TW534898B - Method for purifying tetrachloroethylene and process for producing hydrofluorocarbons - Google Patents

Method for purifying tetrachloroethylene and process for producing hydrofluorocarbons Download PDF

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Publication number
TW534898B
TW534898B TW091114962A TW91114962A TW534898B TW 534898 B TW534898 B TW 534898B TW 091114962 A TW091114962 A TW 091114962A TW 91114962 A TW91114962 A TW 91114962A TW 534898 B TW534898 B TW 534898B
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Taiwan
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chloro
tetrafluoroethane
hydrogen fluoride
trifluoroethane
gas
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TW091114962A
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Chinese (zh)
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Hiromoto Ohno
Toshio Ohi
Makoto Miyamura
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Showa Denko Kk
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Priority claimed from JP2001206882A external-priority patent/JP5105672B2/en
Priority claimed from JP2002086500A external-priority patent/JP2003286207A/en
Priority claimed from JP2002117341A external-priority patent/JP2003313146A/en
Application filed by Showa Denko Kk filed Critical Showa Denko Kk
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Publication of TW534898B publication Critical patent/TW534898B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Tetrachloroethylene containing a stabilizer is contacted with a zeolite having an average pore size of 3.4 to 11 Å and/or a carbonaceous adsorbent having an average pore size of 3.4 to 11 Å in a liquid phase to obtain a high purity tetrachloroethylene. A halogenated alkene and/or a halogenated alkane are reacted with hydrogen fluoride in the presence of a fluorination catalyst to produce a first hydrofluorocarbon, a halogenated alkene and/or a halogenated alkane are reacted with hydrogen fluoride in the presence of a fluorination catalyst to produce a second hydrofluorocarbon, and these products are joined and then distilled to obtain the first and second hydrofluorocarbons.

Description

534898 A7 B7 五、發明説明（巧） 技術領域 本發明是關於四氯化乙烯之精製方法及氫氟化碳之製 (請先閲讀背面之注意事項再填寫本頁) 造方法。 技術背景 關於四氯化乙烯（CC12= CC12 )(以下，亦稱爲「 PCE」）之製造方法，例如：（1)四氯甲院之熱分解法 ’（2 )同時進行氯化鏈烯烴之氯化及脫去鹽酸之方法， (3 )以天然氣或液化石油氣等之碳氫化合物與氯爲原料 之方法。這些方法中，爲確保四氯化乙烯之安全性，添力口 安定劑，一般添加數百至數千ppm之安定劑。另外，四 氯化乙烯之用途可作爲乾洗用溶媒，氟氯碳化物之製造原 料及溶劑等之用途。 經濟部智慧財產局員工消費合作社印製 另一方面，關於五氟乙烷（CF3CHF2)之製造方法， 例如··（ 1 )以氟化氫氟化四氯化乙烯或其氟化物之方法 (特表平9—511515號公報等），（2 )將氯五氟乙烷（ CC1F2CF3 )氫解作用之方法（特開平5 — 97728號公報等 )及（3)使具鹵素之乙烯於氟素氣體中反應之方法（特 開平1 — 3 8034號公報等）。 例如，四氯化乙烯與氟化氫以氣相於氟化催化劑之存 在下進行反應，製造五氟乙烷之方法，這是依據反應條件 各異之2階段反應所進行。亦即是，依據使四氯化乙烯與 氟化氫（HF )，於氟化催化劑之存在下，以氣相進行反 應，生成以1，1—二氯—2，2，2 —三氟乙烷（CHChCF3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -4 - 534898 A7 _ __B7__ 五、發明説明（2 ) (請先閱讀背面之注意事項再填寫本頁) )以及1一氯—1，2，2，2-四氟乙烷（CHCIFCF3 )爲主 之第1反應以及使第1反應所生成之以CHChCF;及 CHC1FCF3爲主之生成物與HF，於氟化催化劑之存在下， 以氣相進行反應，達生成以五氟乙烷爲主之第2反應進行 反應。 關於此方法，第1反應中原料之一之四氯化乙烯中， 爲抑制分解時產生酸份等，通常含有數十質量ppm至數 百質量ppm左右之安定劑。例如，包含苯酚及甲酚等之 具有羥基之芳香族化合物，四氯化乙烯中若未含安定劑時 ’則四氯化乙烯缺乏安定性，進行產生酸份等之副反應。 然而，四氯化乙烯中所含之安定劑，例如製造四氯化 乙烯時’是成爲所使用之催化劑之活性劣化之原因，所以 不希望含有安定劑。因此，例如最好是於第1反應之前除 去安定劑，但是以以往之分別蒸餾等除去之方法，則有操 作煩雜且實用裝置上須大量的費用之問題。 經濟部智慈財產局8工消費合作社印製 另外，氫氟化碳（以下，亦稱爲「HFC」）類，具有 破壞臭氧層係數爲零之特徵，即使在氫氟化碳類中，五氟 乙烷（以下，亦稱爲「HFC — 125」）或1，1，1，2 —四 氟乙院（以下，亦稱爲「HFC - 134a」），如作爲冷媒時 是有用的化合物。 關於五氟乙烷之製造爲，使四氯化乙烯、2，2一二氯 —1，1，1一三氟乙烷（以下，亦稱爲「HCFC — 123」） 或2—氯—1，1，i，2—四氟乙烷（以下，亦稱爲「HCFC - 1 24」）與氟化氫於氟化催化劑之存在下進行反應之已534898 A7 B7 V. Description of the Invention (Technical Field) The present invention relates to a method for refining ethylene tetrachloride and a method for producing hydrofluorocarbons (please read the precautions on the back before filling this page). Technical background Regarding the manufacturing method of ethylene tetrachloride (CC12 = CC12) (hereinafter, also referred to as "PCE"), for example: (1) Thermal Decomposition of Tetrachloromethane Academy '(2) Simultaneously performing chlorinated olefins Methods for chlorinating and removing hydrochloric acid, (3) A method using hydrocarbons such as natural gas or liquefied petroleum gas and chlorine as raw materials. In these methods, in order to ensure the safety of ethylene tetrachloride, a stabilizer is added, and generally a stabilizer of several hundreds to several thousand ppm is added. In addition, the use of ethylene tetrachloride can be used as a solvent for dry cleaning, as a raw material for production of chlorochlorocarbons, and as a solvent. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs On the other hand, regarding the production method of pentafluoroethane (CF3CHF2), for example, (1) a method of fluorinating ethylene tetrachloride or its fluoride with hydrogen fluoride (Special Table Flat) 9-511515, etc.), (2) a method for hydrogenolysis of chloropentafluoroethane (CC1F2CF3) (Japanese Patent Laid-Open No. 5-97728, etc.) and (3) reacting ethylene with halogen in a fluorine gas Method (Japanese Unexamined Patent Publication No. 1-8034, etc.). For example, a method of producing pentafluoroethane by reacting ethylene tetrachloride with hydrogen fluoride in the presence of a gas phase in the presence of a fluorination catalyst is carried out according to a two-stage reaction with different reaction conditions. That is, according to the reaction of ethylene tetrachloride and hydrogen fluoride (HF) in the presence of a fluorination catalyst in the gas phase to produce 1,1-dichloro-2,2,2-trifluoroethane ( CHChCF3 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -4-534898 A7 _ __B7__ V. Description of the invention (2) (Please read the precautions on the back before filling this page) and 1-chlorine —The first reaction consisting mainly of 1,2,2,2-tetrafluoroethane (CHCIFCF3) and the products produced by the first reaction consisting mainly of CHChCF; and CHC1FCF3 and HF in the presence of a fluorination catalyst The reaction is carried out in the gas phase, so that the second reaction, which mainly produces pentafluoroethane, is performed. In this method, the ethylene tetrachloride, which is one of the raw materials in the first reaction, usually contains a stabilizer in the range of several tens of mass ppm to several hundreds of mass ppm in order to suppress generation of acids and the like during decomposition. For example, if an aromatic compound having a hydroxyl group, such as phenol, cresol, or the like does not contain a stabilizer in ethylene tetrachloride, then ethylene tetrachloride lacks stability and undergoes side reactions that generate acid and the like. However, the stabilizer contained in ethylene tetrachloride, for example, when producing ethylene tetrachloride, is the cause of deterioration of the activity of the catalyst used, and therefore it is not desirable to include a stabilizer. Therefore, for example, it is preferable to remove the stabilizer before the first reaction. However, the conventional method of removing the stabilizer by separate distillation or the like has a problem of complicated operation and a large amount of cost in a practical device. Printed by the 8th Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, HFCs (hereinafter, also referred to as "HFC") are characterized by a zero ozone depletion coefficient. Ethane (hereinafter, also referred to as "HFC-125") or 1,1,1,2,2-tetrafluoroethane (hereinafter, also referred to as "HFC-134a") is a compound useful as a refrigerant. Regarding the production of pentafluoroethane, ethylene tetrachloride, 2,2-dichloro-1,1,1,1-trifluoroethane (hereinafter, also referred to as "HCFC-123") or 2-chloro-1 1,1, i, 2-tetrafluoroethane (hereinafter, also referred to as "HCFC-1 24") and hydrogen fluoride have been reacted in the presence of a fluorination catalyst.

534898 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（3 ) 知方法。 另外，如上所述，亦可使用2階段法，使四氯化乙烯 與氟化氫於氟化催化劑之存在下進行反應，將以五氟乙烷 之中間體之HCFC — 123及/或HCFC — 124爲主要成份之氣 體作爲中間生成物製造，再使這些包含中間體之氣體與氟 化氫於氟化催化劑之存在下進行反應，而製成五氟乙烷之 方法。亦即是，在第1反應器中，如下述之式1及/或式2 所示，使四氯化乙烯與氟化氫進行反應，生成含有多量之 中間體之HCFC — 123及/或HCFC — 124之中間生成物，其 次是於第2反應器中，如下述之式3及/或式4所示，各 中間體與氟化氫進行反應，而得到含有目的物之五氟乙烷 之生成物。 CC 12 -CC 12 + 3HF — CF3 CHC 12 +2HC 1 (式 ι) CC 12 -CC 12 +4HF — CF3 CHC 1 F+ 3HC 1 (式 2) CF3 CHC 12 +2HF — CF3 CHF2 + 2HC 1 (式 3) CF3 CHC1F+HF — CF3 CHF2 +HC 1 (式4) 另外，關於1，1，1，2 -四氟乙烷之製造，例如， 使三氯化乙烯或2-氯一 1，1，1一三氟乙烷（以下，亦 稱爲「HCFC - 133a」）與氟化氫於氟化催化劑之存在下 進行反應之已知方法。此時，與上述之五氟乙烷同樣地可 使用2階段法。亦即是，在第1反應器中，如下述之式5 所示，使三氯化乙烯與氟化氫進行反應，生成含有多量之 中間體之HCFC - 13 3a之中間生成物，其次是於第2反應 (請先閱讀背面之注意事項再填寫本頁) 訂 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6- 534898 A7 B7 " " ^一 ----^ 五、發明説明（4 ) 器中，如下述之式6所示，HCFC — 133a與氟化氫進行反 應，而得到含有目的物之1，1，1，2-四氟乙烷之生成 (請先閱讀背面之注意事項再填寫本頁} 物。 CC 12 =CHC 1 +3HF — CF3 CH2 C 1 + 2HC 1 (式 5) CF3 CH2 C 1 +HF QF3 CH2 F+HC 1 (式 6、 另外，提出同時製造2種以上之氫氟化碳之製造方法 。例如，W095/1 5937號公報中記載，使HCFC — 133a與氟 化氫進行反應，生成1，1，1，2 —四氟乙烷，在此1，1 ，1，2-四氟乙烷之存在下，使二氯甲烷及三氯化乙烯與 氟化氫進行反應之方法。 4. 特表平7 - 507787號公報中記載，例如，使三氯化乙 烯與氟化氫進行反應生成HCFC — 133a，其次再使HCFC〜 133a與氟化氫進行反應，生成1，1，1，2-四氟乙烷之 步驟中，因添加HCFC — 123及/或HCFC — 124，共同生成 1，1，1，2-四氟乙烷及五氟乙烷之方法。 經濟部智慧財產局員工消費合作社印製 另外，在特開平8 — 27046號公報中記載，例如，在 第1反應器中，使HCFC — 133a及HCFC — 123與氟化氫進 行反應，於此反應生成物中，混合四氯化乙烯，供予第2 反應器，以異於第1反應器之反應條件進行反應，而得到 含有1，1，1，2-四氟乙烷及五氟乙烷之生成物。 然而，上述之方法留下，使用特別常用材料之四氯化 乙烯及三氯化乙烯，可同時地、在經濟上有效地製造高純 度之五氟乙烷及1，1，1，2 —四氟乙烷之課題。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -7- 534898 A7 B7 五、發明説明（5 ) (請先閲讀背面之注意事項再填寫本頁) 其理由是’例如在上述之式1至式6所表示之各反應 條件，各有很大的差異。關於五氟乙烷之製造，若具體顯 示適宜之反應條件，在式1及式2所表示之步驟中，例如 可於0.3 5MPa之反應壓力，310°C之反應溫度，氟化氫/四 氯化乙烯之莫耳數比爲10之條件下進行。並且，在式3 及式4所表示乏步驟中，例如可於〇.4MPa之反應壓力， 3 40°C之反應溫度，氟化氫/ HCFC — 123 + HCFC — 124之莫 耳數比爲8之條件下進行。 關於1’ 1，1，2-四氟乙烷之製造，若具體顯示適 宜之反應條件，在式5所表示之步驟中，例如可於 〇.35MPa之反應壓力，270°C之反應溫度，氟化氫/三氯化 乙烯之莫耳數比爲1 5之條件上進行。並且，在式6所表 示之步驟中，可於0.4MPa之反應壓力，340°C之反應溫度 ，氟化氫/ HCFC — 133a之莫耳數比爲6之條件下進行。 經濟部智慧財產局S工消費合作社印製 特別是因爲各步驟中所使用之出發原料與氟化氫反應 之適宜的反應溫度，彼此間差異大，若使用以往之方法時 ’會因爲反應溫度之差異太大而造成使未反應原料帶給催 化劑不好影響，或造成不喜歡之不純物增加等情況。 發明之說明 關於本發明，因爲是在上述背景下所產生的，以提供 能除去含於四氯化乙烯中之安定劑，且容易操作，在工業 上可實施之四氯化乙烯之精製法以及使用此精製法製造五 氟乙烷之方法爲目的。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -8 - 534898 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（6 ) 本發明中，並且提供在工業上有效地製造可作爲冷媒 使用之2種不同的高純度之氫氟化碳之製造方法爲目的 〇 本發明者等人，爲達成上述之第1目的，努力檢討之 結果，將含安定劑之四氯化乙烯以液相與3.4至1 1 A之平 均細孔徑之沸石及/或3 · 4至1 1A之平均細孔徑之碳質吸 著劑相接觸，發現可減少安定劑。進而，因使用已減低安 定劑之四氯化乙烯爲原料，發現可有效率地製造五氟乙烷 ，而完成本發明。 亦即是’本發明是提供將含有具有經基之芳香族化合 物爲安定劑之四氯化乙烯，以液相與3.4至11A之平均細 孔徑之沸石及/或3.4至11A之平均細孔徑之碳質吸著劑 相接觸，減低含有上述安定劑之四氯化乙嫌之精製方法。 本發明並提供，包含使用上述之精製方法，減低含有 具有羥基之芳香族化合物爲安定劑之四氯化乙烯之製造方 法。 本發明並提供包含以下二個步驟之五氯乙院之製造方 法。 (1) 使用上述之精製方法，減低四氯化乙烯中所含具 有羥基之芳香族化合物之步驟。 (2) 依據上述步驟（1 )，將上述之已減低含有具有羥 基之芳香族化合物之四氯化乙烯，於氧化鋁-氧化鉻催化 劑之存在下，以氣相與氟化氫進行反應，得到含有1，1 —二氯—2，2，2 —三氟乙烷以及1 一氯—1，2，2，2 — (請先閱讀背面之注意事項再填寫本頁) 、^1 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -9 - 534898 A 7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（7) 四氟乙烷之混合氣體之步驟。 (3)將上述之步驟（2)所得到之含有1，1一二氯一 2 ’ 2’ 2 —二氣乙院以及1—氯—1’ 2’ 2’ 2-四氣乙院之 混合氣體，於氧化鋁-氧化鉻催化劑之存在下，以氣相與 赢化氨進彳了反應，得到五氯乙院之步驟。 