200403206 ⑴ 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，㈣該方法製 得之五氟乙烷製造六氟乙烷之方自，以及五氟乙烷之用途 【先前技術】 五氟乙院（即、、CFsCHF2 〃）可用作例如，低溫冷 媒、触刻热體’及作爲六赢乙燒（即、、C 3 C f 3 〃 ）之製 造原料。 五氟乙院之製造方法，向來已知有下列，例如 (1) 四氯乙烯（即、、CC12 = CC12 ")或其氧化物 以氟化氫氟化之方法（日本專利特開平8-26 893 2號公報、 特表平9 - 5 1 1 5 1 5號公報）， (2) 氯五氟乙烷（即CF3CF2C1 〃 ）之氫化分解 方法（專利第2 5 4 〇 4 0 9號公報）， (3 ) 含鹵乙烯以氟氣反塵之方法（特開平1 - 3 8 0 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 於避免臭氧層之破壞，有種種純化方法之提議。尤以氯五 (2) . (2) .200403206 氟乙院因與五氟乙院沸點接近’通常之蒸靜難以分離’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 0 1 8 0 1號 公報）， (3 ) 氯五氟乙烷以氟化氫（HF )氟化後去除之方 法（特開2 ο 〇 1 -4 8 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- 5 0 8 62 7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1，1，1-三氟乙烷（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m —三 鲁 氟乙院之去除方法，已知有萃取蒸餾法。然而，該方法因 須多套蒸飽塔等昂貴設備，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、触刻氣體、或高純度六氟乙烷製造原料之高純度五 氯乙院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) (3)200403206 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（i) ’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 程。 (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 氧化合物接觸之過程 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 °C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 (4) (4)200403206 氟代甲烷、二氟甲烷、氟代乙烷、1，1-二氟乙烷、1，2_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150至400 °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、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1 5 0至4 0 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〇.1至2〇體積％爲佳。 本發明係經上述任一製造方法所得，雜質總量占5〇〇 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 (5) (5)200403206 六氟乙烷之過程 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（η -10- (6) 200403206 四氯乙烯之氟化以得含雜質之粗五氟乙烷之過卷 )觸媒存在下，使上述粗五氟乙烷與氧及/或含 接觸之過程。過程（1 )之方法無特殊限制，可 存在下，用氟化氫（HF )將四氯乙烯二段氟化 氟乙烷。 本發明係使五氟乙烷中所含，如氫氟化碳（ 雜質於接觸存在下，以氣相在1 5 0至4 0 0 之高7」 或含氧化合物接觸，使所含雜質氫氟化碳類氧化 C〇2等。例如，五氟乙烷中所含之二氟甲烷及1 乙烷，推測係經氧如下述式（a )、式（b )進行 〇 CH2F2 + 〇2_> C〇2 + 2HF 式（a) CF3CH3 + 2〇2— 2C02 + 3HF 式(b ) 主要氧化產物係C02，副產物係HF。 以該反應轉化爲C Ο 2之化合物有氟代甲烷、 、氟代乙烷、1，1-二氟乙烷、1，2 -二氟乙烷、ι，ι， 烷、1，1，2-三氟乙烷等。這些化合物用於包含氫 程之製造方法或純化方法時，於五氟乙烷中通常 的數千P P m。這些雜質從五氟乙烷的高度純化之 去除。 本發明的五氟乙烷之製造方法中，粗五氟乙 氟化碳（HFC )等雜質總量以2體積％以下又更< 積％以下更佳’ 0.3體積。/。以下又更佳。氫氟化碳 含量若超過2體積％，則反應溫度高，觸媒壽命 I，及（2 氧化合物 於觸媒之 ，得粗五 HFC )之 昆與氧及/ ，轉化爲 ,1 , 1 -二氣 氧化反應 二氟甲烷 1 -三氟乙 化分解過 約占總纛 觀點須予 烷所含氫 圭，0.5體 類等雜質 短0 -11 - (7) (7)200403206 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（Π )主要成分係選自鈀、鍺、 釕、鍊、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1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、铑、釕 、鍊、鈾及/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。200403206 玖 发明, description of the invention [Technical field to which the invention belongs] The present invention relates to a method for producing pentafluoroethane. The pentafluoroethane produced by this method is used to produce hexafluoroethane, and pentafluoroethane. Uses [Prior art] Pentafluoroethanes (ie, CFsCHF2 〃) can be used as, for example, low-temperature refrigerants, engraved hot bodies' and as raw materials for the production of six-win acetic acid (ie, C 3 C f 3 〃) . The manufacturing method of Pentafluoroethane House has been known as follows, for example (1) Tetrachloroethylene (ie, CC12 = CC12 ") or a method of fluorinating it with hydrogen fluoride (Japanese Patent Laid-Open No. 8-26 893 (2) Hydrogenation method of chloropentafluoroethane (that is, CF3CF2C1 〃) (Patent No. 2 504 0409), (3) A method for anti-dusting of halogenated ethylene with fluorine gas (Japanese Patent Application Laid-Open No. 1-3 0 034) and the like. When these manufacturing methods are used, the target product pentafluoroethane contains impurities such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). To obtain high-purity pentafluoroethane, these impurities must be removed as much as possible. Among these impurities, in addition to the purpose of highly purified CFCs, various purification methods have been proposed based on avoiding damage to the ozone layer. Especially chlorine five (2). (2) .200403206 Fluoroethane is close to Pentafluoroe in the boiling point of 'usual