體以氣 相層析之TCD法、FID法、ECD法及GC_MS法分析，結果 列於表4。 -18- (14) 1266759 表4 成分 濃度[體積％] cf3cf3 >99.9998% cf4 <0.4 體積 ppm cf3cf2ci <0.1 體積 ppm CF3CHF2 <〇. 5 體積 ppm sf6 <〇·4 體積 ppm 由表4之分析結果可知，六氟乙烷幾乎不含其它雜質 ，得高純度六氯乙烷。 〔發明之效果〕 ^ 如以上說明，利用本發明之純化方法，可得高純度之 · 五氟乙烷。本發明所得之五氟乙烷可用作低溫冷媒，高純 度六氟乙烷製造用原料。 -19-(Example 3) A nickel reactor having an inner diameter of 1 inch and a length of 50 cm (heated by an electric heater, and the reactor was subjected to non-dynamic treatment by 500 volts of fluorine gas), and supplied by a total of three gas inlet ports. A standard liter/hour flow rate of nitrogen was maintained at a reactor temperature of 42 °C. Next, a HF having a flow rate of 50 standard liters/hour was introduced from the two gas inlet ports, and a flow rate of 3.5 liters per hour was introduced from a gas inlet port. The main component of the standard liter/hour was a mixed gas of pentafluoroethane. The reaction was carried out by introducing a fluorine gas at a flow rate of 3.8 5 liters/hour from another gas introduction port. After 3 hours, the gas from the reactor was contacted with an aqueous solution of potassium hydroxide and a solution of potassium iodide to remove HF and unreacted fluorine gas. Next, it is contacted with a dehydrating agent to be dried, and the collected drying gas is cooled and then distilled and purified. The purified gas was analyzed by gas chromatography, TCD method, FID method, ECD method and GC_MS method, and the results are shown in Table 4. -18- (14) 1266759 Table 4 Concentration of components [% by volume] cf3cf3 >99.9998% cf4 <0.4 Volume ppm cf3cf2ci <0.1 Volume ppm CF3CHF2 <〇. 5 Volume ppm sf6 <〇·4 Volume ppm by Table As can be seen from the analysis of 4, hexafluoroethane contains almost no other impurities, and high purity hexachloroethane is obtained. [Effects of the Invention] As described above, the high-purity pentafluoroethane can be obtained by the purification method of the present invention. The pentafluoroethane obtained by the present invention can be used as a raw material for producing a high-purity hexafluoroethane as a low-temperature refrigerant. -19-