另外，本發明者等人，若使用包含，將鹵化鏈烯及/ 或鹵化鏈烷與氟化氫，於氟化催化劑之存在下進行反應， 生成第1個氫氟化碳之步驟（A)，將鹵化鏈烯及/或鹵化 鏈烷與氟化氫，於氟化催化劑之存在下進行反應，生成第 2個氫氟化碳之步驟（B )，以及將步驟（A )及步驟（B )之生成物合流後蒸餾而製成第1個氫氟化碳及第2個氫 氟化碳之步驟（C)之方法，發現可達成上述之第2個目 的，而完成本發明。 因此本發明又提供，包含（A )將鹵化鏈烯及/或鹵化 鏈烷與氟化氫，於氟化催化劑之存在下進行反應，生成第 1個氫氟化碳之步驟，（B)將鹵化鏈烯及/或鹵化鏈烷與 氟化氫，於氟化催化劑之存在下進行反應，生成第2個氫 氟化碳之步驟，以及（C )合流步驟（A )及步驟（B )之 生成物後蒸餾而製成第1個氫氟化碳及第2個氫氟化碳之 步驟之製造方法。 圖面之簡單說明 圖1是表示，實施有關於本發明中氫氟化碳之製造方 法之裝置之一例之槪略圖。 (請先閲讀背面之注意事項再填寫本頁) —· 訂 -^wi. 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公廣） -10- 534898 A7 ____B7 _五、發明説明（8 ) 圖2是表示，實施有關於本發明中氫氟化碳之製造方 法之裝置之另一例之槪略圖。 關於圖中，1爲反應器A，2爲反應器B，3爲反應器 C，4爲反應器D，5爲第1蒸餾塔，6爲第2蒸餾塔及7 經濟部智慧財產局g(工消費合作社印製 爲第 3蒸餾塔。 主要元件對照表 1 反應器A 2 反應器B 3 反應器C 4 反應器D 5 第1蒸餾塔 6 第2蒸餾塔 7 第3蒸餾塔 (1) P C E (2) 氟化氫 (3) 第1生成物 (4) H C F C - 1 2 4 (5) H C F C - 1 2 3 / H F (6) 氟化氫 (7) 第2生成物 (10) 氟化氫 (11) T C Ε (12) 氟化氫 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X29*7公釐） -11 - 534898 A7 B7 五、發明説明（9 ) 經濟部智慧財產局員工消費合作社印製 (13) 第 二 生 成 物 (14) Η C F C — 1 3 3 a / Η F (15) 氟 化 氫 (16) 第 4 生 成 物 (17) 回 收 之 氟 化 氫 (21) 合 流 生 成 物 (22) 第 1 塔 頂 餾 出 部 份 (23) 第 1 塔 底 餾 出 部 份 (24) Η C 1 (25) Η F C — 1 3 4 a / Η F C (26) Η C F C — 1 2 4 (27) Η C F C — 1 3 3 a / Η F (28) Η C F C — 1 2 3 / Η F (29) 氟 化 氫 (31) Ρ C Ε (32) 氟 化 氫 (33) 第 1 生 成 物 (34) Η C F C — 1 2 4 (35) Η C F C — 1 2 3 / Η F (36) 氟 化 氫 (37) 第 2 生 成 物 (40) 氟 化 氫 (41) Τ C Ε (42) 氟 化 氫 (請先閱讀背面之注意事項再填寫本頁) — 訂 _· 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12 - 534898 B7 A7 …發明説明（10) (43) 第3生成物 (44) HCFC — 133a/ H F (45) 氟化氫 (46) 第4生成物 (47) 回收之氟化氫 (51) 合流生成物 (52) 第1塔頂餾出部份 (53) 第1塔底餾出部份 (54) 第2塔頂餾出部份 (55) HFC — 134a/H F C (56) HCFC-124 (57) 第2塔底餾出部份 (58) 第3塔頂餾出部份 (59) HCFC — 123/H F (60) 氟化氫 ① 表示互相連接 ② 表示互相連接 ③ 表示互相連接 —— d — (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 實施發明之最佳形態 以下，詳細說明關於本發明之合適形式。 首先’詳細說明關於四氯化乙烯之精製方法。 關於本發明中四氯化乙烯之製造方法，其中所使用之 沸石’以具有3.4至11A之平均細孔徑爲宜，其中以具有 本紙張尺度適用中國國家標準（CNS ) A4規格（210父297公釐） -13- 534898 經濟部智慧財產局員工消費合作社印製 A7 _ B7五、發明説明（Μ) 3.4至10Α之平均細孔徑尤佳。沸石之平均細孔徑若大於 1 1 A時，則四氯化乙烯之吸著量變多，而沸石之平均細孔 徑若小於3.4A時，則吸著安定劑之能力變小。 另外沸石中之Si/Al之比率以2以下爲宜，此比率若 大於2時，發現有不能選擇性吸著安定劑的傾向。沸石以 至少 1 種選自分子篩（molecular sieve) 4A ( MS — 4A)， 分子篩5A(MS— 5A)，分子篩10X(MS— 10X)以及分 子篩13X ( MS - 13X)所成群之沸石爲宜。因使用這些沸 石亦可同時減低四氯化乙烯中之水份。 關於碳質吸著劑，以具有3.4至11A之平均細孔徑爲 宜。碳質吸著劑之平均細孔徑若大於11A時，則四氯化 乙烯之吸著量變多，而碳質吸著劑之平均細孔徑若小於 3.4A時，則吸著安定劑之能力變小。作爲碳質吸著劑， 以分子飾碳4A及/或分子篩碳5A爲宜。 從吸著劑再生之觀點考量，沸石與碳質吸著劑分別單 獨使用爲宜，但亦可以混合使用，沸石與碳質吸著劑之混 合比率，並無特別限制，但若考量亦可減低四氯化乙烯中 之水分時，以含有多量沸石之混合比率爲宜。 可使用回分式，連續式等已知之方法爲，使含有安定 劑之四氯化乙烯以液相與沸石及/或碳質吸著劑相接觸之 方法。在工業上，以連續流通吸著劑固定床之方法爲宜， 依據安定劑之濃度及四氯化乙烯之處理量，可選擇適當的 液體基準之空間速度（LHSV )。通常在1至50h厂1之範 圍爲宜。另外，爲在工業上實施減低四氯化乙烯中之安定 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -14- 534898 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（12) 劑之方法，亦可使用設置2座吸著塔，使2塔輪流切換以 連續地進行精製之方法。 將四氯化乙烯以液相精製時之處理溫度爲，以- 20 至+ 80°C爲宜，其中以0至50°C之範圍尤佳。處理溫度 若高於80°C時，加熱或耐壓之裝置等項目使設備費用大 增；而低於- 2(TC時，則需要冷卻設備等。並且，壓力以 0至3MPa之範圍內爲宜，其中以〇至IMPa之範圍尤佳 ，壓力若大於3MPa時，需要耐壓設備等項目，並不符合 經濟效益。 如上述之說明，依據使用本發明之精製方法，可減低 四氯化乙烯中所含之安定劑。本發明之精製方法，特別適 用於苯環上具有羥基之化合物，苯環上具有羥基之化合物 如苯酚、曱酚、2，6—二一叔一丁基一對—甲酚及胺基甲 基苯酚等。 含安定劑之四氯化乙烯以液相與上述之沸石及/或碳 質吸著劑，於上述之條件下相接觸，可得到減低安定劑至 30質量ppm以下之四氯化乙烯。亦可得到減低安定劑至 1 0質量p p m以下之四氯化乙烯，甚至可得到減低安定劑 至5質量ppm以下之四氯化乙烯。 其次，說明關於五氟乙烷之製造方法。 關於本發明中五氟乙烷之製造方法，包含如上述之（ 1 ) 、（ 2 )及（3 )步驟。 經由（1 )步驟所得到之四氯化乙烯，以已減低具有 _基之芳香族至30質量ppm以下之四氯化乙烯爲宜，其 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐） -15- 534898 A7 __B7_五、發明説明（13) 中以已減低具有羥基之芳香族至10質量ppm以下之四氯 化乙烯尤佳，已減低至5質量ppm以下最好。使用已減 低具有羥基之芳香族至30質量ppm以下之四氯化乙烯爲 原料時，可達到提高製造步驟中所使用催化劑之壽命，並 且可有效率地，經濟地製造五氟乙烷。 關於本發明之五氟乙烷之製造方法以反應式表示時， 如下所示。534898 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (3) Known methods. In addition, as described above, a two-stage method can also be used to react ethylene tetrachloride and hydrogen fluoride in the presence of a fluorination catalyst. The HCFC-123 and / or HCFC-124 intermediates of pentafluoroethane are used as The main component gas is produced as an intermediate product, and then these intermediate gas-containing gases are reacted with hydrogen fluoride in the presence of a fluorination catalyst to form pentafluoroethane. That is, in the first reactor, as shown in the following formula 1 and / or formula 2, ethylene tetrachloride and hydrogen fluoride are reacted to form HCFC — 123 and / or HCFC — 124 containing a large amount of intermediates. The intermediate product is next in a second reactor, and each intermediate is reacted with hydrogen fluoride as shown in the following formula 3 and / or formula 4 to obtain a product of pentafluoroethane containing the target substance. CC 12 -CC 12 + 3HF — CF3 CHC 12 + 2HC 1 (Formula) CC 12 -CC 12 + 4HF — CF3 CHC 1 F + 3HC 1 (Formula 2) CF3 CHC 12 + 2HF — CF3 CHF2 + 2HC 1 (Formula 3 ) CF3 CHC1F + HF — CF3 CHF2 + HC 1 (Formula 4) In addition, regarding the production of 1,1,1,2-tetrafluoroethane, for example, ethylene trichloride or 2-chloro-1,1,1 A known method in which trifluoroethane (hereinafter, also referred to as "HCFC-133a") is reacted with hydrogen fluoride in the presence of a fluorination catalyst. In this case, a two-stage method can be used similarly to the pentafluoroethane described above. That is, in the first reactor, as shown in the following formula 5, ethylene trichloride and hydrogen fluoride are reacted to produce an intermediate product of HCFC-13 3a containing a large amount of an intermediate, followed by the second Response (Please read the notes on the back before filling this page) Order-This paper size applies to China National Standard (CNS) A4 (210X297 mm) -6- 534898 A7 B7 " " ^ 一 ---- ^ 5. Description of the invention (4) In the device, as shown in the following formula 6, HCFC-133a reacts with hydrogen fluoride to obtain the formation of 1,1,1,2-tetrafluoroethane containing the target substance (please read first Note on the back, fill in this page again} CC 12 = CHC 1 + 3HF — CF3 CH2 C 1 + 2HC 1 (Equation 5) CF3 CH2 C 1 + HF QF3 CH2 F + HC 1 (Equation 6, A method for producing two or more kinds of hydrofluorocarbons. For example, it is described in the publication No. W095 / 1 5937 that HCFC-133a is reacted with hydrogen fluoride to produce 1,1,1,2-tetrafluoroethane. Here, 1 A method of reacting dichloromethane and ethylene trichloride with hydrogen fluoride in the presence of 1,1,2-tetrafluoroethane. 4. Table 7-507787 describes, for example, reacting ethylene trichloride and hydrogen fluoride to form HCFC-133a, and then reacting HCFC ~ 133a with hydrogen fluoride to produce 1,1,1,2-tetrafluoroethane In this step, HCFC-123 and / or HCFC-124 are added to co-generate 1,1,1,2-tetrafluoroethane and pentafluoroethane. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In Japanese Patent Application Laid-Open No. 8-27046, for example, HCFC-133a and HCFC-123 are reacted with hydrogen fluoride in a first reactor, and ethylene tetrachloride is mixed in the reaction product and supplied to the second reactor. The reactor is reacted under reaction conditions different from those of the first reactor, and a product containing 1,1,1,2-tetrafluoroethane and pentafluoroethane is obtained. However, the above-mentioned method is left behind, and the use is particularly The commonly used materials of ethylene tetrachloride and ethylene trichloride can simultaneously and economically produce high-purity pentafluoroethane and 1,1,1,2, tetrafluoroethane. The paper size is applicable China National Standard (CNS) A4 specification (210X297 mm) -7- 534898 A7 B7 V. Description of the invention (5) (Please read the precautions on the back before filling out this page) The reason is that, for example, each of the reaction conditions shown in the above formulas 1 to 6 has great differences. With regard to the production of pentafluoroethane, if specific reaction conditions are shown specifically, in the steps represented by Formula 1 and Formula 2, for example, a reaction pressure of 0.3 5 MPa, a reaction temperature of 310 ° C, hydrogen fluoride / quad It is carried out under the condition that the molar ratio of ethylene chloride is 10. In addition, in the depleted steps represented by Formulas 3 and 4, for example, a reaction pressure of 0.4 MPa, a reaction temperature of 3 40 ° C, and a condition that the molar number ratio of hydrogen fluoride / HCFC — 123 + HCFC — 124 is 8 can be used. Carry on. Regarding the production of 1 '1,1,2-tetrafluoroethane, if suitable reaction conditions are specifically shown, in the step represented by Formula 5, for example, a reaction pressure of 0.35 MPa, a reaction temperature of 270 ° C, The molar ratio of hydrogen fluoride / ethylene trichloride was 15. In addition, the step represented by Formula 6 can be performed under a reaction pressure of 0.4 MPa, a reaction temperature of 340 ° C, and a molar number ratio of hydrogen fluoride / HCFC-133a of 6. Printed by the Industrial and Commercial Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, especially because the appropriate reaction temperature of the starting materials used in each step and the reaction of hydrogen fluoride is greatly different from each other. If the conventional method is used, the difference in reaction temperature will be too It may cause unfavorable influence of unreacted raw materials on the catalyst, or increase the amount of undesired impurities. DESCRIPTION OF THE INVENTION The present invention is produced under the above-mentioned background to provide a stabilizer capable of removing the stabilizer contained in ethylene tetrachloride and is easy to handle. The industrially applicable purification method of ethylene tetrachloride and The purpose of the method for producing pentafluoroethane using this purification method. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -8-534898 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) In the present invention, and it is industrially effective The purpose is to produce two different high-purity hydrofluorocarbons that can be used as refrigerants. The inventors and others, in order to achieve the first objective described above, have worked hard to review the results. Ethylene was brought into contact with a liquid phase with a zeolite having an average pore size of 3.4 to 1 1 A and / or a carbonaceous sorbent having an average pore size of 3.4 to 11 A, and it was found that the stabilizer could be reduced. Furthermore, it was found that pentafluoroethane can be efficiently produced by using ethylene tetrachloride with reduced stabilizer as a raw material, and completed the present invention. That is, the present invention is to provide a zeolite containing ethylene tetrachloride containing an aromatic compound having a radical as a stabilizer, a zeolite with a liquid phase and an average pore diameter of 3.4 to 11A, and / or an average pore diameter of 3.4 to 11A. The carbonaceous sorbent is in contact with each other to reduce the purification method of ethyl tetrachloride containing the above-mentioned stabilizer. The present invention also provides a method for reducing ethylene tetrachloride containing an aromatic compound having a hydroxyl group as a stabilizer by using the aforementioned purification method. The present invention also provides a method for the production of pentachloroethane containing the following two steps. (1) A step of reducing the aromatic compound having a hydroxyl group contained in ethylene tetrachloride by using the above purification method. (2) According to the above step (1), the above-mentioned reduced ethylene tetrachloride containing an aromatic compound having a hydroxyl group is reacted with hydrogen fluoride in the gas phase in the presence of an alumina-chromium oxide catalyst to obtain a compound containing 1 ， 1—dichloro—2,2,2 —trifluoroethane and 1 chloro—1,2,2,2 — (Please read the precautions on the back before filling this page), ^ 1 This paper size applies to China National Standard (CNS) A4 Specification (210X 297 mm) -9-534898 A 7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (7) Mixture of Tetrafluoroethane. (3) Mixing 1,1,2-dichloro-1,2'2'2-diqiyiyuan and 1-chloro-1'2'2'2-four-qiyiyuan obtained in step (2) above The gas, in the presence of an alumina-chromium oxide catalyst, reacted with Yinghua Ammonia in the gas phase to obtain PeCB. In addition, the present inventors and others, if using step (A) containing a halogenated alkene and / or halogenated alkane and hydrogen fluoride in the presence of a fluorination catalyst to generate a first hydrofluorocarbon, Step (B) of reacting halogenated alkene and / or halogenated alkane with hydrogen fluoride in the presence of a fluorination catalyst to form a second hydrofluorocarbon, and the product of step (A) and step (B) The method of the step (C) of producing the first hydrofluorocarbon and the second hydrofluorocarbon after the confluence is distilled, and it is found that the above-mentioned second object can be achieved, and the present invention has been completed. Therefore, the present invention further provides (A) a step of reacting a halogenated olefin and / or a halogenated alkane with hydrogen fluoride in the presence of a fluorination catalyst to form a first hydrofluorocarbon, and (B) converting the halogenated chain The step of reacting olefins and / or halogenated alkane with hydrogen fluoride in the presence of a fluorination catalyst to form a second hydrofluorocarbon, and (C) combining the products of steps (A) and (B) after distillation A method for manufacturing the first hydrofluorocarbon and the second hydrofluorocarbon. Brief Description of the Drawings Fig. 1 is a schematic diagram showing an example of an apparatus in which a method for producing a hydrofluorocarbon in the present invention is implemented. (Please read the notes on the back before filling this page) — · Order- ^ wi. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 public broadcasting) -10- 534898 A7 ____B7 _V. Description of the invention (8 ) FIG. 2 is a schematic diagram showing another example of an apparatus in which the method for producing a hydrofluorocarbon in the present invention is implemented. In the figure, 1 is reactor A, 2 is reactor B, 3 is reactor C, 4 is reactor D, 5 is the first distillation column, 6 is the second distillation column, and 7 is the Intellectual Property Bureau of the Ministry of Economic Affairs g ( Printed by the Industrial and Commercial Cooperative as the third distillation column. Table 1 shows the main components. Reactor A 2 Reactor B 3 Reactor C 4 Reactor D 5 First distillation column 6 Second distillation column 7 Third distillation column (1) PCE (2) Hydrogen fluoride (3) First product (4) HCFC-1 2 4 (5) HCFC-1 2 3 / HF (6) Hydrogen fluoride (7) Second product (10) Hydrogen fluoride (11) TC Ε ( 12) Hydrogen fluoride (please read the precautions on the back before filling this page) The paper size applies to the Chinese National Standard (CNS) A4 specification (21 × 29 * 7 mm) -11-534898 A7 B7 V. Description of the invention (9) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (13) Second product (14) Η CFC — 1 3 3 a / Η F (15) Hydrogen fluoride (16) Fourth product (17) Recovered hydrogen fluoride (21) Confluent product (22) 1st overhead distillation section (23) 1st bottom distillation Section (24) Η C 1 (25) Η FC — 1 3 4 a / Η FC (26) Η CFC — 1 2 4 (27) Η CFC — 1 3 3 a / Η F (28) Η CFC — 1 2 3 / Η F (29) hydrogen fluoride (31) PG C Ε (32) hydrogen fluoride (33) first product (34) Η CFC — 1 2 4 (35) Η CFC — 1 2 3 / Η F (36) Hydrogen fluoride (37) 2nd product (40) Hydrogen fluoride (41) TC C E (42) Hydrogen fluoride (Please read the precautions on the back before filling this page) — Order _ · This paper size applies to Chinese National Standard (CNS) A4 Specifications (210X297 mm) -12-534898 B7 A7… Description of invention (10) (43) Third product (44) HCFC — 133a / HF (45) Hydrogen fluoride (46) Fourth product (47) Recovered hydrogen fluoride (51) Combined products (52) First overhead fraction (53) First overhead fraction (54) Second overhead fraction (55) HFC — 134a / HFC (56) HCFC-124 (57) Distillation at the bottom of the second column (58) Distillation at the top of the third column (59) HCFC — 123 / HF (60) Fluorine Hydrogen ① means interconnected ② means interconnected ③ means interconnected —— d — (Please read the precautions on the back before filling out this page) The best form for implementing the invention printed by the employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is detailed below A description is given of a suitable form of the present invention. First, a method for purifying ethylene tetrachloride will be described in detail. Regarding the method for producing ethylene tetrachloride in the present invention, it is preferable that the zeolite used therein has an average pore diameter of 3.4 to 11A, in which the Chinese national standard (CNS) A4 specification (210 father 297 company) is applicable to the paper size -13- 534898 Printed by A7 _ B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of Invention (M) The average pore diameter of 3.4 to 10A is particularly good. If the average pore diameter of the zeolite is greater than 1 1 A, the adsorption amount of ethylene tetrachloride becomes larger, and if the average pore diameter of the zeolite is less than 3.4 A, the ability to adsorb the stabilizer becomes small. In addition, the ratio of Si / Al in the zeolite is preferably 2 or less, and if the ratio is more than 2, it is found that there is a tendency that the stabilizer cannot be selectively adsorbed. Preferably, at least one zeolite is selected from the group consisting of molecular sieve 4A (MS-4A), molecular sieve 5A (MS-5A), molecular sieve 10X (MS-10X), and molecular sieve 13X (MS-13X). The use of these zeolites can also reduce the water content in ethylene tetrachloride. As the carbonaceous sorbent, it is preferable to have an average pore diameter of 3.4 to 11A. If the average pore diameter of the carbonaceous sorbent is greater than 11A, the adsorption amount of ethylene tetrachloride becomes larger, and if the average pore diameter of the carbonaceous sorbent is less than 3.4A, the ability to adsorb the stabilizer becomes smaller. . As the carbonaceous sorbent, molecular trimmed carbon 4A and / or molecular sieve carbon 5A is preferable. From the standpoint of sorbent regeneration, it is advisable to use zeolite and carbonaceous sorbent separately, but they can also be mixed. The mixing ratio of zeolite and carbonaceous sorbent is not particularly limited, but it can also be reduced if considered. In the case of water in ethylene tetrachloride, a mixing ratio containing a large amount of zeolite is appropriate. A known method, such as a fractionation method, a continuous method, and the like, is a method in which ethylene tetrachloride containing a stabilizer is brought into contact with a zeolite and / or a carbonaceous sorbent in a liquid phase. In the industry, it is advisable to use a continuous bed of a fixed bed of sorbent. Depending on the concentration of the stabilizer and the amount of ethylene tetrachloride treated, an appropriate liquid-based space velocity (LHSV) can be selected. It is usually suitable to be in the range of 1 to 50h. In addition, in order to reduce the stability of ethylene tetrachloride in industry (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -14- 534898 Economy The method of printing A7 B7 by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau V. Invention Description (12) The method can also be used to set up two suction towers and switch the two towers in turn to continuously refine. The processing temperature when the ethylene tetrachloride is refined in a liquid phase is preferably -20 to + 80 ° C, and a range of 0 to 50 ° C is particularly preferred. If the processing temperature is higher than 80 ° C, the cost of equipment such as heating or pressure-resistant equipment will increase greatly; while it is lower than -2 (TC, cooling equipment is required.) And the pressure in the range of 0 to 3 MPa is It is preferable that the range is from 0 to 1 MPa, and if the pressure is greater than 3 MPa, pressure-resistant equipment and other items are required, which is not economical. As explained above, according to the use of the purification method of the present invention, ethylene tetrachloride can be reduced Stabilizer contained in the compound. The refining method of the present invention is particularly suitable for compounds having a hydroxyl group on a benzene ring, compounds having a hydroxyl group on a benzene ring such as phenol, resorcinol, 2,6-di-tert-butyl pair— Cresol, aminomethylphenol, etc. Stabilizer-containing ethylene tetrachloride is contacted with the above zeolite and / or carbonaceous sorbent in the liquid phase under the above-mentioned conditions to reduce the stabilizer to 30 mass Ethylene tetrachloride below ppm. It is also possible to obtain ethylene tetrachloride with stabilizers reduced to 10 mass ppm or less, and it is even possible to obtain ethylene tetrachloride with stabilizers reduced to 5 mass ppm or lower. Next, the pentafluoroethyl Method for producing alkane. The method for producing pentafluoroethane in the present invention includes the steps (1), (2), and (3) as described above. The ethylene tetrachloride obtained through the step (1) is used to reduce the aromaticity of the _ group. It is suitable to use ethylene tetrachloride with a mass of less than 30 mass ppm. (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X29? Mm) -15- 534898 A7 __B7_ V. Description of the Invention (13) In particular, ethylene tetrachloride, which has been reduced in its aromatic content with hydroxyl groups to 10 mass ppm or less, is preferred, and has been reduced to less than 5 mass ppm. The use of aromatics in which hydroxyl groups have been reduced When ethylene tetrachloride of less than 30 mass ppm is used as a raw material, the life of the catalyst used in the production step can be improved, and pentafluoroethane can be efficiently and economically produced. About the production of pentafluoroethane of the present invention When the method is expressed by a reaction formula, it is as follows.