vaporization is difficult to separate' and there are proposals for the following purification methods', such as ~ (1) extractive distillation ( Japanese Patent Publication No. 9-508626) '-(2) Hydrogenation of chloropentafluoroethane (Japanese Unexamined Patent Publication No. 8-3 0 1 8 0 1), (3) Chloropentafluoroethane with hydrogen fluoride (HF ) Removal method after fluorination (Japanese Patent Application Laid-Open No. 2 ο 〇1-4 8 8 16) and the like. On the other hand, separation and purification of HFCs and HFCs are rarely proposed. For example, only the extractive purification method of JP 9- 5 0 8 62 7 method. Among the hydrofluorocarbons and hydrofluorocarbons, difluoromethane (ie, ★ CH2F2〃) and 1,1,1-trifluoroethane (ie, CF3CH3〃) are known to form Boiling mixtures are compounds that are very difficult to separate from pentafluoroethane. When pentafluoroethane is produced by a method involving hydrodecomposition, as a result of excessive hydrodehalogenation reaction, the possibility of forming by-product 1,1,1-trifluoroethane is increased. The content of pentafluoroethane is relatively high. Extraction distillation method is known as the method of removing pentafluoroethane m-Sanlu. However, this method requires multiple sets of expensive equipment, such as a steam-saturation tower, and has a problem that equipment costs increase. [Problems to be Solved by the Invention] Against this background, the subject of the present invention is to provide a high-purity pentachloroethene industry that can be used as a low-temperature refrigerant, a contact gas, or a high-purity hexafluoroethane production material. Advantageous manufacturing method, industrially advantageous manufacturing method of high-purity pentafluoroethane, and manufacturing method of hexafluoroethyl (3) (3) 200403206 alkane of pentafluoroethane obtained by the method, and pentafluoroethane use. [Summary of the Invention] [Means to Solve the Problems] The present inventors have carefully studied the results to solve the above problems and found that the process (i) of the use of fluorination containing tetrafluoroethylene to obtain crude pentafluoroethane containing impurities is In the presence of a medium, the method for producing pentafluoroethane in the process (2) of contacting the crude pentafluoroethane containing impurities with oxygen and / or oxygen-containing compounds can solve the above problems and finally complete the present invention. The method for producing pentafluoroethane according to the present invention is characterized by including the following processes. (1) the process of fluorinating tetrafluoroethylene to obtain crude pentafluoroethane (2) the process of contacting the above crude pentafluoroethane with oxygen and / or oxygen-containing compounds in the presence of a catalyst is used in the process (2) The crude pentafluoroethane is preferably obtained by contact with hydrogen. The temperature of the process (2) is preferably 150 to 400 ° C. The catalyst is preferably a supported type or a block type catalyst whose main component is trivalent chromium oxide. The catalyst is preferably a supported catalyst whose main component is at least one metal selected from the group consisting of palladium, germanium, ruthenium, osmium, platinum, and gold. The carrier used for the supporting catalyst is preferably aluminum oxide, fluorinated alumina or zeolite. The main constituent of crude pentafluoroethane is pentafluoroethane, which may contain impurities and is selected from (4) (4) 200403206 fluoromethane, difluoromethane, fluoroethane, 1,1-difluoroethane, At least one of the group consisting of 1,2-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 by contacting crude pentafluoroethane with oxygen and / or oxygen-containing compounds at a temperature of 150 to 400 ° C in the presence of a catalyst whose main component is trivalent alumina, Secondly, impurities are separated by distillation. In addition, the method for producing pentafluoroethane according to the present invention is characterized in that the main component is in the presence of a supported