TWI272262B - Process for purifying pentafluoroethane, process for producing the same, and use thereof - Google Patents
Process for purifying pentafluoroethane, process for producing the same, and use thereof Download PDFInfo
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- TWI272262B TWI272262B TW092117959A TW92117959A TWI272262B TW I272262 B TWI272262 B TW I272262B TW 092117959 A TW092117959 A TW 092117959A TW 92117959 A TW92117959 A TW 92117959A TW I272262 B TWI272262 B TW I272262B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
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Abstract
Description
1272262 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關五氟化乙烷之精製方法及製造方法、以 及五氟化乙烷之用途。 【先前技術】 五氟化乙烷（以下或作、、cf3chf2〃 ）係用作例如， 低溫冷媒、蝕刻氣體’以及六氟乙烷（以下或作、、CF3cf3 〃）之製造原料。 五氟化乙烷之製造，習知方法如下。例如， (1)四氫乙烯（以下或作、、CC12=CC12〃 ）或其氟 化物以氟化氫氟化之方法（日本專利特開平8-268932號 公報等）， (2 )氯五氟化乙烷（以下或作'、c F 3 C1F 2 〃 ）之還原 氫化法（專利2 54〇4〇9號公報等）， (3)含鹵乙烯以氟氣反應之方法（特開平38〇34 號公報等） 等。 以此等方法製造之五氟化乙烷含氫氯碳（HCC )類、 氯氟碳（CFC)類、氫氯氟碳（HCFC)類、氫氟碳（HFC )類等種種雜質。 爲得高純度之五氟化乙烷，這些雜質須層可能去除。 這些雜質當中之氯氟碳類等除爲純化以外，爲防臭氧層之 破壞，有種種精製方法之提議。氯五氟化乙烷沸點與五氟 -4 - 1272262 (2) 化乙烷相近，難藉通常之蒸餾分離，但可用例如以下之精 製方法。 (1)萃取蒸餾法（特表平9— 508626號公報等）， (2 )氯五氟化乙烷的還原氫化法（特開平8 — 301801號公報等）， (3 )氯五氟化乙烷以氟化氫（HF )氟化後去除之方 法（特開平200 1 - 48 8 1 6號公報等）， (4 )以吸附劑吸附去除之方法（特開平6 — 9 2 8 7 9號 公報等）。 相對於此，氫氯碳類之一，氯甲烷（以下或作 CHgCK )與五氟化乙烷形成共沸混合物、共沸用混合物 ’極難與五氟化乙烷分離。而氫氟碳類之一、二氟甲烷（ 以下或作、、CH2F2〃 ）及1，1，1 一三氟乙烷（以下或作 ''CF3CH3〃 ）與五氟化乙烷形成共沸混合物、共沸用混 合物，亦極難與五氟化乙烷分離。 如此之難以分離的氫氯碳類、氫氟碳類雜質，其精製 去除方法已知有例如，萃取蒸餾精製法、以活性碳吸附去 除之精製方法。然而，萃取蒸餾精製法因需多數之蒸餾塔 等昂貴設備，有設備成本高之問題。而以活性碳吸附之精 製方法亦不得充分之效果。 【發明內容】 本發明在如此之背景下，其目的在提供可用作低溫冷 媒、蝕刻氣體之高純度五氟化乙烷的工業上有利之精製方 -5- 1272262 (3) 法。又，本發明之目的在提供，五氟化乙烷之製造方法及 五氟化乙烷的用途。 本發明人爲達上述目的，精心探討終於發現，使含至 少一種選自含一碳原子之氫氟碳類、含一碳原子之氫氯氟 碳類及含一碳原子之氫氯碳類所成群之化合物的粗五氟化 乙烷，與平均孔徑3埃至6埃，並且矽/鋁比在2.0以下 之沸石及/或平均孔徑3 · 5埃至6埃的碳吸附劑所成之吸 附劑接觸，降低粗五氟化乙烷中上述雜質化合物之含量的 方法，可用以達成上述目的，而完成本發明。本發明即以 下〔1〕至〔1 3〕之五氟化乙烷的精製方法及製造方法、 以及其用途。 〔1〕五氟化乙烷之精製方法，其特徵爲：使含至少 一種選自含一碳原子之氫氯碳類、含一碳原子之氫氯氟碳 類及含一碳原子之氫氯碳類所成群之化合物的粗五氟化乙 烷，與平均孔徑3埃至6埃，並且矽/鋁之比2.0以下之 沸石及/或平均孔徑3 . 5埃至6埃的碳吸附劑所成之吸附 劑接觸，以降低粗五氟化乙烷中所含雜質，上述化合物之 含量。 〔2〕如〔1〕之方法，其中上述含一碳原子之氫氟碳 類係至少一種選自氟甲烷、二氟甲烷及三氟甲烷所成群之 化合物。 〔3〕如〔1〕之方法，其中上述含一碳原子之氫氯氟 碳類係氯二氟甲烷。 〔4〕如〔1〕之方法，其中上述含一碳原子之氫氯碳 -6 - 1272262 (4) 類，係至少一選自氯甲烷、二氯甲院及三氧甲烷所成群之 化合物。 〔5〕如〔1〕之方法’其中粗五氟化乙烷含雜質，上 述化合物之總含量在1體積％以下。 〔6〕如〔1〕之方法，其中粗五氟化乙烷與上述吸附 劑之接觸壓力在1百萬帕以下。 〔7〕如〔1〕之方法，其中粗五氟化乙烷所含雜質， 上述化合物之總含量降低至1 5 0體積PPm以下。 〔8〕如〔1〕之方法’其中粗五氟化乙烷所含雜質， 含—碳原子之氫氟碳類的總含量降低至1〇0體積ppm以 下。 〔9〕如〔1〕之方法，其中粗五氟化乙烷所含雜質， 含一碳原子之氫氟碳類的總含量降低至5 0體積ppm以下 〇 〔1 〇〕如〔1〕之方法，其中粗五氟化乙烷係得自包 含以下過程之方法。 (1)使選自四氯乙烯、2，2 —二氯一 1，1，1 一三 氣乙烷及2 —氯—1，1，1，2 —四氟乙烷所成群之至少~ ® ’與氟化氫在氟化觸媒的存在下反應以得五氟化乙烷之 過程。 (2 )使過程（1 )得之五氟化乙烷與氫接觸之過程 ’ @程（1 )得之五氟化乙烷與氧及/或含氧化合物接 ® t @程，或使過程（丨）得之五氟化乙烷與氫接觸，再 @ _及/或含氧化合物接觸之過程。 1272262 (5) 〔1 1〕五氟化乙烷之製造方法，其特徵爲：包含以下 過程。 (1)使選自四氯乙烯、2，2 —二氯一 1，1，1〜Η 氟乙院及2 —氯—1，1，1，2-四氟乙院所成群之至少〜 種與氟化氫在氟化觸媒之存在下反應，得五氟化乙烷之過 程 使過程（1 )得之五氟化乙烷與氫接觸之過程，使 過程（1 )得之五氟化乙烷與氧及/或含氧化合物接觸之 過程’或使過程（丨）得之五氟化乙烷與氫接觸，再與氧 及/或含氧化合物接觸之過程 (3)過程（2)得之五氟化乙院用〔1〕至〔1〇〕 中的任一方法精製之過程 〔12〕六氟乙烷之製造方法，其特徵爲：用〔1〕至 〔10〕中任一方法精製之五氟化乙烷，使之與氟氣反應。 〔1 3〕冷媒’其特徵爲：含經〔1〕至〔1 〇〕中任一 方法精製之五氟化乙烷。 【實施方式】 以下詳細說明本發明。 以上’五氟化乙烷之製造方法已知有例如，四氯乙烯 或其氣化物，於氟化觸媒之存在下以氟化氫（HF )氟化 之方法。 乂 方法製造五化乙院時，雖施以一般蒸|留操作等 之精製過程’仍含難與五氟化乙烷分離之雜質。該等雜質 -8 - 1272262 (6) 有例如，氫氟碳類、氫氯氟碳類、氫氯碳類。這些雜質， 在使用氯五氟化乙烷於觸媒存在下以氫還原之方法時亦同 樣含有。因此，爲精製五氟化乙烷以高度純化，這些雜質 須予去除。 本發明之五氟化乙烷的精製方法，其特徵爲：使含至 少一種選自含一原子之氣氣類、含一碳原子之氫氯氟 碳類及含一碳原子之氫氯碳類所成群的化合物之粗五氟化 乙烷，與平均孔徑3埃至6埃，且矽/鋁比2.0以下之沸 石及/或平均孔徑3 · 5埃至6埃的碳吸附劑所成之吸附劑 接觸，降低粗五氟化乙烷中所含雜質，上述化合物之含量 〇 含於粗五氟化乙烷之雜質，含一碳原子之氫氟碳類， 係至少一種選自氟甲烷、二氟甲烷及三氟甲烷所成群之化 合物。含一碳原子之氫氯氟碳類，係氯二氟甲烷；含一碳 原子之氫氯碳類係至少一種選自氯甲烷、二氯甲烷及三氯 甲烷所成群之化合物。含這些雜質之粗五氟化乙烷難以僅 經蒸餾操作精製，本發明人等乃考量吸附劑之極性、孔徑 等，一再變化吸附劑之種類、吸附條件等，重複探討。 結果發現，以平均孔徑3埃至6埃，且矽/鋁比（Si / A1比）2.0以下之沸石接觸，可選擇性吸附去除上述雜 質。矽/鋁比2.0以下，若平均孔徑不及3埃或超過6埃 之沸石仍不見有減少上述雜質之效果。又，平均孔徑在3 埃至6埃之範圍，而矽/鋁比超過2 · 0之沸石，亦不見有 減少上述雜質之效果。 -9- 1272262 (7) 又發現，與平均孔徑·3 .5埃至6埃之碳吸附 篩碳）接觸，可選擇性吸附去除上述雜質。但， 孔徑不及3.5埃或超過6埃之碳吸附劑時，則不 述雜質之效果。例如，一般所用平均孔徑在3 5 活性碳，已知具高度吸附能力，卻不見有減少上 效果。 上述沸石，上述碳吸附劑可各單獨使用，亦 比例組合二者使用。 粗五氟化乙烷所含雜質，上述雜質之總含量 %以下爲佳，0.5體積％以下更佳。雜質總含量1 上時吸附劑之用量變大，設備成本亦高故不佳。 本發明之五氟化乙烷的精製方法中，使含上 粗五氟化乙烷與上述吸附劑接觸之方法無特殊限 例如，氣相接觸法、或液相接觸法之任一，液相 率高而較佳。液相接觸法可用批次式、連續式等 ，可用例如，設二固定床式吸附塔，其一達飽和 換再生之方法。使粗五氟化乙烷與吸附劑接觸之 1百萬帕以下爲佳，該壓力若高於1百萬帕則設 高而不佳。 粗五氟化乙院較佳者爲得自包含以下過程之 (1)選自四氯乙烯、2，2 —二氯—1，1，1 烷及2-氯一 1，1，1，2-四氟乙烷所成群之至 氟化氫’於氟化觸媒之存在下反應得五氟化乙烷_ (2 )使過程（1 )所得之五氟化乙烷與氫接 劑（分子 使用平均 見減少上 埃左右之 述雜質之 可以任意 以1體積 體積％以 述雜質之 制，可係 接觸法效 已知方法 吸附時切 壓力以在 備成本提 方法者。 一三氟乙 少一種與 之過程， 觸之過程 -10- 1272262 (8) ’使過程（1 )所得之五氟化乙烷與氧及/或含氟化合物 接觸之過程，或使過程（1 )所得之五氟化乙烷與氫接觸 ’其次與氧及/或含氟化合物接觸之過程。 過程（1 )可用，以例如四氯乙烯爲起始原料，於氟 化觸媒之存在下與氟化氫行二段氟化反應，得五氟化乙烷 之方法。氟化觸媒之較佳者爲，以三價氧化鉻爲主成分之 載持型或塊狀型觸媒。 過程（2 )中，使過程（1 )所得之五氟化乙烷與氫接 觸時，其觸媒可係選自鈀、铑、釕、銶、鈾及金所成群之 至少一種載持於載體之載持型觸媒。反應溫度係在1 5 0至 4 0 0 °C之範圍，經與氫接觸行例如氫氯碳類之還原氫化反 應。 又，過程（2 )中使過程（1 )所得之五氟化乙烷與氧 及/或含氧化合物接觸時，其觸媒可係以三價氧化鉻爲主 成分之載持型觸媒或塊狀型觸媒，或選自鈀、铑、釕、銶 、鉑及金所成群之至少一種載持於載體之載持型觸媒。反 應溫度在150至400 °C之範圍。含氧化合物可用一氧化氮 (NO)、氧化亞氮（N20)、二氧化氮（N02)或臭氧（ 〇3 )。經該處理，所含雜質氫氟碳類可氧化成C02等。 過程（2 )較佳者爲，使過程（1 )所得之五氟化乙烷與氫 接觸後，與氧及/或氧化合物接觸。 粗五氟化乙烷中所含雜質，上述化合物經上述吸附劑 之處理後，五氟化乙烷中所含上述化合物總含量可降低至 150體積ppm以下，甚至100體積ρρηι以下。又，以本 -11 . 1272262 (9) 發明之精製方法精製之五氟化乙烷中所含雜質，含一碳原 子之氫氟碳類總含囊可減少至100體積ppm以下，甚至 50體積ppm以下。而含一碳原子氫氯碳類總含量可降低 至50體積Ppm以下，甚至30體積ppm以下。五氟化乙 太完中所含雜質’上述化合物含量之測定可藉氣體層析（ GC )法之TCD法、FID法或氣體層析質譜分析（gC 一 MS )法等爲之。 本發明提供包含以下過程的五氟化乙烷製造方法。 (1)使選自四氯乙烯、2，2一二氯—i，i，1 一三氟 乙烷及2 —氯一 1，丨，丨.