CC12 =CC12 + 3HF -> CF3 CHC 12 + 2HC 1 CC12 =CC12 +4HF — CF3 CHC 1 F + 3HC 1 CF3 CHC 12 +2HF — CF3 CHF2 +2HC 1 CF3 CHC 1 F+HF CF3 CHF2 +HC 1 (式1) (式2) (式3) (式4) (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 上述之反應，於氧化鋁-氧化鉻催化劑之存在下，以 氣相進行反應，其反應條件各異，例如在式1及式2所表 示之第1反應中，可於約0.3MPa之反應壓力，約300°C 之反應溫度，HF/PCE爲6 (莫耳比）之條件上進行。在 式3及式4所表示之第2反應中，可於〇.4MPa之反應壓 力，3 30〇C 之反應溫度，HF/ ( CF3 CHCh+ CF3CHC1F)爲 4 至8 (莫耳比）之條件下進行。 其次，說明關於氫氟化碳之製造方法。 說明關於本發明中氫氟化碳之製造方法，包含（A ) 使鹵化鏈烯及/或鹵化鏈烷與氟化氫，於氟化催化劑之存 在下進行反應，生成第1個氫氟化碳之步驟，（B )使鹵 化鏈烯及/或鹵化鏈烷與氟化氫，於氟化催化劑之存在下 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） •16- 534898 A7 B7 經濟部智慈財產局員工消費合作社印製 五、發明説明（14) 進行反應，生成第2個氫氟化碳之步驟，以及（C )合流 步驟（A )及步驟（B )之生成物後蒸餾而得到第1個氫 氟化碳及第2個氫氟化碳之步驟。 使用此方法可製造之氫氟化碳，可舉例如二氟乙烷、 三氟乙烷、1，2 —二氟乙烷、1，1，1—三氟乙烷、1，1 ’ 1’ 2—四氯乙院及五氨乙院等。 可作爲原料之鹵化鏈烯，可舉例如氯化乙烯、1，1 -二氯化乙烯、三氯化乙烯、三氟化乙烯、四氯化乙烯、四 氟化乙烯及氯化三氟化乙烯等。而鹵化鏈烷，例如二氯甲 烷、氯氟甲烷、三氯甲烷、氯二氟甲烷、2 —氯—1，1，1 —二赢乙院、2，2 — —^氯—1，1，1一二氣乙院及2-氯 —1，1，1，2—四氟乙烷等。 關於步驟（A)，例如生成以五氟乙烷爲第1個氫氟 化碳時，以從四氯化乙烯、2，2 —二氯—1，1，1—三氟 乙烷及2 —氯一 1，1，1，2 —四氟乙烷之成群中至少可選 出1種，與氟化氫於氟化催化劑之存在下進行反應爲宜。 另外，步驟（A )包含使四氯化乙烯與氟化氫於氟化 催化劑之存在下，在第1反應帶進行反應，生成含有2, 2 —二氯—1，1，1—三織乙院及/或2 —氯—1，1，1’ 2 — 四氟乙院之氣體之步驟（1)，以及使含有2，2-二氯一 1，1，1—三氟乙烷及/或2 —氯一 1，1，1，2 —四氟乙烷 之氣體與氟化氫於氟化催化劑之存在下，在第2反應帶進 行反應，生成含有五氟乙院之氣體之步驟（2)爲宜。 例如，以生成以五氟乙烷爲第1個氫氟化碳，生成以 (請先閲讀背面之注意事項再填寫本頁) • —.CC12 = CC12 + 3HF-> CF3 CHC 12 + 2HC 1 CC12 = CC12 + 4HF — CF3 CHC 1 F + 3HC 1 CF3 CHC 12 + 2HF — CF3 CHF2 + 2HC 1 CF3 CHC 1 F + HF CF3 CHF2 + HC 1 ( (Formula 1) (Formula 2) (Formula 3) (Formula 4) (Please read the notes on the back before filling out this page) Order the above-mentioned reaction printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs on the alumina-chromium oxide catalyst In the presence of gas, the reaction is performed in the gas phase, and the reaction conditions are different. For example, in the first reaction represented by Formula 1 and Formula 2, the reaction pressure can be about 0.3MPa, the reaction temperature is about 300 ° C, and the HF / The PCE was performed on a condition of 6 (mole ratio). In the second reaction represented by the formulas 3 and 4, it can be used under the conditions of a reaction pressure of 0.4 MPa, a reaction temperature of 3 300 ° C, and HF / (CF3 CHCh + CF3CHC1F) of 4 to 8 (molar ratio). get on. Next, a method for producing hydrofluorocarbon will be described. The method for producing a hydrofluorocarbon in the present invention includes (A) a step of reacting a halogenated alkene and / or a halogenated alkane with hydrogen fluoride in the presence of a fluorination catalyst to generate a first hydrofluorocarbon (B) Use halogenated alkenes and / or halogenated alkanes and hydrogen fluoride in the presence of a fluorination catalyst. This paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm) • 16- 534898 A7 B7 Ministry of Economic Affairs Printed by the Consumer Property Cooperative of the Citizenship Bureau. 5. Description of the invention (14) The step of reacting to generate the second hydrofluorocarbon, and (C) the combined products of step (A) and step (B) are obtained by distillation. The first step of HFC and the second step of HFC. Hydrofluorocarbons that can be produced using this method include, for example, difluoroethane, trifluoroethane, 1,2-difluoroethane, 1,1,1-trifluoroethane, 1,1 '1' 2—Tetrachloroethane hospital and five ammonia hospital. Examples of halogenated alkenes that can be used as raw materials include ethylene chloride, vinylidene chloride, ethylene trichloride, ethylene trifluoride, ethylene tetrachloride, ethylene tetrafluoride, and ethylene trifluoride. Wait. And halogenated alkanes, such as dichloromethane, chlorofluoromethane, chloroform, chlorodifluoromethane, 2-chloro-1,1,1—winning academies, 2,2 -— ^ chloro-1,1, 1 1-2 Gas Yiyuan and 2-chloro-1,1,1,2-tetrafluoroethane, etc. With regard to step (A), for example, when pentafluoroethane is used as the first hydrofluorocarbon, ethylene tetrachloride, 2,2-dichloro-1,1,1-trifluoroethane and 2- At least one of the group of chlorine-1,1,1,2-tetrafluoroethane can be selected, and it is suitable to react with hydrogen fluoride in the presence of a fluorination catalyst. In addition, step (A) includes reacting ethylene tetrachloride and hydrogen fluoride in the presence of a fluorination catalyst in a first reaction zone to produce 2, 2-dichloro-1, 1, 1, 1-trisodium and And / or 2—chloro-1,1,1 ′ 2—gas of tetrafluoroethane (1), and making 2,2-dichloro-1,1,1-trifluoroethane and / or 2 —Chlorine-1,1,1,2—Tetrafluoroethane gas and hydrogen fluoride in the presence of a fluorination catalyst are reacted in a second reaction zone to generate step (2) of a gas containing pentafluoroethane. . For example, to generate pentafluoroethane as the first hydrofluorocarbon, generate (Please read the precautions on the back before filling this page) • —.

、1T - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 534898 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（15) 1，1，1，2-四氟乙烷爲第2個氫氟化碳時，在上述之步 驟（A )加上步驟（B )，使三氯化乙烯及/或2 -氯—1， 1，1 -三氟乙烷與氟化氫於氟化催化劑之存在下進行反應 ，生成以1，1，1，2-四氟乙烷爲第2個氫氟化碳爲宜 〇 另外，步驟（B )中以包含使三氯化乙烯與氟化氫於 氟化催化劑之存在下，在第3反應帶進行反應，生成含有 2-氯一 1，1，1一三氟乙烷之氣體之步驟（3)，以及使 含有2-氯一 1，1，1-三氟乙烷之氣體與氟化氫於氟化 催化劑之存在下，在第4反應帶進行反應，生成含有1， 1，1，2-四氟乙烷之氣體之步驟（4)爲宜。 步驟（C )是合流步驟（A )所得到之含有五氟乙烷 之氣體以及步驟（B )所得到之含有1，1，1，2 -四氟乙 烷之氣體後進行蒸餾爲宜。 生成以五氟乙烷爲第1個氫氟化碳，生成以1，1，1 ，2 -四氟乙烷爲第2個氫氟化碳時，以步驟（A)包含 (1 )使四氯化乙烯與氟化氫於氟化催化劑之存在下，在 第1反應帶進行反應，得到含有氯化氫、2，2 -二氯一 1 ，1，1—三氟乙烷、2 —氯—1，1，1，2 —四氟乙烷、五 氟乙烷及/或氟化氫之氣體之步驟，以及（2)使含有2，2 —二氯—1，1，1—三氟乙烷及/或2 —氯—1，1，1，2-四氟乙烷之氣體與氟化氫於氟化催化劑之存在下，在第2 反應帶進行反應，得到含有氯化氫、五氟乙烷、2，2 -二 氯—1，1，1—二氧乙院、2 —氯—1，1，1，2-四氟乙院 (請先閲讀背面之注意事項再填寫本頁) 訂 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 534898 A7 B7 經濟部智慧財產局S工消費合作社印製 五、發明説明（16) 及/或氟化氫之氣體之步驟；步驟（B)包含（3)使三氯 化乙烯與氟化氫於氟化催化劑之存在下，在第3反應帶進 行反應，生成含有氯化氫、2-氯—1，1，1—三氟乙院及 /或氟化氫之氣體之步驟，以及（4)使含有2-氯- 1，1 ’ 三氟乙院之氣體與氟化氫於氟化催化劑之存在下， 在第4反應帶進行反應，生成含有氯化氫、1，1，1，2 — 四氟乙烷、2—氯—1，1，1—三氟乙烷及/或氟化氫之氣 體之步驟，步驟（C )是（5 )合流上述步驟（1 )至（4 ) 所得到之氣體後，導入蒸餾塔中蒸餾而得到五氟乙烷及1 ，1，1，2 —四氟乙烷之步驟爲宜。 關於此法，例如分別實施由四氯化乙烯與氟化氫製造 五氟乙烷之2個反應步驟，以及由三氯化乙烯與氟化氫製 造1，1，1，2 -四氟乙烷之2個反應步驟，可有效率地 實施控制反應條件。因此，可避免影響催化劑活性及不純 物的增加等。由於合流上述之反應步驟之生成物爲一導入 蒸餾塔，可以簡單的裝置，有效率地製造高純度之五氟乙 烷及1，1，1，2—四氟乙烷。 第1反應帶至第4反應帶之任一反應帶之反應壓力， 以大氣壓力至〇.9MPa之範圍內爲宜，另外，第2反應帶 之壓力比第1反應帶之壓力高，第4反應帶之壓力比第3 反應帶之壓力高爲宜。 此法中所使用之氟化催化劑，可使用目前已知之氟化 催化劑。關於此法中，雖可在製造2個不同化合物之各個 步驟中，選擇最適合之催化劑，但氟化催化劑是以三價之 本紙張尺度適用中國國家標準( CNS )八4規格（210X297公釐） ~ -19 - (請先閱讀背面之注意事項再填寫本頁) 534898 A7 B7 五、發明説明（17) 氧化鉻爲主要成份之載體型或塊狀型催化劑爲宜。 (請先閲讀背面之注意事項再填寫本頁) 關於此法中，將上述各步驟所製成之含有2種氫氟化 碳之氣體後，合流各生成氣體並導入蒸餾塔。例如合流上 述之步驟（1 )至（4 )所得到氣體導入第1蒸餾塔，由塔 頂分離出氯化氫、2 —氯—1’ 1，1一三氟乙院、2 —氯一 1 ，1，1，2 —四氟乙烷’五氟乙烷及/或1，1，1，2 —四氟 乙烷，由塔底分離出氟化氫、2，2 —二氯一 1，1，1—三 赢乙院及/或2-氯一 1，1，1—二氟乙院爲宜。 此時，使第1蒸餾塔之塔底所分離出之氟化氫、2，2 一二氯一 1，1，1—三氟乙院及/或2 —氯—1，1，1 一三氟 乙烷於反應步驟中循環爲宜。另外，使第1蒸餾塔之塔底 所分離出之氟化氫、2’ 2-二氯一 1，1，1一三氟乙烷及/ 或2-氯一 1，1，1一三氟乙烷導入第2蒸餾塔，分離精 製後，於反應步驟中循環爲宜。 — 經濟部智慈財產局員工消費合作社印製 使第2蒸餾塔所分離出之氟化氫，至少於上述之第i 反應帶至第4反應帶之任一反應帶中循環爲宜。另外，使 第2蒸餾塔所分離出之含有2, 2-二氯一 1，1，1一三氟 乙烷之氣體於第2反應帶循環爲宜；而第2蒸餾塔所分離 出之含有2-氯一 1，1，1一三氟乙烷之氣體則於第4反 應帶循環爲宜。 將第1蒸餾塔之塔頂所分離出之氯化氫、2 一氯一 1， 1，1—三氟乙烷、2 —氯—1，1，1，2 —四氟乙烷，五氟 乙烷及/或1，1，1，2 —四氟乙烷導入第3蒸餾塔，由塔 頂所得到之氣體以多量含有1，1，1，2 -四氟乙烷爲宜 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -20- 534898 A7 B7 經濟部智慈財產局員工消費合作社印製 五、發明説明（18) 。另外，關於此法中，各蒸餾塔之塔內壓力以大氣壓力至 3Mpa之範圍內爲宜。 或者是，關於本發明之氫氟化碳之製造方法，以包含 (A)由四氯化乙烯、2，2 —二氯—1，1，1一三氟乙烷及 2-氯一 1，1，1，2 —四氟乙烷之成群中至少選出一種與 氟化氫於氟化催化劑之存在下進行反應，生成五氟乙烷之 步驟，（B)三氯化乙烯及/或2-氯—1，1，1—三氟乙 烷與氟化氫於氟化催化劑之存在下進行反應，生成1，1 ，1，2 -四氟乙烷之步驟，以及（C )合流步驟（A )及 步驟（B )所得到之生成物後導入蒸餾塔，由塔頂分離出 以氯化氫爲主要成份之氣體，由塔底分離出含有五氟乙院 及1，1，1，2—四氟乙烷之氣體，蒸餾由塔底所得到之 氣體，而得到五氟乙烷及1，1，1，2-四氟乙烷之步驟 爲宜。 此時，歩驟（A )以包含使四氯化乙烯與氟化氫於氟 化催化劑之存在下，在第1反應帶進行反應，生成含有2 ，2-二氯—1，1，1—三氟乙烷及/或2 —氯—1，1，1，2 —四氟乙烷之氣體之步驟（1)，以及使含有2，2-二氯 —1，1，1—三氟乙烷及/或2 —氯—1，1，1，2 —四氟乙 烷之氣體與氟化氫於氟化催化劑之存在下，在第2反應帶 進行反應，生成含有五氟乙烷之氣體之步驟（2)爲宜。 步驟（B )中以包含使三氯化乙烯與氟化氫於氟化催 化劑之存在下，在第3反應帶進行反應，生成含有2-氯 一 1，1，1一三氟乙烷之氣體之步驟（3)，以及使含有2 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -21 - 534898 A 7 B7 經濟部智慧財產局8工消費合作社印製 五、發明説明（19) -氯- 1，1，1一三氟乙烷之氣體與氟化氫於氟化催化劑 之存在下，在第4反應帶進行反應，生成含有1，1，1， 2-四氟乙烷之氣體之步驟（4)爲宜。 另外，關於此法，步驟（A )包含（1 )使四氯化乙 烯與氟化氫於氟化催化劑之存在下，在第1反應帶以氣相 進行反應，生成含有氯化氫、2，2 —二氯一 1，1，1一三 氟乙烷、2 —氯—1，1，1，2—四氟乙烷、五氟乙烷及/或 氟化氫之氣體之步驟，以及（2)使含有2，2-二氯一 1 ，1，1—三氟乙烷及/或2 —氯—1，1，1，2 —四氟乙烷之 氣體與氟化氫於氟化催化劑之存在下，在第2反應帶以氣 相進行反應，生成含有氯化氫、五氟乙烷、2，2-二氯-1，1，1—三氟乙烷、2 —氯—1，1，1，2 —四氟乙烷及/ 或氟化氫之氣體之步驟，步驟（B)包含（3)使三氯化 乙烯與氟化氫於氟化催化劑之存在下，在第3反應帶以氣 相進行反應，生成含有氯化氫、2-氯一 1，1，1一三氟乙 烷及/或氟化氫之氣體之步驟，以及（4)使含有2-氯- 1 ，1，1 -三氟乙烷之氣體與氟化氫於氟化催化劑之存在下 ，在第4反應帶以氣相進行反應，生成含有氯化氫、1，1 ，1，2 —四氟乙烷、2-氯—1，1，1 一三氟乙烷及/或氟 化氫之氣體之步驟，步驟（C )是（5 )合流上述步驟（1 )至（4 )所得到之氣體後導入蒸餾塔中，由塔頂分離出 以氯化氫爲主要成份之氣體，由塔底分離出含有五氟乙院 及1，1，1，2-四氟乙烷之氣體，蒸餾由塔底所得到之 氣體，而得到五氟乙烷及1，1，1，2-四氟乙烷之步驟 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22- 534898 A7 B7 五、發明説明（20) 爲宜。 (請先閲讀背面之注意事項再填寫本頁) 關於此法，由於分別實施由四氯化乙烯與氟化氫製造 五氟乙烷之2個反應步驟，以及由三氯化乙烯與氟化氫製 造1，1，1，2-四氟乙院之2個反應步驟，可有效率地 實施控制反應條件。因此，可避免影響催化劑活性及不純 物的增加等。由於合流上述之4個反應步驟之生成物爲一 導入蒸餾塔，可以簡單的裝置，有效率地製造高純度之五 每乙院及1，1，1，2 —四赢乙院。 第1反應帶至第4反應帶之任一反應帶之反應壓力’ 以大氣壓力至0.9MPa之範圍內爲宜，另外，第2反應帶 之壓力比第1反應帶之壓力高，第4反應帶之壓力比第3 反應帶之壓力高爲宜。 此法中所使用之氟化催化劑，可使用目前已知之氟化 催化劑。關於此法中，在製造2個不同化合物之各個步驟 中，可選擇最適合之催化劑，但氟化催化劑以三價之氧化 鉻爲主要成份之載體型或塊狀型催化劑爲宜。 經濟部智慧財/$笱員工消費合作社印製 關於此法中，得到上述各步驟所製成之含有五氟乙烷 及1，1，1，2-四氟乙烷之氣體後，合流各生成氣體並 導入蒸餾塔。例如以合流上述之步驟（1 )至（4 )所得到 氣體導入第1蒸餾塔，由塔頂分離出氯化氫，由塔底分離 出含有以2 —氯—1，1，1一三氟乙烷、2，2-二氯—1， 1，1—二氟乙院、2 —氯—1，1，1，2-四氟乙院、五氣 乙烷、1，1，1，2-四氟乙烷及/或氟化氫爲主之氣體爲 宜。 $紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐] _ -23- 534898 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（21) 將第1蒸餾塔之塔底所分離出含有以2-氯- 1，1， 1—三氟乙烷、2，2 —二氯—1，1，1—三氟乙烷、2 —氯 —1，1，1，2 —四氟乙烷、五氟乙烷、1，1，1，2 -四 氟乙烷及/或氟化氫爲主之氣體，導入第2蒸餾塔，由第 2蒸餾塔之塔頂分離出五氟乙烷、1，1，1，2-四氟乙烷 及/或2 —氯—1，1，1，2 -四氟乙烷，由塔底分離出2 —氣—1，1’ 1—二氣乙院、2’ 2 —二氯—1，1，1—二氣 乙烷及/或氟化氫爲宜。由第2蒸餾塔之塔頂所得到之氣 體以多量含有1，1，1，2 —四氟乙烷爲宜。 將第2蒸餾塔之塔底分離出含有2-氯一 1，1，1一 三氟乙烷、2，2-二氯—1，1，1一三氟乙烷及/或氟化氫 之氣體，導入第3蒸餾塔，各成份分離精製後，使之循環 於反應步驟爲宜。另外，使第3蒸餾塔所分離出之氟化氫 至少於第1反應帶至第4反應帶之任一反應帶中循環爲宜 〇 使第3蒸餾塔所分離出以含有2，2 -二氯一 1，1，1 -三氟乙烷爲主之氣體於第2反應帶循環爲宜；而第3蒸 餾塔所分離出以含有2-氯一 1，1，1一三氟乙烷爲主之 氣體則於第4反應帶循環爲宜。 