catalyst of at least one metal selected from the group consisting of palladium, rhodium, ruthenium, chains, platinum, and gold. The crude pentafluoroethane is contacted with oxygen and / or oxygen-containing compounds at 150 to 400 ° C, followed by distillation to separate impurities. Crude pentafluoroethane may contain at least trifluoroethane as an impurity. The concentration of oxygen and / or oxygen-containing compounds is preferably from 0.1 to 20% by volume. The present invention is obtained by any one of the above manufacturing methods, and the total amount of impurities is pentafluoroethane of 500 volume ppm or less. The content of the 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 according to the present invention is characterized by including the following processes. (1) Process of fluorinating tetrachloroethylene to obtain crude pentafluoroethane (2) Process of contacting the above crude pentafluoroethane with oxygen and / or oxygen-containing compounds to obtain pentafluoroethane in the presence of a catalyst (3) The process of pentafluoroethane obtained by process (2) is reacted with fluorine gas to obtain (5) (5) 200403206 The process of hexafluoroethane is used in the process of (2) to produce crude pentafluoroethane It is preferred to obtain the hydrogen contact process. [Embodiment] The present invention will be described in detail below. As described above, pentafluoroethane can be produced by a method of fluorinating tetrachloroethylene or its fluoride with hydrogen fluoride (HF), or a method of hydrolyzing chloropentafluoroethane. Regardless of the method used, the pentafluoroethane obtained through purification processes such as general distillation operations contains chloropentafluoroethane, an impurity that 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 a requirement for non-chloropentafluoroethane. As the method for separating chloropentafluoroethane contained in pentafluoroethane, as mentioned above, there have been proposed hydrogenation decomposition method, extractive distillation method, and adsorption method. Among these methods, in consideration of the equipment cost, etc., those capable of producing pentafluoroethane at low cost are hydrogenolysis methods. Here, when the method for producing or purifying pentafluoroethane is selected to include a method of hydrolytic decomposition, there will be a result of excessive hydrogenation reaction. 'Hydrofluorination such as 1,1,1-trifluoroethane, which is difficult to separate, is produced. Carbon (HFC). In particular, the boiling points of difluoromethane and trifluoroethane are very close to those of pentafluoroethane, and it is known that azeotropic mixtures can be formed, which are difficult to separate by general purification methods such as distillation. The separation method of hydrofluorocarbon (HCF) contained in pentafluoroethane Although the above-mentioned extractive distillation method is proposed, there are problems that expensive equipment such as multiple distillation columns is required, and the equipment cost is inflated. The method for producing pentafluoroethane according to the present invention is characterized in that: the catalyst containing (η -10- (6) 200403206 fluorination of tetrachloroethylene to obtain crude pentafluoroethane containing impurities is used) in the presence of a catalyst; The process of contacting the above crude pentafluoroethane with oxygen and / or containing. The method of the process (1) is not particularly limited, and in the presence of hydrogen fluoride (HF), tetrachloroethylene is fluorinated in two stages. The present invention involves contacting pentafluoroethane, such as hydrofluorocarbon (impurities in the presence of contact, in the gas phase at a height of 1 500 to 4 0 7 ″ or oxygen-containing compounds to make the contained hydrogen hydrogen Carbon fluoride is used to oxidize CO2, etc. For example, difluoromethane and 1 ethane contained in pentafluoroethane are presumed to be subjected to oxygen such as the following formula (a) and formula (b): 〇CH2F2 + 〇2_ > Co2 + 2HF Formula (a) CF3CH3 + 2〇2-2C02 + 3HF Formula (b) The main oxidation product is C02 and the by-product is HF. The compounds converted into C 0 2 by this reaction are fluoromethane, fluoro Ethane, 1,1-difluoroethane, 1,2-difluoroethane, ι, ι, alkane, 1,1,2-trifluoroethane, etc. These compounds are used in the production process including the hydrogen range Or purification method, usually thousands of PP m in pentafluoroethane. These impurities are removed from the highly purified pentafluoroethane. In the method for producing pentafluoroethane of the present invention, crude pentafluoroethane fluoride The total amount of impurities such as (HFC) is 2% by volume or less; < Volume% or better is better than 0.3%. The following is even better. If the content of hydrofluorocarbon exceeds 2% by volume, the reaction temperature is high. , Catalyst life I, and (2 oxygen compounds in the catalyst, to get crude five HFC) and Kun and oxygen and /, converted to, 1, 1-two-gas oxidation reaction difluoromethane 1-trifluoroacetic decomposition About the total amount of tritium, the content of hydrogen contained in alkane, 0.5 and other impurities is shorter than 0 -11-(7) (7) 200403206 The catalyst used for the reaction is based on (i) trivalent chromium oxide as the main component. Supported or massive catalysts, or (Π) supported catalysts of at least one metal selected from the group consisting of palladium, germanium, ruthenium, chains, platinum, or gold. These metals can be used as raw materials for oxidation Materials or salts, etc. In addition, alumina, fluorinated alumina, or zeolite can be used as a carrier. The method of preparing the catalyst (i) whose main component is trivalent chromium oxide is, for example, ammonia. After the alkaline substance is dropped into the chromium metal salt aqueous solution to precipitate chromium hydroxide, it is washed and filtered. The dried chromium hydroxide is formed, and then heated in the presence of an inert gas such as nitrogen. The main components are palladium, The preparation method of the supported catalyst (ii) of rhodium, ruthenium, chain, uranium and / or gold may be, for example, the above-mentioned metal salt Solutions, for example, a water-soluble solvent such as water, methanol or acetone, dipping the support to adsorb the necessary elements. Then the solvent was distilled off, and the like for heating the hydrogen 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2 0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) (8)200403206 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C Ο 2、非主反 應所致氫氟化碳類等副產物、HF等酸分，故以將C 02、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C 02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15〇至 4 0 0 °C接觸，其次以蒸餾分離雜質之五氟乙院製造方法 〇 又’本發明係其特徵爲：主要成分係選自鈀、鍺、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’使粗五氟乙院與氧及/或含氧化合物於150至4〇〇 。〇接 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，可經一般所用之蒸飽 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2百萬帕則須局壓系之設備而不佳。例如用氧進行 上述之接觸反應時，含氧之低沸分自蒸飽塔頂抽出，高沸 -13- (9) (9) 200403206 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’可得筒純度五氟乙院。雜質含量在 5〇〇體積ppm以下。純度99.95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。 φ 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/丨，112 -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 鲁 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（丨）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 上述粗五氟乙院與氧及/或含氧化合物接觸之過程，以及 (3 )經過程（2 )所得五氟乙烷與氟氣反應之過程的六氟 乙烷之製造方法。 -14- (10) (10)200403206 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’尚純度五赢乙院，或與H e、N 2 ' A r等惰性氣 ，HC1、〇2、I等之混合氣體，可用作半導體裝置之製程 中，蝕刻過程之蝕刻氣體。LSI、TFT、有機EL等半導體 裝置之製程中，係用C VD法、濺鍍法或蒸鍍法等形成薄膜 、厚膜，爲形成電路圖型進行蝕刻時，含上述五氟乙烷之 混合氣體可用作蝕刻氣體。使用五氟乙烷之蝕刻方法，可 於電漿蝕刻、微波蝕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〇。