，2 _四氟乙烷所成群之至少一種 與氟化氫於氟化觸媒之存在下反應，得五氟化乙烷之過程 (2 )使過程（〗）所得之五氟化乙烷與氫接觸之過程 ’使過程（1 )所得之五氟化乙烷與氧及/或含氧化合物 接觸之過程’或使過程（1 )所得之五氟化乙烷與氫接觸 ，再與氧及/或含氧化合物接觸之過程 (3 )過程（2 )所得之五氟化乙烷用上述方法精製之 過程 其次說明用本發明之精製方法所得之五氟化乙烷的用 途。 高純度五氟化乙烷，係用作低溫冷凍機作動流體的氟 二氯甲烷（CHC1F2 )之替代品，可用於例如二氟甲烷/ 五氟化乙烷/ 1，1，1 ’ 2 —四氟乙烷之混合冷媒。亦可用 於二氟甲烷/五氟化乙烷之混合冷媒。 又，高純度五氟化乙烷亦可用作六氟乙烷之製造原料 -12- 1272262 (10) 。尤以於五氟化乙烷與氟氣反應製造六氟乙烷之方法中， 以高純度五氟化乙院用作原料，可抑制難與目標產物六氣 乙烷分離之雜質的產生。以高純度五氟化乙烷用作原料， 氟化反應條件之設定範圍大，可穩定控制反應，簡化精製 過程。 又，高純度五氟化乙烷，或與He、N2、Ar等惰性氣 體，HC1、02、H2等之混合氣體，可用作半導體裝置製程 中蝕刻過程的蝕刻氣體。LSI、TFT、有機EL等半導體裝 置之製程中以CVD法、濺鍍法或蒸鍍法等形成薄膜、厚 膜、爲形成電路圖型施行蝕刻之際，可用含上述之五氟化 乙烷的氣體作爲蝕刻氣體。使用五氟化乙烷之蝕刻方法， 可於電漿蝕刻、微波鈾刻等各種乾式蝕刻條件下施行。 〔實施例〕 以下藉實施例詳細說明本發明，惟本發明不限於此等 實施例。 〔粗五氟化乙烷的調製例1〕（原料例1 ) 於充塡有觸媒之第一反應器導入四氟乙烯及氟化氫， 產生主成分係中間體2，2 —二氯一 1，1，1—三氟乙烷及 氯一丨’ 1，1，2—四氟乙烷之氣體，將之連同HF導入第 二反應器製造五氟化乙烷。蒸餾該五氟化乙烷，得含雜質 氯五氟化乙烷、氟甲烷、二氟甲烷、氯甲烷、氯二氟甲烷 及1 ’ 1，1 一三氟甲烷等之五氟化乙烷。五氟化乙烷之純 -13- (11) 1272262 度約9 9 · 4體積％。其次，使該五氟化乙院於市售氫化觸媒 之存在下與氫反應（反應壓力0.15百萬帕、反應溫度220 °C )。含於主成分係五氟化乙烷之產物的酸分用已知方法 去除，再經蒸餾得粗五氟化乙烷。所得粗五氟化乙烷經氣 體層析分析知組成如表1。1272262 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a method for purifying pentane fluoride, a method for producing the same, and a use of pentane fluoride. [Prior Art] Ethane pentafluoride (hereinafter, cf3chf2) is used as a raw material for production of, for example, a low-temperature refrigerant, an etching gas, and hexafluoroethane (hereinafter referred to as CF3cf3). The production of pentane fluoride is known as follows. For example, (1) tetrahydroethylene (hereinafter referred to as CC12=CC12〃) or a method in which a fluoride thereof is fluorinated with hydrogen fluoride (Japanese Patent Laid-Open No. Hei 8-268932, etc.), (2) chloropentafluoride Reduction hydrogenation method of alkane (hereinafter referred to as ', c F 3 C1F 2 〃 ) (Patent No. 2 54〇4〇9, etc.), (3) Method for reacting halogen-containing ethylene with fluorine gas (Special Kaiping 38〇34 Bulletin, etc.). The pentafluoroethane produced by such methods contains various impurities such as hydrochlorocarbon (HCC), chlorofluorocarbon (CFC), hydrochlorofluorocarbon (HCFC), and hydrofluorocarbon (HFC). In order to obtain high purity pentafluoroethane, these impurity layers may be removed. Among the impurities, chlorofluorocarbons and the like are purifications, and in addition to purification, there are various proposals for purification methods for the destruction of the ozone layer. The boiling point of chloropentafluoroethane is similar to that of pentafluoro-4-4272262 (2) ethane, which is difficult to separate by ordinary distillation, but can be obtained, for example, by the following purification method. (1) Extractive distillation method (Special Table 9-508626, etc.), (2) Reduction hydrogenation method of chloropentafluoroethane (Japanese Patent Laid-Open No. Hei 8-301801, etc.), (3) Chloropentane fluoride A method in which an alkane is removed by fluorination of hydrogen fluoride (HF) (JP-A-2001 - 48 8 1 6 or the like), (4) a method of adsorbing and removing an adsorbent (Japanese Patent Publication No. 6-92978) ). On the other hand, one of the hydrochlorocarbons, methyl chloride (hereinafter referred to as CHgCK) and the pentafluoroethane form an azeotrope, and the azeotrope mixture is extremely difficult to separate from the pentafluoroethane. And one of hydrofluorocarbons, difluoromethane (hereinafter, as, CH2F2〃) and 1,1,1-trifluoroethane (hereinafter referred to as ''CF3CH3〃) form an azeotrope with pentane fluoride The azeotrope is also extremely difficult to separate from the pentane fluoride. As a method for purifying and removing such hydrochlorocarbon-based or hydrofluorocarbon-based impurities which are difficult to separate, for example, an extractive distillation purification method or a purification method in which activated carbon adsorption is removed is known. However, the extractive distillation refining method requires expensive equipment such as a distillation tower, and has a high cost of equipment. The refined method of adsorption with activated carbon also does not have sufficient effects. SUMMARY OF THE INVENTION In this context, the object of the present invention is to provide an industrially advantageous refining method for high-purity pentafluoroethane which can be used as a low-temperature refrigerant or an etching gas, which is a method of refining -5 - 1272262 (3). Further, the object of the present invention is to provide a method for producing pentane fluoride and a use of pentane fluoride. In order to achieve the above object, the present inventors have finally discovered that at least one selected from the group consisting of hydrofluorocarbons containing one carbon atom, hydrochlorofluorocarbons containing one carbon atom, and hydrochlorocarbons containing one carbon atom are used. a group of crude pentane fluorides, with a zeolite having an average pore diameter of 3 angstroms to 6 angstroms and a cerium/aluminum ratio of 2.0 or less and/or a carbon adsorbent having an average pore diameter of 3 · 5 angstroms to 6 angstroms. The method of contacting the adsorbent and reducing the content of the above-mentioned impurity compound in the crude pentafluoroethane can be used to achieve the above