另外，將第2蒸觀塔之塔頂所分離出之含有五氟乙院 、1，1，1，2 —四氟乙烷及/或2 —氯—1，1，1，2 —四氟 乙烷之氣體，導入第4蒸餾塔，由塔頂分離出五氟乙烷及 1，1，1，2 —四氟乙烷，由塔底分離出2 —氯—1，1，1 ，2 —四氟乙烷，使2 —氯—1，1，1，2-四氟乙烷於第2 (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -24- 534898 經濟部智慧財產局g(工消費合作社印製、 1T-This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) -17- 534898 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (15) 1,1,1,2 -When tetrafluoroethane is the second hydrofluorocarbon, add step (B) to step (A) above to make trichloroethylene and / or 2-chloro-1,1,1-trifluoroethyl Alkane and hydrogen fluoride are reacted in the presence of a fluorination catalyst to form 1,2,1,2-tetrafluoroethane as the second hydrofluorocarbon. In addition, in step (B), Step (3) of reacting ethylene with hydrogen fluoride in the presence of a fluorination catalyst in a third reaction zone to generate a gas containing 2-chloro-1,1,1,1-trifluoroethane, and A step of generating a gas containing 1,1,1,2-tetrafluoroethane by reacting a gas of 1,1,1-trifluoroethane with hydrogen fluoride in the presence of a fluorination catalyst in a fourth reaction zone ( 4) is appropriate. Step (C) is a confluence of the gas containing pentafluoroethane obtained in step (A) and the gas containing 1,1,1,2-tetrafluoroethane obtained in step (B), and then distillation is preferred. When pentafluoroethane is generated as the first hydrofluorocarbon and when 1,1,1,2-tetrafluoroethane is generated as the second hydrofluorocarbon, step (A) includes (1) to make four In the presence of a fluorination catalyst, ethylene chloride and hydrogen fluoride are reacted in a first reaction zone to obtain hydrogen chloride, 2,2-dichloro-1,1,1,1-trifluoroethane, and 2-chloro-1,1 1,1,2-tetrafluoroethane, pentafluoroethane and / or hydrogen fluoride gas step, and (2) making 2,2-dichloro-1,1,1-trifluoroethane and / or 2 —Chlorine—1,1,1,2-tetrafluoroethane gas and hydrogen fluoride in the presence of a fluorination catalyst are reacted in a second reaction zone to obtain hydrogen chloride, pentafluoroethane, and 2,2-dichloro —1,1,1—dioxane hospital, 2 —chlorine—1,1,1,2-tetrafluoroethane hospital (please read the precautions on the back before filling this page) The standard of the paper is applicable to Chinese national standards ( CNS) A4 specification (210X297 mm) -18- 534898 A7 B7 Printing steps of the Intellectual Property Bureau of the Ministry of Economic Affairs and Industrial Cooperatives 5. Printing of the invention (16) and / or the steps of hydrogen fluoride gas; Step (B) contains (3) Make trichloride A step of reacting ethylene with hydrogen fluoride in the presence of a fluorination catalyst in a third reaction zone to generate a gas containing hydrogen chloride, 2-chloro-1,1,1-trifluoroethane, and / or hydrogen fluoride, and (4) The gas containing 2-chloro-1,1 'trifluoroethane and hydrogen fluoride were reacted in the presence of a fluorination catalyst in a fourth reaction zone to generate hydrogen chloride, 1,1,1,2,4-tetrafluoroethane 2, 2-chloro-1,1,1-trifluoroethane and / or hydrogen fluoride gas step, step (C) is (5) confluence of the gas obtained in the above steps (1) to (4), and then introduced into distillation The step of distilling in the column to obtain pentafluoroethane and 1,1,1,2-tetrafluoroethane is preferred. In this method, for example, two reaction steps for producing pentafluoroethane from ethylene tetrachloride and hydrogen fluoride and two reactions for producing 1,1,1,2-tetrafluoroethane from ethylene trichloride and hydrogen fluoride are separately performed. Step, the reaction conditions can be effectively controlled. Therefore, it is possible to avoid affecting catalyst activity and increase of impurities. Since the products of the above-mentioned reaction steps are combined into a distillation column, high-purity pentafluoroethane and 1,1,1,2-tetrafluoroethane can be efficiently produced with a simple device. The reaction pressure of any of the first reaction zone to the fourth reaction zone is preferably in the range of atmospheric pressure to 0.9 MPa. In addition, the pressure of the second reaction zone is higher than the pressure of the first reaction zone. The pressure in the reaction zone is preferably higher than the pressure in the third reaction zone. As the fluorination catalyst used in this method, a conventionally known fluorination catalyst can be used. In this method, although the most suitable catalyst can be selected in each step of manufacturing 2 different compounds, the fluorination catalyst is based on the trivalent paper size and applies the Chinese National Standard (CNS) 8-4 specification (210X297 mm) ) ~ -19-(Please read the notes on the back before filling this page) 534898 A7 B7 V. Description of the invention (17) Carrier or bulk catalyst with chromium oxide as the main component is suitable. (Please read the precautions on the back before filling out this page.) In this method, the two HFC-containing gases made in the above steps are combined, and each gas is combined to be introduced into a distillation column. For example, the gases obtained in the above steps (1) to (4) are combined and introduced into a first distillation column, and hydrogen chloride, 2-chloro-1 '1,1-trifluoroethane, and 2-chloro-1,1 are separated from the top of the column. 1,1,2-tetrafluoroethane 'pentafluoroethane and / or 1,1,1,2-tetrafluoroethane, hydrogen fluoride, 2,2-dichloro-1,1,1- Win-Win II Hospital and / or 2-Chloro-1,1,1-Difluoro-II Hospital is preferred. At this time, hydrogen fluoride, 2,2 dichloro-1,1,1,1-trifluoroethane and / or 2-chloro-1,1,1, trifluoroethyl separated from the bottom of the first distillation column were made. The alkane is preferably recycled in the reaction step. In addition, hydrogen fluoride, 2 '2-dichloro-1,1,1,1-trifluoroethane, and / or 2-chloro-1,1,1,1-trifluoroethane separated from the bottom of the first distillation column were used. After introduction into the second distillation column, after separation and purification, it is preferable to circulate in the reaction step. — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs It is advisable to circulate the hydrogen fluoride separated from the second distillation column in at least one of the i-th reaction zone to the fourth reaction zone. In addition, it is appropriate to circulate the gas containing 2, 2-dichloro-1,1,1,1-trifluoroethane separated in the second distillation column in the second reaction zone; and the content separated in the second distillation column The gas of 2-chloro-1,1,1-trifluoroethane is preferably circulated in the fourth reaction zone. Hydrogen chloride, 2-chloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,1,2-tetrafluoroethane, pentafluoroethane separated from the top of the first distillation column And / or 1,1,1,2,4-tetrafluoroethane is introduced into the third distillation column, and the gas obtained from the top of the column contains a large amount of 1,1,1,2-tetrafluoroethane is suitable. This paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) -20- 534898 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs. 5. Description of the invention (18). In addition, in this method, the pressure in the column of each distillation column is preferably in the range of atmospheric pressure to 3 MPa. Alternatively, the method for producing a hydrofluorocarbon of the present invention includes (A) ethylene tetrachloride, 2,2-dichloro-1,1,1,1-trifluoroethane, and 2-chloro-1, At least one selected from the group of 1,1,2, tetrafluoroethane to react with hydrogen fluoride in the presence of a fluorination catalyst to form pentafluoroethane, (B) ethylene trichloride and / or 2-chloro —1,1,1-trifluoroethane and hydrogen fluoride are reacted in the presence of a fluorination catalyst to produce 1,1,1,2-tetrafluoroethane, and (C) the confluent step (A) and steps (B) The obtained product is introduced into a distillation column, and a gas containing hydrogen chloride as a main component is separated from the top of the column, and pentafluoroethane and 1,1,1,2-tetrafluoroethane are separated from the bottom of the column. The gas is preferably a step of distilling the gas obtained from the bottom of the column to obtain pentafluoroethane and 1,1,1,2-tetrafluoroethane. At this time, step (A) includes reacting ethylene tetrachloride and hydrogen fluoride in the presence of a fluorination catalyst in a first reaction zone to generate 2,2-dichloro-1,1,1-trifluoro Step (1) of ethane and / or 2-chloro-1,1,1,2-tetrafluoroethane gas, and making 2,2-dichloro-1,1,1-trifluoroethane and And / or 2-chloro-1,1,1,2-tetrafluoroethane gas and hydrogen fluoride in the presence of a fluorination catalyst to react in a second reaction zone to generate a gas containing pentafluoroethane (2 ) Is appropriate. Step (B) includes a step of reacting ethylene trichloride and hydrogen fluoride in the presence of a fluorination catalyst in a third reaction zone to generate a gas containing 2-chloro-1,1,1-trifluoroethane. (3), and make it contain 2 (Please read the notes on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -21-534898 A 7 B7 Intellectual property of the Ministry of Economic Affairs Printed by Bureau 8 Industrial Cooperative Cooperative. V. Description of the Invention (19) -Chlorine-1,1,1-trifluoroethane gas and hydrogen fluoride are reacted in the fourth reaction zone in the presence of a fluorination catalyst. The step (4) of 1,1,2-tetrafluoroethane gas is suitable. In addition, in this method, step (A) includes (1) reacting ethylene tetrachloride and hydrogen fluoride in the presence of a fluorination catalyst in a first reaction zone in a gas phase to generate hydrogen chloride, 2,2-dichloro A step of 1,1,1, trifluoroethane, 2-chloro-1,1,1,1,2-tetrafluoroethane, pentafluoroethane and / or hydrogen fluoride, and (2) the step of 2-Dichloro-1,1,1,1-trifluoroethane and / or 2-chloro-1,1,1,2-tetrafluoroethane gas and hydrogen fluoride in the presence of a fluorination catalyst in a second reaction The reaction is carried out in the gas phase to produce hydrogen chloride, pentafluoroethane, 2,2-dichloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,2, tetrafluoroethane And / or a step of hydrogen fluoride gas, step (B) includes (3) reacting ethylene trichloride and hydrogen fluoride in the presence of a fluorination catalyst in a third reaction zone in a gas phase to generate hydrogen chloride, 2-chlorine A step of 1,1,1,1-trifluoroethane and / or hydrogen fluoride, and (4) the presence of a gas containing 2-chloro-1,1,1-trifluoroethane and hydrogen fluoride in the presence of a fluorination catalyst The reaction proceeds in the gas phase in the fourth reaction zone to generate a gas containing hydrogen chloride, 1,1,1,2-tetrafluoroethane, 2-chloro-1,1,1,1-trifluoroethane and / or hydrogen fluoride. Step, step (C) is (5) confluence The gas obtained in the above steps (1) to (4) is introduced into the distillation column, the gas containing hydrogen chloride as the main component is separated from the top of the column, and the A process of difluoromethane and 1,1,1,2-tetrafluoroethane gas, distillation of the gas obtained from the bottom of the column to obtain pentafluoroethane and 1,1,1,2-tetrafluoroethane ( Please read the notes on the back before filling out this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -22- 534898 A7 B7 5. The invention description (20) is appropriate. (Please read the precautions on the back before filling out this page.) As for this method, the two reaction steps for the production of pentafluoroethane from ethylene tetrachloride and hydrogen fluoride and the production of ethylene trichloride and hydrogen fluoride are performed separately. The two reaction steps of 1,2-tetrafluoroethane can effectively control the reaction conditions. Therefore, it is possible to avoid affecting catalyst activity and increase of impurities. Since the products of the four reaction steps mentioned above are combined into one distillation column, a simple device can be used to efficiently produce high-purity No. 5 and every 1,1,1,2,4 win-win second-academies. The reaction pressure in any of the first reaction zone to the fourth reaction zone is preferably in the range of atmospheric pressure to 0.9 MPa. In addition, the pressure in the second reaction zone is higher than the pressure in the first reaction zone, and the fourth reaction zone The pressure of the belt is preferably higher than the pressure of the third reaction belt. As the fluorination catalyst used in this method, a conventionally known fluorination catalyst can be used. In this method, the most suitable catalyst can be selected in each step of manufacturing two different compounds, but a fluorinated catalyst is preferably a carrier-type or bulk-type catalyst containing trivalent chromium oxide as a main component. Printed by the Ministry of Economic Affairs ’Smart Money / Employee Consumption Cooperative. In this method, after obtaining the gas containing pentafluoroethane and 1,1,1,2-tetrafluoroethane produced in the above steps, the confluence is generated. The gas is introduced into the distillation column. For example, the gases obtained in the above steps (1) to (4) are combined to be introduced into the first distillation column, hydrogen chloride is separated from the top of the column, and 2-chloro-1,1,1-trifluoroethane is separated from the bottom of the column. , 2,2-dichloro-1,1,1,1-difluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane Gases based on fluoroethane and / or hydrogen fluoride are preferred. $ Paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) _ -23- 534898 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) The bottom of the first distillation tower Isolates containing 2-chloro-1,1,1-trifluoroethane, 2,2-dichloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,2,4- Gases based on fluoroethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane and / or hydrogen fluoride are introduced into the second distillation column, and pentafluoroethane is separated from the top of the second distillation column. , 1,1,1,2-tetrafluoroethane and / or 2-chloro-1,1,1,2-tetrafluoroethane, which separates 2-gas-1,1'1-digas from the bottom of the column Yiyuan, 2 '2-dichloro-1,1,1-digas ethane and / or hydrogen fluoride are suitable. The gas obtained from the top of the second distillation column contains a large amount of 1,1,1,2,- Tetrafluoroethane is preferred. The bottom of the second distillation column was separated to contain 2-chloro-1,1,1,1-trifluoroethane and 2,2-dichloro-1,1,1,1-trifluoroethane. And / or hydrogen fluoride gas is introduced into the third distillation column, after each component is separated and refined, it is circulated in the reaction It is preferable that the hydrogen fluoride separated in the third distillation column is circulated in at least one of the reaction zones from the first reaction zone to the fourth reaction zone. The third distillation column is separated to contain 2, It is appropriate that 2-dichloro-1,1,1-trifluoroethane-based gas is circulated in the second reaction zone; and the third distillation column is separated to contain 2-chloro-1,1,1-trifluoro Ethane-based gas is preferably circulated in the fourth reaction zone. In addition, the top of the second steam observation tower containing the pentafluoroethane, 1,1,1,2, tetrafluoroethane and / Or 2-chloro-1,1,1,2-tetrafluoroethane gas is introduced into the fourth distillation column, and pentafluoroethane and 1,1,1,2-tetrafluoroethane are separated from the top of the column, 2-Chloro-1,1,1,2-tetrafluoroethane is separated from the bottom of the tower, and 2-chloro-1,1,1,2-tetrafluoroethane is separated from the 2nd (please read the precautions on the back first) (Fill in this page again) The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -24- 534898 Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperative)

A7 B7五、發明説明（22) 反應帶循環爲宜。另外，關於此法中，各蒸餾塔之塔內壓 力以大氣壓力至3Mpa之範圍內爲宜。 依據關於本發明中氫氟化碳之製造方法，有關各反應 步驟中未反應之出發原料及中間體，可以蒸餾方式分離， 使其循環於各反應步驟，因而可提高目的化合物之回收率 〇 關於本發明中氫氟化碳之製造方法，依據如上所述， 爲由2種以上之原料化合物及氟化氫製造2種不同之氫氟 化碳之方法’爲克服對應所製造之氫氟化碳之最適合之催 化；=dj祖成及最適合之反應條件之差異’導入相異之固體催 化劑或相異之溫度進行反應，將2個以上之反應器並排連 接’在各自的反應器，供給適當的反應原料進行反應。 以下是以實施例與比較例進一步說明本發明，但本發 明不以這些實施例爲限。 原料例 以氣相層析法（氣相層析管：毛細管式/火焰離子化 偵測法，FID法）分析市售之四氯化乙烯，其中含有總量 爲150質量ppm之安定劑之苯酚及甲酚，四氯化乙烯中 之水分約爲50質量ppm。 實施例1 於內容積爲200ml之不銹鋼圓筒中，充塡20g之沸石 [分子篩5A ( Union昭和株式會社製，平均細孔徑爲4.2 A (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） •25- 534898 經濟部智慧財產局員工消費合作社印製 A7 _____B7 _五、發明説明（23) ，SWA1比=1 )]。將沸石真空乾燥後，邊冷卻鋼筒邊充 塡100g之上述原料例所示之四氯化乙烯，保持在20°C下 時時攪拌’約4小時後，採取液相部之一部份以上述之原 料例之氣相層析法之條件下分析。其結果爲，未檢出苯酚 及甲酚中任何一種安定劑。另外，使用卡爾一費歇法（ Karl Fischer’s )分析處理後之四氯化乙烯中之水份時，其 水分値爲3質量ppm以下。 實施例2 於內容積爲200ml之不銹鋼圓筒中，充塡20g之碳質 吸著劑[分子篩碳5 A，武田藥品工業株式會社製，平均細 孔徑爲5 A]。將碳質吸著劑真空乾燥後，邊冷卻鋼筒邊 充塡80g之上述原料例所示之四氯化乙烯，保持在20°C 下時時攪拌，約5小時後，採取液相部之一部份以上述之 原料例之氣相層析法之條件下分析。其結果爲，未檢出苯 酚及甲酚中任何一種安定劑。 實施例3 以20g之沸石[分子篩13X ( Union昭和株式會社製， 平均細孔徑爲10 A，Si/A1比=0.81 )]爲吸著劑充塡外 ，其餘同實例1之操作及條件下處理，其結果爲，未檢出 苯酚及甲酚中任何一種安定劑。 比較例1 本紙張尺度賴巾關家縣（CNS ) A4驗（210X297公楚) 賴 -26- (請先閲讀背面之注意事項再填寫本頁)A7 B7 V. Description of the invention (22) The reaction zone is preferably circulated. In this method, it is preferable that the internal pressure of each distillation column is in the range of atmospheric pressure to 3 MPa. According to the method for producing hydrofluorocarbon in the present invention, the unreacted starting materials and intermediates in each reaction step can be separated by distillation and recycled in each reaction step, thereby improving the recovery rate of the target compound. The method for producing hydrofluorocarbon in the present invention is based on the method for producing two different hydrofluorocarbons from two or more kinds of raw material compounds and hydrogen fluoride as described above. Suitable catalysis; = dj Zucheng and the difference between the most suitable reaction conditions 'Introduce different solid catalysts or different temperatures for reaction, connect 2 or more reactors side by side' in their respective reactors, and supply appropriate The reaction raw materials are reacted. Hereinafter, the present invention will be further described with examples and comparative examples, but the present invention is not limited to these examples. Examples of raw materials were analyzed by commercially available ethylene tetrachloride by gas chromatography (gas chromatography tube: capillary / flame ionization detection method, FID method), which contained 150 mass ppm of phenol as a stabilizer. The moisture in cresol and ethylene tetrachloride is about 50 ppm by mass. Example 1 A 200 ml stainless steel cylinder was filled with 20 g of zeolite [molecular sieve 5A (manufactured by Union Showa Corporation, with an average pore diameter of 4.2 A (please read the precautions on the back before filling in this page)) The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) • 25- 534898 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7 _V. Description of the invention (23), SWA1 ratio = 1)]. After the zeolite was vacuum-dried, 100 g of ethylene tetrachloride shown in the above raw material example was charged while cooling the steel cylinder, and kept stirring at about 20 ° C for about 4 hours. The above raw material examples were analyzed under the conditions of gas chromatography. As a result, none of the stabilizers of phenol and cresol was detected. In addition, when the moisture in the ethylene tetrachloride after the treatment was analyzed by Karl Fischer's method, the moisture content was not more than 3 ppm by mass. Example 2 A stainless steel cylinder having an inner volume of 200 ml was charged with 20 g of a carbonaceous sorbent [molecular sieve carbon 5 A, manufactured by Takeda Pharmaceutical Industry Co., Ltd., with an average pore diameter of 5 A]. After the carbonaceous sorbent was vacuum-dried, 80 g of the ethylene tetrachloride shown in the above raw material example was charged while cooling the steel cylinder, and kept stirring at 20 ° C. After about 5 hours, the liquid phase was collected. Part of the analysis was performed under the conditions of the gas chromatography method of the above raw material examples. As a result, none of the stabilizers of phenol and cresol was detected. Example 3 20 g of zeolite [molecular sieve 13X (manufactured by Union Showa Corporation, average pore size 10 A, Si / A1 ratio = 0.81)] was charged as a sorbent, and the rest were treated under the same operation and conditions as in Example 1. As a result, none of the stabilizers in phenol and cresol was detected. Comparative Example 1 Paper Size Lai Jin Guanjia County (CNS) A4 Inspection (210X297 Gongchu) Lai -26- (Please read the precautions on the back before filling this page)