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) 200403206 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 cf3cf2ci 0.0005 CF3CH2F 0.020 1 CF3CH3 0.262 1 CHF3 0.0002The temperature of process (2) is preferably 150 to 400 ° C, and more preferably 180 to 3 70 ° C. If the reaction temperature is higher than 400 ° C, the catalyst life tends to be short, and the types and amounts of by-products not due to the main reaction increase. The concentration of oxygen and / or oxygen-containing compounds in the reaction matrix gas is preferably 0.1 to 20% by volume. The oxygen may be high-purity oxygen or air, and high-purity oxygen is preferred. When the oxygen concentration is less than 0.1% by volume, although it varies with the type and amount of the hydrofluorocarbons contained in the pentafluoroethane, the oxygen is not enough for the reaction and the conversion rate is low. If the oxygen concentration is higher than 20% by volume, an excessive reaction occurs, and the main component of the reaction matrix gas, pentafluoroethane, undergoes a decomposition reaction, and the consumption of pentafluoroethane is increased in an economically unfavorable manner. As the oxygen-containing compound, nitric oxide (NO), nitrous oxide (N20), nitrogen dioxide (NO2), or odorous (8) (8) 200403206 oxygen (〇3) can be used. The method for producing pentafluoroethane according to the present invention can be carried out under the above reaction conditions, but the reaction products other than pentafluoroethane contain C 0 2, by-products such as hydrofluorocarbons caused by non-main reactions, HF and other acids, so it is better to remove C 02 and acids. The acid can be removed by, for example, a method of contacting a purifying agent, a method of contacting water, an alkaline aqueous solution, and the like. The gas from which the acid has been removed is preferably dehydrated with a dehydrating agent such as zeolite, and then C02 is distilled off, and at the same time, by-products caused by the above-mentioned non-main reaction are preferably removed. The present invention is also characterized in that crude pentafluoroethane is contacted with oxygen and / or an oxygen-containing compound at 150 to 400 ° C in the presence of a catalyst containing trivalent chromium oxide as a main component, followed by distillation. Method for producing pentafluoroethane for separation of impurities. The present invention is characterized in that the main component is a supported catalyst containing at least one metal selected from the group consisting of palladium, germanium, ruthenium, chain, platinum, and gold. Next 'put the crude pentafluoroacetate with oxygen and / or oxygenates at 150 to 400. 〇 Contacting a method for producing pentafluoroethane followed by distillation and separation of impurities. After the reaction, the purification method is not particularly limited, and it can be purified by steam-saturation generally used. For the distillation, the following method can be used, for example. Crude pentafluoroethane and oxygen and / or oxygenate gas contacted in the reactor at 150 to 400 ° C are introduced into the distillation column. The pressure in the distillation column is preferably in the range of atmospheric pressure to 2 million Pascals. If it is lower than atmospheric pressure, it must be decompressed. If it exceeds 2 million Pa, it must be depressurized. For example, when carrying out the above-mentioned contact reaction with oxygen, the low boiling point containing oxygen is extracted from the top of the steam-saturated column, and the high boiling point is extracted from the bottom of the distillation column. At this time, the components extracted from the top and bottom of the column include the target component pentafluoroethane, which can be introduced into a distillation column to purify and recover pentafluoroethane. When the separation component is an intermediate for the production of pentafluoroethane, it can be returned to the reaction process-reuse. After such purification ', the cartridge purity of pentafluoroethane was obtained. The impurity content is 500 ppm by volume or less. An analysis method of pentafluoroethane having a purity of 99.95% by volume or more includes a gas chromatography (GC) method of TCD, a FID method, or a gas chromatography-mass spectrometry (GC-MS) method. φ Next, the use of pentafluoroethane obtained by the production method of the present invention will be explained. 