object, and the present invention has been completed. The present invention is a method for purifying pentane fluoride of [1] to [13], a method for producing the same, and a use thereof. [1] A method for purifying pentane fluoride, characterized in that it contains at least one hydrochlorocarbon selected from the group consisting of a carbon atom, a hydrochlorofluorocarbon containing one carbon atom, and a hydrogen chloride containing one carbon atom. a crude pentane fluoride of a compound of a carbon group, a zeolite having an average pore diameter of 3 angstroms to 6 angstroms and a cerium/aluminum ratio of 2.0 or less and/or a carbon adsorbent having an average pore diameter of 3.5 angstroms to 6 angstroms. The formed adsorbent is contacted to reduce the content of the above compound in the impurities contained in the crude pentafluoroethane. [2] The method according to [1], wherein the hydrofluorocarbon containing one carbon atom is at least one compound selected from the group consisting of fluoromethane, difluoromethane and trifluoromethane. [3] The method according to [1], wherein the hydrochlorofluorocarbon containing one carbon atom is chlorodifluoromethane. [4] The method according to [1], wherein the above-mentioned hydrochlorocarbon-6 - 1272262 (4) containing one carbon atom is at least one compound selected from the group consisting of methyl chloride, dichloromethane and trioxane. . [5] The method according to [1] wherein the crude pentane fluoride contains impurities, and the total content of the above compounds is 1% by volume or less. [6] The method according to [1], wherein the contact pressure of the crude pentane fluoride with the above adsorbent is 1 MPa or less. [7] The method according to [1], wherein the impurities contained in the crude pentafluoroethane are reduced to a total content of the above compound to 150 ppm by volume or less. [8] The method according to [1] wherein the total content of the impurities contained in the crude pentafluoroethane and the hydrofluorocarbon containing the carbon atom is reduced to less than 1.0 ppm by volume. [9] The method according to [1], wherein the total content of the impurities contained in the crude pentafluoroethane and the hydrofluorocarbon having one carbon atom is reduced to 50 ppm by volume or less [1 〇] as in [1] The process wherein the crude pentyl fluoride is derived from a process comprising the following process. (1) at least one selected from the group consisting of tetrachloroethylene, 2,2-dichloro-1,1,1-tri-ethane and 2-chloro-1,1,1,2-tetrafluoroethane ® 'The process of reacting with hydrogen fluoride in the presence of a fluorinated catalyst to obtain pentane fluoride. (2) The process of contacting the pentafluorinated ethane with hydrogen in the process (1) is obtained by the process of @五(1), and the oxygen and/or oxygenate is connected to the process, or the process is (丨) The process of contacting the pentane fluoride with hydrogen, and then contacting @ _ and/or oxygenates. 1272262 (5) [11] A method for producing pentane fluoride, which comprises the following process. (1) Having at least one group selected from the group consisting of tetrachloroethylene, 2,2-dichloro-1, 1,1~Η fluorophene and 2-chloro-1,1,1,2-tetrafluoroethane The process of reacting with hydrogen fluoride in the presence of a fluorinated catalyst, the process of obtaining pentane fluoride, the process of contacting the pentafluoroethane with hydrogen in process (1), and obtaining the pentafluoride of process (1) The process of contacting an alkane with oxygen and/or an oxygenate' or the process of contacting the process with a hydrogen fluoride and/or an oxygenate (3) process (2) Process for the purification of hexafluoroethane by the method of any one of [1] to [1], which is characterized by using any one of [1] to [10] The refined pentafluoroethane is reacted with fluorine gas. [13] The refrigerant ' is characterized by containing pentane fluoride purified by any one of [1] to [1]. [Embodiment] Hereinafter, the present invention will be described in detail. The above method for producing pentane fluoride is known, for example, by a method in which tetrachloroethylene or a vapor thereof is fluorinated with hydrogen fluoride (HF) in the presence of a fluorinated catalyst.乂 When the method is used to manufacture Wuhuayiyuan, the purification process, such as general steaming and leaving operation, still contains impurities that are difficult to separate from pentane fluoride. These impurities -8 - 1272262 (6) include, for example, hydrofluorocarbons, hydrochlorofluorocarbons, and hydrochlorocarbons. These impurities are also contained in the same manner as in the case of hydrogen reduction using chloropentafluoroethane in the presence of a catalyst. Therefore, in order to purify the pentane fluoride to be highly purified, these impurities must be removed. The method for purifying pentane fluoride according to the present invention is characterized in that at least one selected from the group consisting of a gas containing one atom, a hydrochlorofluorocarbon containing one carbon atom, and a hydrochlorocarbon having one carbon atom The crude pentane fluoride of the group of compounds is formed with a zeolite having an average pore diameter of 3 angstroms to 6 angstroms and a cerium/aluminum ratio of 2.0 or less and/or a carbon adsorbent having an average pore diameter of 3 · 5 angstroms to 6 angstroms. Contacting the adsorbent to reduce impurities contained in the crude pentane fluoride, the content of the above compound 〇 contained in the crude pentane fluoride, the hydrogen fluoride containing one carbon atom, at least one selected from the group consisting of fluoromethane, A compound of difluoromethane and trifluoromethane. Hydrochlorofluorocarbons containing one carbon atom are chlorodifluoromethane; hydrochlorocarbons containing one carbon atom are at least one compound selected from the group consisting of methyl chloride, dichloromethane and chloroform. The crude pentane fluoride containing these impurities is difficult to be purified only by the distillation operation. The present inventors have considered the polarity and pore diameter of the adsorbent, and repeatedly changed the type of the adsorbent, the adsorption conditions, and the like, and repeated discussions. As a result, it was found that the above-mentioned impurities can be selectively adsorbed by contact with a zeolite having an average pore diameter of 3 angstroms to 6 angstroms and a yttrium/aluminum ratio (Si / A1 ratio) of 2.0 or less. When the 矽/aluminum ratio is 2.0 or less, if the average pore diameter is less than 3 angstroms or more than 6 angstroms, the effect of reducing the above impurities is not observed. Further, the average pore diameter is in the range of 3 angstroms to 6 angstroms, and the zeolite having a lanthanum/aluminum ratio exceeding 2,000 does not have the effect of reducing the above impurities. -9- 1272262 (7) It has also been found that the above impurities can be selectively adsorbed by contact with carbon adsorption screen carbon having an average pore diameter of 3.5 angstroms to 6 angstroms. However, when the carbon adsorbent having a pore diameter of less than 3.5 angstroms or more than 6 angstroms is absent, the effect of impurities is not described. For example, an average pore size of 3 5 activated carbon is generally used, which is known to have a high adsorption capacity, but there is no reduction in the effect. In the above zeolite, the above carbon adsorbents may be used singly or in combination of two. The impurities contained in the crude pentane fluoride are preferably at least the total content of the above impurities, and more preferably 0.5% by volume or less. When the total content of impurities is 1 , the amount of adsorbent becomes large, and the equipment cost is also high, which is not good. In the method for purifying the pentafluoroethane of the present invention, the method of contacting the crude pentane fluoride with the above adsorbent is not particularly limited, for example, any one of a gas phase contact method or a liquid phase contact method, and a liquid phase. The rate is high and better. The liquid phase contact method may be a batch type, a continuous type, or the like, and for example, a fixed bed type adsorption tower may be used, and one of them may be saturated for regeneration. It is preferred that the crude pentane fluoride is contacted with the adsorbent at a pressure of 1 MPa or less, and if the pressure is higher than 1 MPa, the height is not preferable. Preferably, the crude pentacene is obtained from (1) selected from the group consisting of tetrachloroethylene, 2,2-dichloro-1,1,1 and 2-chloro-1,1,1,2. - a group of tetrafluoroethane to hydrogen fluoride reacted in the presence of a fluorinated catalyst to give pentane fluoride _ (2) a pentafluoroethane and a hydrogen hydride agent obtained by the process (1) On average, it can be determined that the impurity is reduced by about 1 vol%, and the method can be used for the method of contact with the known method. Process, the process of contacting -10- 1272262 (8) 'The process of contacting the pentafluoroethane obtained by the process (1) with oxygen and/or a fluorine-containing compound, or the pentafluoride B obtained by the process (1) The process of contacting an alkane with hydrogen followed by contact with oxygen and/or a fluorochemical. Process (1) can be carried out, for example, by using tetrachloroethylene as a starting material, in the presence of a fluorination catalyst, a two-stage fluorination reaction with hydrogen fluoride. A method of obtaining pentane fluoride. The preferred one of the fluorinated catalyst is a carrier type or a block type mainly composed of trivalent chromium oxide. In the process (2), when the pentafluoroethane obtained in the process (1) is brought into contact with hydrogen, the catalyst may be at least one selected from the group consisting of palladium, rhodium, ruthenium, osmium, uranium and gold. The carrier-type catalyst supported on the carrier, the reaction temperature is in the range of 150 to 400 ° C, and is subjected to a reductive hydrogenation reaction with hydrogen, for example, by a hydrochlorocarbon. Further, in the process (2) When the pentafluoroethane obtained in the process (1) is contacted with oxygen and/or an