0 High-purity pentafluoroethane can be used as a substitute for chlorodifluoromethane (CHF2C1), which is currently used as a cryogenic freezer as a fluid. It can also be used as a raw material for other refrigerants such as difluoromethane / pentafluoroethane / 112, tetrafluoroethylene, difluoromethane / pentafluoroethane. Also, 'high-purity pentafluoroethane can be used as a raw material for producing high-purity hexafluoroethane. In particular, in the production process for producing hexafluoroethane by reacting pentafluoroethane with fluorine gas (F2), the use of high-purity pentafluoroethane as a raw material prevents the generation of impurities that are difficult to separate from hexafluoroethane. The range of fluorination reaction conditions is expanded, which can be stably controlled, and the purification process is simplified. Therefore, the present invention is characterized by: a process comprising (丨) fluorination of tetrachloroethylene to obtain crude pentafluoroethane containing impurities, (2) in the presence of a catalyst, the above crude pentafluoroethane compound and oxygen and / Or a process of contacting an oxygen-containing compound, and (3) a method for producing hexafluoroethane in the process of reacting pentafluoroethane obtained from the process (2) with fluorine gas. -14- (10) (10) 200403206 The crude pentafluoroethane in process (2) is preferably the one obtained by contact with hydrogen. It's still pure and clean, and can be used as an etching gas in the etching process of semiconductor devices in the manufacturing process of semiconductor devices, such as inert gases such as He, N2'Ar, and HC1, 02, and I. In the manufacturing process of LSI, TFT, organic EL and other semiconductor devices, thin films and thick films are formed by CVD method, sputtering method, or evaporation method. When etching is performed to form a circuit pattern, a mixed gas containing the above pentafluoroethane is used. Can be used as an etching gas. The etching method using pentafluoroethane can be performed under various dry etching conditions such as plasma etching and microwave etching. [Embodiments] The present invention will be described in more detail by the following examples, but the present invention is not limited to these examples. (Examples of raw materials of pentafluoroethane) Introduction of tetrachloroethylene and hydrogen fluoride into the first reactor filled with a catalyst to produce a main component of the intermediate 1,1,1-trifluoro-2,2-dichloroethane And 1,1,1,2-tetrafluoro-2-chloroethane gas is introduced into the second reactor together with HF to produce pentafluoroethane. The pentafluoroethane was distilled to obtain the impurity pentafluoroethane. 5% pentafluoroethane. The above pentafluoroethane was reacted with hydrogen in the presence of a commercially available hydrogenation catalyst (reaction pressure 0.3 5 MPa, reactor temperature 280 ° C, H2 / chloropentafluoroethane mole ratio = 5). The acid was removed from the obtained mixed gas by a known method, and then purified by distillation to obtain a distillate containing pentafluoroethane as a main component. The distillate was analyzed by gas chromatography (15)-(11) 200403206. The composition of the distillate is shown in Table 1 as a mixed gas. Table 1 Ingredient Concentration (% by volume) CF3CHF2 99.7171 cf3cf2ci 0.0005 CF3CH2F 0.020 1 CF3CH3 0.262 1 CHF3 0.0002
(觸媒之製造例） （觸媒i) 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 1 2 〇 °c乾燥。所得固體予以粉碎，混合以石墨，用打锭 成形機％I料化。該粒料在N2氣流下於4 〇 〇 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fe入以吸附鈉鹽。然後於1 0 0它I留去溶劑，在3 〇 〇它 空氣中锻燒後，於3 5 0 。(：進行氫還原。所得鉑觸媒2之鉑 載持率爲〇 . 2 5 %。 (實施例1 ) 內徑1英吋’長i米之因科鎳6〇〇反應器內充塡以觸 -16- (12) 200403206(Production example of catalyst) (Catalyst i) Chromium nitrate 9 hydrate was dissolved in water, and 28% by weight of ammonia water 'was mixed with stirring to obtain a chromium hydroxide slurry. It was filtered, rinsed carefully with water, and dried at 120 ° C. The obtained solid was pulverized, mixed with graphite, and pelletized with an ingot molding machine% I. The pellets were calcined under a stream of N2 at 400 for 4 hours to obtain Catalyst 1 whose main component is trivalent chromium oxide. (Production granules of catalyst) (Catalyst 2) Dissolve platinum chloride in water, and add a 3 mm 0 spherical alumina support fe to adsorb sodium salts. Then the solvent was removed at 100 ° C, and it was calcined in air at 3500 ° C, at 350 ° C. (: Hydrogen reduction is performed. The platinum loading ratio of the obtained platinum catalyst 2 is 0.25%. (Example 1) The Inco nickel 600 reactor with an inner diameter of 1 inch and a length of 1 meter was charged with Touch-16- (12) 200403206