oxygen-containing compound, the catalyst may be a supported catalyst or a block catalyst which is mainly composed of trivalent chromium oxide, or may be selected. At least one group of palladium, rhodium, ruthenium, osmium, platinum, and gold supported on a carrier. The reaction temperature is in the range of 150 to 400 ° C. Oxygen compounds can be used as nitric oxide (NO). Nitrous oxide (N20), nitrogen dioxide (N02) or ozone (〇3). After this treatment, the impurity hydrofluorocarbons can be oxidized to CO 2 , etc. Process (2) is preferred to make the process ( 1) the obtained pentafluoroethane is contacted with hydrogen and/or an oxygen compound after contact with hydrogen. The impurities contained in the crude pentafluoroethane, the above compound is passed through the above adsorbent After that, the total content of the above-mentioned compound contained in the pentane fluoride can be reduced to 150 ppm by volume or less, or even 100 ρρηι or less. Further, the pentafluoride B refined by the purification method of the invention of -11.272628 (9) The impurities contained in the alkane, the hydrofluorocarbon-containing total capsule containing one carbon atom can be reduced to less than 100 ppm by volume, or even less than 50 ppm by volume, and the total content of hydrochlorocarbons containing one carbon atom can be reduced to less than 50 volumes of Ppm. , even 30 ppm by volume or less. Impurities contained in Ethylpentafluoride 'The content of the above compounds can be determined by gas chromatography (GC) TCD method, FID method or gas chromatography mass spectrometry (gC-MS) method Wait for it. The present invention provides a process for producing pentafluoroethane comprising the following process. (1) at least one selected from the group consisting of tetrachloroethylene, 2,2-dichloro-i, i, 1-trifluoroethane and 2-chloro-1, hydrazine, hydrazine, and 2 _tetrafluoroethane A process of reacting with hydrogen fluoride in the presence of a fluorinated catalyst to obtain pentane fluoride (2) a process of contacting the pentafluoroethane obtained by the process (〗) with hydrogen 'the process (1) a process in which fluorinated ethane is contacted with oxygen and/or an oxygenate or a process in which the pentafluoroethane obtained in process (1) is contacted with hydrogen and then contacted with oxygen and/or an oxygenate (3) process ( 2) The process of purifying the obtained pentafluoroethane by the above method, and secondly, the use of the pentafluoroethane obtained by the purification method of the present invention. High-purity pentafluoroethane, a substitute for fluorodichloromethane (CHC1F2) used as a cryogenic refrigerator actuating fluid, for example, difluoromethane/pentafluoroethane/ 1,1,1 ' 2 - four A mixed refrigerant of fluoroethane. It can also be used as a mixed refrigerant of difluoromethane/pentafluoroethane. Further, high-purity pentane fluoride can also be used as a raw material for the production of hexafluoroethane -12-1272262 (10). In particular, in the method for producing hexafluoroethane by reacting pentane fluoride with fluorine gas, high-purity pentafluoride is used as a raw material to suppress generation of impurities which are difficult to separate from the target product hexasilane. High-purity pentane fluoride is used as a raw material, and the fluorination reaction conditions are set in a large range, and the reaction can be stably controlled to simplify the purification process. Further, a high-purity pentane fluoride or a mixed gas such as He, N2, Ar or the like, and a mixed gas of HC1, 02, H2 or the like can be used as an etching gas for the etching process in the semiconductor device process. 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 gas containing the above-described pentafluoroethane is used for etching a circuit pattern. As an etching gas. The etching method using ethylene pentafluoride can be carried out under various dry etching conditions such as plasma etching and microwave uranium etching. [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited to the examples. [Preparation Example 1 of Crude Pentafluoride Ethane] (Material Example 1) Tetrafluoroethylene and hydrogen fluoride were introduced into a first reactor charged with a catalyst to produce a main component intermediate 2,2-dichloro-1. A gas of 1,1-trifluoroethane and chloroindole ' 1,1,2-tetrafluoroethane was introduced into the second reactor together with HF to produce pentane fluoride. The pentafluoroethane is distilled to obtain pentane fluoride which contains impurities such as chloropentafluoroethane, fluoromethane, difluoromethane, methyl chloride, chlorodifluoromethane and 1' 1,1 trifluoromethane. Pure pentafluoroethane -13- (11) 1272262 degrees about 9 9 · 4 vol%. Next, the pentafluoride was reacted with hydrogen in the presence of a commercially available hydrogenation catalyst (reaction pressure: 0.15 MPa, reaction temperature: 220 ° C). The acid component of the product of the main component, pentane fluoride, is removed by a known method and then distilled to obtain crude pentane fluoride. The crude pentane fluoride was analyzed by gas chromatography to give a composition as shown in Table 1.
-14- 1272262 (12) 表1 化合物 濃度（體積％) CF3CHF2 99.8404 CF3CC1F2 0.0082 CF3CH2F 0.0024 CF3CH3 0.0879 CH2F2 0.0482 CHF3 0.002 1 CHC1F2 0.0020 CH3C1 0.0088-14- 1272262 (12) Table 1 Compound Concentration (% by volume) CF3CHF2 99.8404 CF3CC1F2 0.0082 CF3CH2F 0.0024 CF3CH3 0.0879 CH2F2 0.0482 CHF3 0.002 1 CHC1F2 0.0020 CH3C1 0.0088
〔粗五氟化乙烷之調製例2〕（原料例2 )[Preparation Example 2 of Crude Pentafluoride Ethane] (Material Example 2)
於充塡有鈀/氧化鋁觸媒之反應器，以（原料例1 ) 所得之五氟化乙烷連同空氣導入，於反應壓力0.2百萬帕 、反應溫度2 8 0 °C之條件下反應。反應器出口氣體中所含 酸分及二氧化碳之一部份，以氫氧化鉀水溶液淸洗去除， 蒸餾得粗五氟化乙烷。所得粗五氟化乙烷以氣體層析分析 知組成如表2。 -15- 1272262 (13) 表2 化合物 濃度（體積％) cf3chf2 99.9522 CF3CC1F2 0.0081 CF3CH2F 0.0018 CF3CH3 0.0088 CH2F2 0.0246 CHF3 0.0019 CHC1F2 0.0020 CH3C1 0.0087In a reactor filled with a palladium/alumina catalyst, the pentafluoroethane obtained in (Starting Material Example 1) was introduced together with air, and reacted at a reaction pressure of 0.2 MPa and a reaction temperature of 280 ° C. . One part of the acid and carbon dioxide contained in the gas at the outlet of the reactor is washed with potassium hydroxide aqueous solution and distilled to obtain crude pentane fluoride. The obtained crude pentafluoroethane was analyzed by gas chromatography to give a composition as shown in Table 2. -15- 1272262 (13) Table 2 Compound Concentration (% by volume) cf3chf2 99.9522 CF3CC1F2 0.0081 CF3CH2F 0.0018 CF3CH3 0.0088 CH2F2 0.0246 CHF3 0.0019 CHC1F2 0.0020 CH3C1 0.0087
〔粗五氟化乙烷之調製例3〕（原料例3 ) 於（原料例2 )所得之粗五氟化乙烷更添加CH2F2及 CH3 C 1調製粗五氟化乙烷原料3。以氣體層析分析知組成 如表3。[Preparation Example 3 of Crude Pentafluoride Ethane] (Starting Material Example 3) Crude pentane fluoride raw material 3 was prepared by further adding CH2F2 and CH3C1 to the crude pentane fluoride obtained in (Starting Material Example 2). The composition was determined by gas chromatography as shown in Table 3.
-16- 1272262 (14) 表3 化合物 濃度（體積％) CF3CHF2 99.6322 cf3ccif2 0.0081 CF3CH2F 0.0018 CF3CH3 0.0087 ch2f2 0.2325 chf3 0.0019 CHC1F2 0.0020 CH3C1 0.1128-16- 1272262 (14) Table 3 Compound Concentration (% by volume) CF3CHF2 99.6322 cf3ccif2 0.0081 CF3CH2F 0.0018 CF3CH3 0.0087 ch2f2 0.2325 chf3 0.0019 CHC1F2 0.0020 CH3C1 0.1128
(實施例1 )(Example 1)
於容積200毫升之不銹鋼管充塡20克之沸石（分子 篩4A ( UNION昭和（股）製：平均孔徑3.5埃，矽/鋁 比二1 . 〇 ))，真空乾燥後一面冷卻管柱一面充塡（原料 例1 )之粗五氟化乙烷約1 〇 〇克，保持溫度於—1 (TC並時 時攪拌，約20小時後以氣體層析分析液相部。分析結果 列於表4。 -17- 1272262 (15) 表4 化合物 濃度（體積％) CF3CHF2 99.8979 CF3CC1F2 0.0082 cf3ch2f 0.0021 CF3CH3 0.0880 CH2F2 0.0001 CHF3 0.0015 CHC1F2 0.0019 CH3C1 0.0003Filled with 20 g of zeolite in a 200 ml stainless steel tube (molecular sieve 4A (manufactured by UNION Showa: average pore size 3.5 angstroms, 矽/aluminum ratio 2 〇)), vacuum-dried and cooled on one side of the column ( Raw material Example 1) The crude pentane fluoride was about 1 gram, and the temperature was maintained at -1 (TC and stirred at the same time. After about 20 hours, the liquid phase was analyzed by gas chromatography. The analysis results are shown in Table 4. 17- 1272262 (15) Table 4 Compound concentration (% by volume) CF3CHF2 99.8979 CF3CC1F2 0.0082 cf3ch2f 0.0021 CF3CH3 0.0880 CH2F2 0.0001 CHF3 0.0015 CHC1F2 0.0019 CH3C1 0.0003
由表4之分析結果知，Ch2F2及CH3C1可選擇性吸附 去除。 (實施例2 )From the analysis results in Table 4, Ch2F2 and CH3C1 were selectively adsorbed and removed. (Example 2)
於容積2 0 0毫升之不銹鋼管充塡以2 0克的如同實施 例1之分子篩4A，真空乾燥後一面冷卻管柱一面充塡約 1 〇 〇克之（原料例2 )的粗五氟化乙烷，保持溫度於室溫 (2 0 °C )時時攪拌，約2 0小時後以氣相層析分析液相部 ，分析結果列於表5。The stainless steel tube having a volume of 200 ml was filled with 20 g of molecular sieve 4A as in Example 1, and after vacuum drying, one side of the column was cooled to a volume of about 1 g of raw material (raw material 2). The alkane was stirred while maintaining the temperature at room temperature (20 ° C), and the liquid phase was analyzed by gas chromatography after about 20 hours. The analysis results are shown in Table 5.