媒（觸媒1 ) l 〇 〇毫升’氮氣流通下保持溫度於3 ο 〇 °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3A ( 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， 以蒸餾純化。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 'of nitrogen was maintained at a temperature of 3 ° C under a nitrogen flow. Next, oxygen was supplied at a flow rate of 2.0 standard liters / hour, and a gas having a composition shown in Table 1 was supplied at a flow rate of 38.0 standard liters / hour, and then the supply of nitrogen was stopped to start the reaction. After 2 hours, the gas from the reactor was washed with an aqueous potassium hydroxide solution to remove the acid, and then dried by contacting with molecular sieve 3A (manufactured by UNION Showa Corporation). The dry main component is pentafluoroethane gas, which is cooled and purified by distillation. The purified gas was analyzed by gas chromatography, and its composition was as shown in Table 2. Table 2 Ingredient Concentration (vol.%) 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，得五氟乙烷。純化 後之氣體以氣相層析分析，知其組成如表3。 -17- (13) (13)200403206 表3 成分 濃度（體積％) cf3chf2 99.9840 CF3CF2C1 0.0004 CF3CH2F 0.0101 CF3CH3 0.0054 CHF3 0.0001(Example 2) Except that the catalyst 2 was used, as in Example 1, pentafluoroethane was obtained. The purified gas was analyzed by gas chromatography, and its composition is shown in Table 3. -17- (13) (13) 200403206 Table 3 Ingredient Concentration (vol.%) Cf3chf2 99.9840 CF3CF2C1 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 〇 〇 °C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) (14)200403206 表4 成分 濃度[體積％] cf3cf3 >99.9998% cf4 <〇·4 體積 ppm cf3cf2ci <〇 . 1 體積 ppm CF3CHF2 <0.5 體積 ppm sf6 <0.4 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 with an inner diameter of 1 inch and a length of 50 cm (heated by an electric heater, and the reactor was treated with non-dynamic treatment by fluorine gas at 500 ° C) was supplied from two gas introduction ports in total. Maintain the reactor temperature at 40 ° C with a nitrogen flow rate of 30 standard liters / hour. Secondly, HF with a total flow rate of 50 standard liters / hour flows into the two gas introduction ports, and the main component is a mixed gas of pentafluoroethane with a flow rate of 3.5 standard liters / hour introduced from one of the gas introduction ports. Fluorine gas with a flow rate of 3.85 standard liters / hour was introduced from another gas introduction port for reaction. After 3 hours, the gas from the reactor was contacted with an aqueous potassium hydroxide solution and an aqueous potassium iodide solution to remove HF and unreacted fluorine gas. It is then dried by contacting with a dehydrating agent, and cooled to capture dry gas, and then purified by distillation. The purified gas was analyzed by TCD, FID, ECD and GC-MS methods of gas chromatography. The results are shown in Table 4. -18- (14) (14) 200403206 Table 4 Component concentration [vol.%] Cf3cf3 > 99.9998% cf4 < 〇4 volume ppm cf3cf2ci < 〇. 1 volume ppm CF3CHF2 < 0.5 volume ppm sf6 < 0.4 volume ppm From the analysis results in Table 4, it can be seen that hexafluoroethane contains almost no other impurities, and high-purity hexachloroethane is obtained. [Effects of the Invention] As described above, by using the purification method of the present invention, high-purity pentafluoroethane can be obtained. The pentafluoroethane obtained by the present invention can be used as a low-temperature refrigerant and a raw material for producing high-purity hexafluoroethane. -19-