-18- 1272262 (16) 表5 化合物 濃度（體積％) cf3chf2 99.9790 cf3ccif2 0.0082 CF3CH2F 0.0017 CF3CH3 0.0087 CH2F2 0.0001 chf3 0.0009 chcif2 0.0012 CH3C1 0.0002-18- 1272262 (16) Table 5 Compound Concentration (% by volume) cf3chf2 99.9790 cf3ccif2 0.0082 CF3CH2F 0.0017 CF3CH3 0.0087 CH2F2 0.0001 chf3 0.0009 chcif2 0.0012 CH3C1 0.0002
由表5之分析結果知，可得純度9 9.9 7體積％以上之 高純度五氟化乙烷。 (實施例3 )From the analysis results of Table 5, it was found that high purity pentafluoroethane having a purity of 9 9.97% by volume or more was obtained. (Example 3)
於容積2 0 0毫升之不銹鋼管充塡3 〇克之如同實施例 1的分子篩4 A，一面冷卻管柱一面充塡約1 〇 〇克（原料3 )之粗五氟化乙烷，真空乾燥後保持溫度於室溫（2 5 t ) 並時時攪拌，約2 0小時後以氣體層析分析液相部’分析 結果列於表6。The stainless steel tube with a volume of 200 ml is filled with 3 g of the molecular sieve 4 A of the first embodiment, and one side of the cooling column is filled with about 1 g of raw material (raw material 3) of crude pentafluoroethane, and dried under vacuum. The temperature was maintained at room temperature (25 t) and stirred occasionally. After about 20 hours, the liquid phase analysis was analyzed by gas chromatography. The results are shown in Table 6.
-19- 1272262 (17) 表6 化合物 濃度（體積％) cf3chf2 99.9789 CF3CC1F2 0.0082 CF3CH2F 0.0016 CF3CH3 0.0087 CH2F2 0.0011 CHF3 0.0006 CHC1F2 0.0008 CH3C1 0.0001-19- 1272262 (17) Table 6 Compound Concentration (% by volume) cf3chf2 99.9789 CF3CC1F2 0.0082 CF3CH2F 0.0016 CF3CH3 0.0087 CH2F2 0.0011 CHF3 0.0006 CHC1F2 0.0008 CH3C1 0.0001
(實施例4 )(Example 4)
於容積200毫升之不銹鋼管充塡20克之碳吸附劑（ 分子篩碳，武田藥品工業（股）製：平均孔徑4埃），真 空乾燥後一面冷卻管柱一面充塡約1 〇〇克之粗五氟化乙烷 ，保持溫度於—2(TC並時時攪拌，約20小時後，以氣相 層析分析液相部。結果列於表7。 -20- 1272262 (18) 表7 化合物 濃度（體積％) C F 3 C H F 2 99.8992 cf3ccif2 0.0082 CF3CH2F 0.0023 CF3CH3 0.0880 CH2F2 0.0003 chf3 0.0006 CHCIF2 0.0012 CH3CI 0.000220 g of stainless steel tube filled with carbon dioxide (molecular sieve carbon, manufactured by Takeda Pharmaceutical Co., Ltd.: average pore size 4 angstroms), vacuum-dried, one side of the cooling column is filled with about 1 gram of crude pentacene The ethane was kept at a temperature of -2 (TC and stirred at the same time. After about 20 hours, the liquid phase was analyzed by gas chromatography. The results are shown in Table 7. -20- 1272262 (18) Table 7 Compound concentration (volume) %) CF 3 CHF 2 99.8992 cf3ccif2 0.0082 CF3CH2F 0.0023 CF3CH3 0.0880 CH2F2 0.0003 chf3 0.0006 CHCIF2 0.0012 CH3CI 0.0002
由表7之分析結果知，CH2F2及CH3C1可選擇性吸附 去除。 (實施例5 )From the analysis results in Table 7, CH2F2 and CH3C1 were selectively adsorbed and removed. (Example 5)
於容積200毫升之不銹鋼管充塡混合15克之用在（ 實施例1 )之分子篩4 A及1 5克之用於（實施例4 )的分 子篩碳，真空乾燥後，一面冷卻管柱一面充塡約1 〇 〇克之 (原料例3 )的粗五氟化乙烷，保持溫度於室溫（2 5 °C ) 並時時攪拌，約2 0小時後以氣體層析分析液相部，分析 結果列於表8。 -21 - 1272262 (19) 表8 化合物 濃度（體積％) CF3CHF2 99.9786 CF3CC1F2 0.0082 CF3CH2F 0.0017 CF3CH3 0.0088 CH2F2 0.0004 CHF3 0.0007 CHC1F2 0.0013 CH3C1 0.0003 (比較例1 ) 於容積200毫升之不銹鋼製管柱充塡20克之沸石（ 分子篩13X ( UNION昭和（股）製：平均孔徑10埃，矽 /鋁比=1 .2 ))，真空乾燥後一面冷卻管柱一面充塡約 1 〇〇克的（原料例2 )之粗五氟化乙烷，保持溫度於室溫 (25 °C )並時時攪拌，約20小時後以氣相層析分析液相 部，分析結果列於表9。 -22- 1272262 (20)15 g of a stainless steel tube having a volume of 200 ml was mixed with 15 g of molecular sieve 4 A and 15 g of molecular sieve carbon (Example 4) used in (Example 1), and after vacuum drying, one side of the column was cooled. 1 Crude pentane fluoride of raw material (raw material example 3), keep the temperature at room temperature (25 ° C) and stir constantly, after about 20 hours, analyze the liquid phase by gas chromatography, and analyze the results. In Table 8. -21 - 1272262 (19) Table 8 Compound concentration (% by volume) CF3CHF2 99.9786 CF3CC1F2 0.0082 CF3CH2F 0.0017 CF3CH3 0.0088 CH2F2 0.0004 CHF3 0.0007 CHC1F2 0.0013 CH3C1 0.0003 (Comparative Example 1) 20 g of zeolite was filled in a 200 ml stainless steel column. (Molecular sieve 13X (manufactured by UNION Showa Co., Ltd.: average pore size 10 angstroms, 矽/aluminum ratio = 1.2)), vacuum-dried, one side of the cooling column is filled with about 1 gram of raw material (raw material example 2) The pentane fluoride was kept at room temperature (25 ° C) and stirred occasionally. After about 20 hours, the liquid phase was analyzed by gas chromatography, and the results are shown in Table 9. -22- 1272262 (20)
化合物 濃度（體 cf3chf2 CF3CC1F2Compound concentration (body cf3chf2 CF3CC1F2
CF3CH2F CF3CH3 CH2F2 chf3 CHC1F2 CH3C1 9 9.94 ^ .00 0.009, 0.02^ 0.00 1 0.00 .000^CF3CH2F CF3CH3 CH2F2 chf3 CHC1F2 CH3C1 9 9.94 ^ .00 0.009, 0.02^ 0.00 1 0.00 .000^
由表9之分析結果知，矽/鋁比在2·〇以 ^ F，平均孔 徑在6埃以上仍無法選擇性吸附去除。From the analysis results in Table 9, it is known that the 矽/aluminum ratio is 2. F and the average pore diameter is above 6 angstroms.
(比較例2 ) 於容積200毫升之不銹鋼管充塡以20克之活性碳（ 粒狀「白鷺」KL，武田藥品工業（股）製：平均孔徑35 埃），真空乾燥後一面冷卻管柱一面充塡約1 〇〇克之（原 料例2 )的粗五氟化乙烷，保持溫度於室溫（2 5 °C )並持 持攪拌，約20小時後以氣相層析分析液相部。結果係如 同比較例1 )無法作選擇性吸附去除，不見具有CH2F2、 CH3C1之減少。 -23- (21) 1272262 (比較例3 ) 於容積200晕:升之不绣鋼管’用沸石（η— ZSM— 5( NE Chemcat (股）製：平均孔徑6埃，砂/銘比二5 ) )以如同（比較例1 )之操作、條件實施、分析，不具有 CH2F2、CH3C1 之減少。 如以上說明’利用本發明之精製方法，可得高純度的五 氟化乙烷。又，本發明所得之五氟化乙烷可用作低溫冷媒、 高純度六氟乙烷的製造原料。 -24-(Comparative Example 2) 20 g of activated carbon (granular "Egretta" KL, manufactured by Takeda Pharmaceutical Co., Ltd.: average pore size 35 angstroms) in a 200 ml stainless steel tube, vacuum-dried and cooled on one side of the column The crude pentane fluoride of about 1 g of the raw material (raw material 2) was kept at room temperature (25 ° C) while stirring, and after about 20 hours, the liquid phase portion was analyzed by gas chromatography. The results were as in Comparative Example 1) and could not be selectively adsorbed and removed, and there was no decrease in CH2F2 and CH3C1. -23- (21) 1272262 (Comparative Example 3) In the volume of 200 halo: liter of non-embroidered steel pipe 'with zeolite (η-ZSM-5 (NE Chemcat): average pore size 6 angstroms, sand / Ming ratio two 5 )) With the operation, conditions, and analysis as in (Comparative Example 1), there was no decrease in CH2F2 and CH3C1. As described above, high purity pentafluoroethane can be obtained by the purification method of the present invention. Further, the pentafluoroethane obtained by the present invention can be used as a raw material for producing a low-temperature refrigerant or high-purity hexafluoroethane. -twenty four-
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| JP4828208B2 (en) * | 2005-11-09 | 2011-11-30 | 昭和電工株式会社 | Method for separating and recovering pentafluoroethane and method for producing pentafluoroethane containing the method |
| JPWO2013151070A1 (en) * | 2012-04-03 | 2015-12-17 | 旭硝子株式会社 | Method for purifying fluoroolefin and method for producing fluoroolefin |
| CN112352029A (en) * | 2018-06-28 | 2021-02-09 | 科慕埃弗西有限公司 | Refrigerant blends having low global warming potential |
| JP7441985B2 (en) * | 2022-02-21 | 2024-03-01 | ダイキン工業株式会社 | Separation method |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525066A (en) * | 1991-07-23 | 1993-02-02 | Daikin Ind Ltd | Production of 1,1,1,2,2-pentafluoro-3,3-dichloropropane and 1,1,2,2,3-pentafluoro-1,3-dichloropropane |
| JPH0692879A (en) * | 1992-09-11 | 1994-04-05 | Daikin Ind Ltd | Method for purifying pentafluoroethane |
| FR2701943B1 (en) * | 1993-02-24 | 1995-05-12 | Atochem Elf Sa | Purification of pentafluoroethane. |
| WO1994020441A1 (en) * | 1993-03-05 | 1994-09-15 | Daikin Industries, Ltd. | Process for producing 1,1,1,2,2-pentafluoroethane, process for producing 2,2-dichloro-1,1,1-trifluoroethane, and method of purifying 1,1,1,2,2-pentafluoroethane |
| EP0693047A1 (en) * | 1993-04-06 | 1996-01-24 | E.I. Du Pont De Nemours And Company | Separation of chloropentafluoroethane from pentafluoroethane |
| JP3516716B2 (en) * | 1994-06-23 | 2004-04-05 | 昭和電工株式会社 | Purification method of trifluoromethane |
| JP2924660B2 (en) * | 1994-09-08 | 1999-07-26 | 昭和電工株式会社 | Purification method of tetrafluoromethane |
| JP3856408B2 (en) * | 1997-04-16 | 2006-12-13 | 昭和電工株式会社 | Method for purifying hexafluoroethane |
| FR2764883B1 (en) * | 1997-06-18 | 1999-07-16 | Atochem Elf Sa | PROCESS FOR THE MANUFACTURE OF HYDROFLUOROALCANES |
| JP4471448B2 (en) * | 2000-04-28 | 2010-06-02 | 昭和電工株式会社 | Tetrafluoromethane purification method and use thereof |
-
2002
- 2002-07-02 JP JP2002192960A patent/JP4666874B2/en not_active Expired - Lifetime
-
2003
- 2003-06-30 KR KR1020047002757A patent/KR100580915B1/en active IP Right Grant
- 2003-07-01 TW TW092117959A patent/TWI272262B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP4666874B2 (en) | 2011-04-06 |
| JP2004035436A (en) | 2004-02-05 |
| TW200401760A (en) | 2004-02-01 |
| KR100580915B1 (en) | 2006-05-17 |
| KR20040044484A (en) | 2004-05-28 |
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