534898 7 A7 B7 經濟部智慧財產局8工消費合作社印製 五、發明説明（24) 以20g之沸石[分子篩XH— 9 ( Union昭和株式會社製 ，平均細孔徑爲3.2 A，Si/Al比=1 )]爲吸著劑充塡外 ，其餘同實例1之操作及條件下處理。其結果爲，幾乎不 能吸著安定劑之苯酣及甲酸’其總量爲132質量ppm。由 此可知，使用平均細孔徑小於3 · 2 A之沸石時安定劑之吸 著效率變低。 比較例2 以2 0g之碳質吸著劑[活性碳：粒狀白鷺KL，武田藥 品工業株式會社製，平均細孔徑爲35 A]爲吸著劑充塡 外，其餘同實例2之操作及條件下處理。其結果爲，幾乎 不能吸著安定劑之苯酚及甲酚，其總量爲11 9質量ppm。 另外，由於吸著四氯化乙烯使吸著熱變大，檢出新的分解 生成物。 實施例4 於內容積爲200ml之不銹鋼圓筒中，將作爲吸著劑之 15g之實施例1所記載之分子篩5A及5g之實施例2所記 載之分子舖碳5 A混合後充塡。將吸著劑真空乾燥後，邊 冷卻鋼筒邊充塡80g之原料例所示之四氯化乙烯，保持在 20°C下時時攪拌，約4小時後，採取液相部之一部份以上 述之原料例之氣相層析法之條件下分析。其結果爲，未檢 出苯酚及甲酚中任何一種安定劑。另外，分析四氯化乙烯 中之水份時，其水分値爲5質量ppm以下。 I i I -.....- - - - - Γ— ί0ί 111 n (請先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） -27- 534898 A7 B7 五、發明説明（25) 實施例5 (請先閲讀背面之注意事項再填寫本頁) 於內容積爲5L之不绣鋼圓筒中，充塡4.8L分子舖 5A ( MS — 5A)，在室溫（15°C )，壓力約0· 3Mpa之條件 下’以lOL/hi*— 1之線速度連續供給四氯化乙烯。採取供 給開始100小時後，300小時後及500小時後之出口液進 行分析。其結果爲，未檢出苯酚及甲酚中任何一種安定劑 ’水分値亦在5質量ppm以下。 其次，充塡氧化鋁-氧化鉻催化劑於反應器，於300 °C之反應溫度，約0.3MPa之反應壓力，HF/PCE爲6 (莫 耳數比），VS爲750h厂1之條件下，以上述所得之四氯 化乙烯及氟化氫爲原料進行連續反應。 開始反應24小時後之PCE轉化率爲99.6%，500小 時後之PCE轉化率爲99.4%，不認爲催化劑之活性降低 〇 比較例3 經濟部智慧財產笱員工消費合作社印製 充塡氧化鋁-氧化鉻催化劑於反應器，使用原料例所 示之含有安定劑（總量爲150質量ppm )之四氯化乙烯及 HF爲原料，於300°C之反應溫度，約0.3MPa之反應壓力 ，HF/PCE爲6 (莫耳數比），空間速度爲750W 1之條件 下，進行連續反應。 開始反應24小時後之PCE轉化率爲99.5%，500小 時後之PCE轉化率爲81.2%，認爲催化劑之活性降低。 由此可知，安定劑與催化劑活性之降低有關。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28- 534898 A7 B7 五、發明説明（26) 實施例6 (請先閲讀背面之注意事項再填寫本頁) 使用圖1所示之裝置，進行以下之操作。關於圖1中 各化合物如下所示。534898 7 A7 B7 Printed by Intellectual Property Bureau, Ministry of Economic Affairs, 8th Industrial Cooperative Cooperative, V. Invention Description (24) 20g of zeolite [Molecular Sieve XH-9 (Made by Union Showa Corporation, average pore diameter is 3.2 A, Si / Al ratio = 1)] Except for filling the sorbent, the rest are treated under the same operation and conditions as in Example 1. As a result, the total amount of phenylhydrazone and formic acid 'which hardly adsorbed the stabilizer was 132 mass ppm. From this, it can be seen that when a zeolite having an average pore diameter of less than 3.2 A is used, the adsorption efficiency of the stabilizer becomes low. Comparative Example 2 20 g of carbonaceous sorbent [activated carbon: granular egret KL, manufactured by Takeda Pharmaceutical Industry Co., Ltd., with an average pore diameter of 35 A] was used as the sorbent, the rest were the same as those in Example 2 and Processing. As a result, the total amount of phenol and cresol which could hardly adsorb the stabilizer was 119 mass ppm. In addition, adsorption of ethylene tetrachloride increased the adsorption heat, and a new decomposition product was detected. Example 4 In a stainless steel cylinder having an internal volume of 200 ml, 15 g of the molecular sieve 5A described in Example 1 as the sorbent and 5 g of the molecular carbon spread 5 A described in Example 2 were mixed and charged. After vacuum drying the sorbent, charge 80g of ethylene tetrachloride as shown in the example of the raw material while cooling the steel cylinder, and keep stirring at 20 ° C. After about 4 hours, take part of the liquid phase. The analysis was performed under the conditions of the gas chromatography method of the above raw material examples. As a result, none of the stabilizers of phenol and cresol was detected. When analyzing the water content in ethylene tetrachloride, the moisture content was 5 mass ppm or less. I i I -.....-----Γ— ί0ί 111 n (Please read the precautions on the reverse side before filling out this page) The size of the paper is applicable to Chinese national standards (CNS> A4 specification (210X297 mm) -27- 534898 A7 B7 V. Description of the Invention (25) Example 5 (Please read the precautions on the back before filling out this page) In a stainless steel cylinder with a volume of 5L, fill with 4.8L molecular coating 5A (MS — 5A), at room temperature (15 ° C) and pressure of about 0.3Mpa, 'continuously supply ethylene tetrachloride at a linear speed of lOL / hi * -1. Take 100 hours after the start of supply, 300 hours later and The outlet solution was analyzed after 500 hours. As a result, no stabilizer, 'moisture content', of phenol and cresol was also detected below 5 mass ppm. Next, the reactor was filled with alumina-chromium oxide catalyst, and A reaction temperature of 300 ° C, a reaction pressure of about 0.3 MPa, a HF / PCE of 6 (molar ratio), and a VS of 750h at Plant 1 under the conditions of using the tetrachloroethylene and hydrogen fluoride obtained above as raw materials for continuous reactions . The PCE conversion rate was 99.6% after 24 hours from the start of the reaction, and the PCE conversion rate was 99.4% after 500 hours. In order to reduce the activity of the catalyst, Comparative Example 3 The Ministry of Economic Affairs, Intellectual Property, and Employee Consumer Cooperatives printed and filled alumina-chromium oxide catalysts in the reactor, using stabilizers (total 150 mass ppm) shown in the example of raw materials. Vinyl chloride and HF are used as raw materials, and the continuous reaction is performed under the conditions of a reaction temperature of 300 ° C, a reaction pressure of about 0.3 MPa, an HF / PCE of 6 (molar number ratio), and a space velocity of 750 W 1. The PCE conversion rate after 24 hours is 99.5%, and the PCE conversion rate after 8 hours is 81.2%, which indicates that the activity of the catalyst is reduced. It can be seen that the stabilizer is related to the decrease of the activity of the catalyst. CNS) A4 specification (210X297 mm) -28- 534898 A7 B7 V. Description of invention (26) Example 6 (Please read the precautions on the back before filling this page) Use the device shown in Figure 1 to perform the following operations The compounds shown in Figure 1 are shown below.

四氯化乙烯：PCE 三氯化乙烯：TCE 2，2 —二氯—1，1，1—三氟乙烷：F123 2—氯—1，1，1，2—四氟乙烷：F124 2 —氯—1，1，1—三氟< 乙院：F— 133a 五氟乙烷：F125 1，1，1，2 —四氯乙院·· F134a 氟化氫：HF 氯化氫：HC1 經濟部智慧財產局員工消費合作社印製 圖1之裝置大略上由可各自充塡相異之催化劑之4個 氣相反應器A、B、C及D，及第1蒸餾塔，精製由第1 蒸餾塔之塔頂分離出含有五氟乙烷及1，1，1，2-四氟 乙烷之氣體之精製系，以及分離精製由第1蒸餾塔之塔底 分離出HCFC - 123等之中間體化合物及未反應之氟化氫 之第2蒸餾塔所構成。 於圖1中’關於反應器A及反應器B，進行生成五氟 乙烷之反應。首先，導入原料之四氯化乙烯（PCE )( 1 )於反應器A。反應器A充塡著最適宜反應之催化劑。同 時第2蒸餾塔所分離之氟化氫（29 )爲（2 )導入反應器 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 -29- 534898 經濟部智慧財產局員工消費合作社印製 A7 _B7五、發明説明（27) A。截化氣因應需要可重新追加導入。反應器中發生如式 1及式2所示之反應以及發生式3及式4所示之部份反應 ，生成包含氯化氫、中間體之HCFC — 123、HCFC — 124及 HFC - 125之第1生成物（3)。合流第1生成物（3)與 後述之第2生成物（7)、第3生成物（13)及第4生成 物（16 )成（21 )後，導入第1蒸餾塔。 導入精製系所分離之HCFC - 1 24 ( 26 )爲（4)於反 應器B (如圖2中，①表示（26 )與（4 )相接續，同樣 地②表示（27)與（14)以及③表示（28)與（5)相接 續）。另外，以第2蒸餾塔所分離之HCFC— 123/HF ( 28 )爲（5 )導入其中，並且亦導入第2蒸餾塔之塔底所分 離之部份氟化氫（HF ) ( 29 )爲（6 )使之循環。反應器 B充塡著最適宜反應之催化劑。反應器B中，依據上述之 式3及式4之反應，生成含有HC1、目的物之HFC — 125 ，未反應之HCFC - 123及HCFC - 124之第2生成物（7 ) 。合流第2生成物（7 )與其他反應器生成之氣體成（21 )後，導入第1蒸餾塔。 另一方面，有關反應器C及D，進行生成1，1，1， 2-四氟乙烷之反應。反應器C中，導入原料之三氯化乙 烯（TCE ) ( 11 )，各自導入新加入之氟化氫（10 )及循 環氟化氫（12)。反應器C中，依據上述之式5之反應， 生成含有以HC1及中間體之HCFC — 133a爲主之第3生成 物（13)，合流第3生成物（13)與其他反應裝置生成之 氣體成（21 )後，導入第1蒸餾塔。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) -30- 534898 A7 B7 五、發明説明（28) (請先閱讀背面之注意事項再填寫本頁) 反應器D中，導入第2蒸餾塔所分離之110?(：-13 3a/HF ( 27 )及循環氟化氫（15 )。依據上述之式6之 反應，生成含有以HC1及目的物之HFC — 134a與未反應 之HCFC— 133a爲主之第4生成物（16)，合流第4生成 物（16)與其他反應器生成之氣體成（21)導入第1蒸餾 塔。 合流第1生成物（3 )、第2生成物（7 )、第3生成 物（13)以及第4生成物（16)成（21)後，導入第1蒸 餾塔。由第1蒸餾塔之塔頂，餾出含有以HC1、HFC-134a、HFC — 125、HCFC — 124、HCFC — 133a 及氟化氫爲 主之第1塔頂餾出部份（22 )。將此第1塔頂餾出部份， 供予精製系，分離出 HC1 ( 24) 、HFC — 134a/HFC — 125 ( 25 ) 、HCFC — 124 ( 26 )及回收之HF ( 17 )等。精製系包 含未在圖中表示之第3蒸餾塔。HCFC - 124及氟化氫可循 環各反應步驟再使用，而回收製品之HC1、HFC — 134a及 HFC - 125。 經濟部智慧財產局”貝工消費合作社印製 由第1蒸餾塔之塔底，餾出含有以HCFC - 123及 HCFC — 13 3a爲主之第1塔底餾出部份（23)。將此第1 塔底餾出部份（23 )導入第2蒸餾塔，由塔頂回收HCFC —133a/HF ( 27 )，使其循環於反應器D。在第2蒸餾塔 之供給部之上方部份設有分部，可提出HCFC — 123/HF ( 28)，使之循環於反應器B。在第2蒸餾塔之塔底回收 HF ( 29 )，可因應反應器A、B、C及D之需要使之循環 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -31 - 534898 A7 B7 五、發明説明（29) 其次是使用圖1所示之裝置，依據上述方法之運轉例 如下所示。 合流生成物（21 )之流量爲100 ( kg/hi*)時，關於步 驟流程（1 )至（7 ) 、（ 10 )至（17 )以及（21 )至（29 )中，各成份之質量配合（質量％)如表1及表2所示。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局g (工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -32- 534898 Δ7 Α7 Β7 五、發明説明（30 ) 經濟部智慧財產局員工消費合作社印製 O CD o r-H L〇 CO O o 〇 o i〇 卜 o <M o O o f-H q o o q 〇· d d d d d d d d d d — 寸 CO 卜 co ΓΜ co o o i〇 CO ο o o o o rH o o o d d o CO ώ (N l〇 CO d d d co ① o o 卜 o 〇 寸 rvi 〇 o o o r-H CO LO o o o o o o o o o d d o d 〇· (M CO d o d d <N CO o rH o L〇 f-H o o o LO (N o o o o CO o o o o ^^ d d o d o CO d d d d 寸 CO o i—1 ιΛ C^l LO o o co lO CO o o o o ιΛ CO CM o o o d d d 〇· CO I> (N d d d CO r-H o o (N o o o 〇 o o l〇 (Μ o o o o o OQ o o o 〇 (N V--^ d o' o d d lO d d d d L〇 o o o o o o o o o 〇q rH o o o o q o o o o o O '>—^ o d d d d d d d d 寸 ^—s o o o o o 卜 o o o o ί O o o o o q 05 o o q o ο 〇· d 〇· d o* CO o d d 〇· CO l〇 o CO ① 00 寸 co o o 寸 CD CO r-H (M o (N rH l〇 o o o rH d d d CD d d d d (N o 〇 o o o IC o o o o £ q 〇 o q o CO o o o o co d 〇· o d d rH o d d d f-H o o o o o 寸 o o o o LO o o 00 q o ① o o o o 寸 d d o d 〇· d d d d l〇 o o o CO rH o o o CD 2 o T—i o CD 00 寸 o o o 〇 d lO o d d d d o’ d 〇· ΙΟ l〇 lO o o 00 rH o o l〇 rH S CO ①· o o co CD o o rH τ-Η d d 〇· d d co rH d d d I> o o r-H o o I> o o o o 00 S q q o q o ΙΛ o q q o ΙΟ d d 〇· d 〇· 寸 d d d d 寸· o o o o o Ο o co o o co S o o o o o q o LO o o ΙΟ d d d d 〇· d o* CN d 〇· ^^ /-—^ 寸 CO 03 ί? (M (N 寸 r<\ CM r*H UT J cd CO Ct co l〇 <N (M 寸 00 (M f-H r-H 00 rH cd 0 6 6 co < 〇 1¾ 〇 co Εη o o o i-H 〇 〇 〇 ο ffi ffi h-* HH K s a ffi fin ㈠ ¥i\ (請先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國冢標準（CNS ) Λ4規格（Ζΐυχζν，么、度； -33- 534898Ethylene tetrachloride: PCE Ethylene trichloride: TCE 2,2-dichloro-1,1,1-trifluoroethane: F123 2-chloro-1,1,1,2-tetrafluoroethane: F124 2 —Chlorine-1,1,1—Trifluoro < Secondary School: F- 133a Pentafluoroethane: F125 1,1,1,2,4-Tetrachloroethane Academy ·· F134a Hydrogen Fluoride: HF Hydrogen Chloride: HC1 Intellectual Property of the Ministry of Economy Bureau's consumer cooperative prints the device in Figure 1. It consists of four gas-phase reactors A, B, C, and D, which can be filled with different catalysts, and the first distillation column. The tower is refined by the first distillation column. Separate the refining system of gas containing pentafluoroethane and 1,1,1,2-tetrafluoroethane, and separate and refine intermediate compounds such as HCFC-123 from the bottom of the first distillation column and The second distillation column of the hydrogen fluoride reacted. In FIG. 1, 'Reactor A and Reactor B are reacted to produce pentafluoroethane. First, ethylene tetrachloride (PCE) (1) as a raw material is introduced into the reactor A. Reactor A is filled with the most suitable catalyst. At the same time, the hydrogen fluoride (29) separated from the second distillation column is (2) introduced into the reactor. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). -29- 534898 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs System A7 _B7 V. Description of the invention (27) A. Intercept gas can be re-introduced as needed. The reactions shown in Formulas 1 and 2 and the partial reactions shown in Formulas 3 and 4 occur in the reactor to form the first generation of HCFC-123, HCFC-124, and HFC-125 containing hydrogen chloride and intermediates.物 (3). The first product (3) is merged with the second product (7), the third product (13), and the fourth product (16) described later to form (21), and then introduced into the first distillation column. The HCFC-1 24 (26) separated by the introduction and purification system is (4) in the reactor B (as shown in FIG. 2, ① indicates that (26) is connected to (4), and similarly ② indicates (27) and (14) And ③ indicates that (28) and (5) continue). In addition, the HCFC-123 / HF (28) separated by the second distillation column was introduced into it as (5), and a part of the hydrogen fluoride (HF) (29) separated from the bottom of the second distillation column was also introduced into (6) ) Make it loop. Reactor B is filled with the most suitable catalyst. In the reactor B, the second product (7) containing HC1, the target substance HFC-125, unreacted HCFC-123, and HCFC-124 is generated in accordance with the reactions of the above-mentioned formulas 3 and 4. The combined second product (7) and the gas (21) produced by other reactors are introduced into the first distillation column. On the other hand, regarding reactors C and D, a reaction for producing 1,1,1,2-tetrafluoroethane is performed. In the reactor C, ethylene trichloride (TCE) (11) as a raw material is introduced, and newly added hydrogen fluoride (10) and cyclic hydrogen fluoride (12) are introduced. In the reactor C, the third product (13) containing HCFC-133a mainly containing HC1 and intermediates is generated in accordance with the reaction of the above-mentioned Formula 5. The gas generated by the combined third product (13) and other reaction devices is generated. After (21), it is introduced into the first distillation column. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) -30- 534898 A7 B7 V. Description of the invention (28) (Please read the precautions on the back first Please fill in this page again) In the reactor D, 110? (: -13 3a / HF (27) and circulating hydrogen fluoride (15)) separated by the second distillation column are introduced. According to the reaction of the above formula 6, HC1 is generated The fourth product (16) consisting mainly of HFC-134a and unreacted HCFC-133a and the target product, and the combined fourth product (16) and the gas produced by other reactors (21) are introduced into the first distillation column. After the first product (3), the second product (7), the third product (13), and the fourth product (16) are combined into (21), the first product is introduced into the first distillation column. At the top of the column, a first overhead section (22) containing HC1, HFC-134a, HFC-125, HCFC-124, HCFC-133a, and hydrogen fluoride is distilled. This first overhead section is distilled. For the refining department, HC1 (24), HFC-134a / HFC-125 (25), HCFC-124 (26), and recovered HF (17) were separated. Refining Contains the third distillation column not shown in the figure. HCFC-124 and hydrogen fluoride can be reused in each reaction step, and the recovered products HC1, HFC-134a and HFC-125 are printed. Printed by the Bureau of Intellectual Property of the Ministry of Economic Affairs, Shellfish Consumer Cooperative The bottom of the first distillation column is produced, and the first bottom distillation section (23) containing HCFC-123 and HCFC-13 3a is distilled off. This first bottom distillation section (23) Introduce the second distillation column, recover HCFC —133a / HF (27) from the top of the column, and circulate it to reactor D. There is a branch above the supply part of the second distillation column, and HCFC — 123 / HF (28), which is circulated in reactor B. HF (29) is recovered at the bottom of the second distillation column, which can be circulated according to the needs of reactors A, B, C, and D. This paper size applies Chinese national standards (CNS) A4 specification (210X297 mm) -31-534898 A7 B7 V. Description of the invention (29) Secondly, using the device shown in Figure 1, the operation example according to the above method is shown below. Confluence product (21) of When the flow rate is 100 (kg / hi *), the steps (1) to (7), (10) to (17), and (21) to (29) ), The mass combination (mass%) of each component is shown in Table 1 and Table 2. (Please read the precautions on the back before filling out this page) Intellectual Property Bureau of the Ministry of Economic Affairs China National Standard (CNS) A4 specification (210X297 mm) -32- 534898 Δ7 Α7 Β7 V. Description of invention (30) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs O CD o rH L〇CO O o 〇oi〇 o < M o O o fH qooq 〇 · dddddddddd — inch CO co ΓΜ co ooi〇CO ο oooo rH oooddo CO free (N l〇CO ddd co ① oo oo o 〇inch rvi 〇ooo rH CO LO oooooooooddod 〇 · (M CO dodd < N CO o rH o L〇fH ooo LO (N oooo CO oooo ^^ ddodo CO dddd inch CO oi—1 ιΛ C ^ l LO oo co lO CO oooo ιΛ CO CM oooddd 〇 · CO I > (N ddd CO rH oo (N ooo 〇ool〇 (Μ ooooo OQ ooo 〇 (N V-^ do 'odd lO dddd L〇ooooooooo ooq rH ooooqooo oo O '> — ^ odddddddd inch ^ —sooooo oooo ί O ooooq 05 ooqo ο 〇 d 〇 · do * CO odd 〇 · CO l〇o CO ① 00 inch co oo inch CD CO rH (M o (N rH l〇ooo rH ddd CD dddd (N o 〇ooo IC oooo £ q 〇oqo CO oooo co d 〇 · odd rH oddd fH ooooo inch oooo LO oo 00 qo ① oooo inch ddod 〇 · ddddl〇ooo CO rH ooo CD 2 o T-io CD 00 inch ooo 〇d lO odddd o 'd 〇 · ΙΟ l〇lO oo 00 rH ool〇rH S CO ① · oo co CD oo rH τ-Η dd 〇 · dd co rH ddd I > oo rH oo I > oooo 00 S qqoqo ΙΛ oqqo ΙΟ dd 〇 d 〇 · inch dddd inch · ooooo 〇 o co oo co S oooooqo LO oo ΙΟ dddd 〇 do * CN d 〇 · ^^ / -— ^ inch CO 03 ί ? (M (N inch r < \ CM r * H UT J cd CO Ct co l0 &N; N (M inch 00 (M fH rH 00 rH cd 0 6 6 co < 〇1¾ 〇co Εη ooo iH 〇〇〇ο ffi ffi h- * HH K sa ffi fin ㈠ ¥ i \ (Please read the notes on the back before filling out this page) The paper size of the paper is in accordance with the Chinese national standard CNS) Λ4 specification (Zΐυχζν, Mod, Degree; -33- 534898

A B \ί/ 31 /[ 明説 明發五 經濟部智慈財產局員工消費合作社印製A B \ ί / 31 / [Printed by Mingfa 5 Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

(29) 0.00 0.00 0.10 0.00 0.00 43.35 0.00 0.00 0.00 0.03 43.49 (28) 0.00 0.00 0.80 0.00 0.00 4.64 1 0.00 0.00 0.00 0.00 5.45 (27) 0.00 0.01 0.01 0.00 ί 29.85 3·61 I 0.00 0.00 0.00 0.65 34.12 (26) 0.00 5.10 0.00 0.03 I 0.31 0.45 0.00 0.00 0.00 0.06 5.96 (25) 1.39 0.27 0.00 3.16 0.00 0.15 0.00 0.00 0.00 0.08 5.05 (24) 0.33 0.00 0.00 | 0.00 0.00 0.00 1 5.55 0.00 0.00 0.00 5.88 (23) 0.00 0.01 0.91 0.00 29.85 51.61 1 0.00 0.00 0.00 0.72 83.11 (22) 1.72 5.37 0.00 3.19 j 0.31 0.60 5.55 0.00 0.00 0.14 16.89 (21) 1.72 5.38 0.91 3.20 30.16 52.21 5.55 0.00 0.00 0.86 100.00 HFC-125 (F125) HCFC-124 (F124) HCFC-123 (F123) HFC-I34a (Fl34a) HCFC-l33a(Fl33a) HF Hd ^ PCE TCE 其他 TOTAL (請先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -34- 534898 A7 B7 經濟部智慧財產局Μ工消費合作社印製 五、發明説明（32 ) 實施例7 使用圖2所示之裝置，進行以下之操作。關於圖2中 各化合物如下所示。 四氯化乙嫌：PCE 三氯化乙烯：TCE 2，2-二氯—1’ 1，1—三氟乙烷：F123 2 —氯一1，1’ 1，2 —四氟乙烷：F124 2-氯—1，1，1一三氟乙烷：F— 133a 五氟乙烷：F125 1，1，1，2—四氟乙烷·· F134a 氟化氫：HF 氯化氫：HC1 圖2之裝置大略上由可各自充塡相異之催化劑之4個 氣相反應器A、B、C及D，及第1蒸餾塔，精製由第2 蒸餾塔之塔頂分離出含有五氟乙烷及1，1，1，2-四氟 乙烷之氣體之精製系，以及分離由第2蒸餾塔之塔底分離 出HCFC - 133a等之中間體化合物及未反應之氟化氫之第 3蒸餾塔所構成。 於圖2中，關於反應器A及反應器B，進行生成五氟 乙烷之反應。首先導入原料之四氯化乙烯（PCE ) ( 31 ) 於反應器A。反應器A充塡著最適宜反應之催化劑。同時 第3蒸餾塔所分離之氟化氫（60)經由氟化氧循環管道成 爲（32)導入反應器A。氟化氫因應需要可重新追加導入 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -35- 534898 經濟部智慧財產局g(工消費合作社印製 A7 B7五、發明説明（33) 。反應器中發生如式1及式2所示之反應以及發生式3及 式4所示之部份反應，生成包含氯化氫、中間體之HCFC —123、HCFC — 124、HFC — 125及未反應之氟化氫之第1 生成物（33)。合流第1生成物（33)與後述之第2生成 物（37)、第3生成物（43)及第4生成物（46)成（51 )後，導入第1蒸餾塔5。 精製系所分離之HCFC — 124 ( 56 )爲（34)導入反應 器B (如圖1中，①表示（56 )與（34 )相接續，同樣地 ②表示（58)與（44)以及③表示（59)與（35)相接續 )。另外，以第3蒸餾塔7所分離之HCFC - 123/HF ( 59 )爲（35 )導入其中，並且亦導入第3蒸餾塔7之塔底所 分離之部份氟化氫（HF) (60)爲（36)使之循環。反 應器B充塡著最適宜反應之催化劑。反應器B中，依據 上述之式3及式4之反應，生成含有HC1、目的物之HFC —125，未反應之HCFC — 123及HCFC — 124之第2生成物 (37 )。合流第2生成物（37 )與其他反應器生成之氣體 成（51 )後，導入第1蒸餾塔5。 另一方面，有關反應器C及D，進行生成1，1，1， 2-四氟乙烷之反應。反應器C中，導入原料之四氯化乙 烯（TCE ) ( 41 )，各自導入新加入之氟化氫（40 )及循 環氟化氫（42)。反應器C中，依據上述之式5之反應’ 生成含有以HC1、中間體之HCFC — 133a及未反應之氟化 氫爲主之第3生成物（43 )，合流第3生成物（43 )與其 他反應裝置生成之氣體成（51)後，導入第1蒸餾塔5° 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 -36- 534898 經濟部智慧財產局Μ工消費合作社印製 A7 B7五、發明説明（34) 反應器D中，以第3蒸餾塔7所分離之HCFC -133a/HF(58)爲（44)導入及以循環氟化氫（60)爲（ 45)導入其中。依據上述之式6之反應，生成含有以HC1 及目的物之HFC — 134a及未反應之HCFC — 133a及氟化氫 爲主之第4生成物（46)，第4生成物（46)與其他反應 器生成之氣體合流成（51)導入第1蒸餾塔5。 合流第1生成物（33)、第2生成物（37)、第3生 成物（43)以及第4生成物（46)成（51)後，導入第1 蒸餾塔5。由第1蒸餾塔5之塔頂，餾出以HC1爲主之第 1塔頂餾出部份（52 )。由第1蒸餾塔5之塔底，餾出以 2，2 —二氯—1，1，1—三氟乙烷、2 —氯—1，1，1，2 — 四氟乙烷、五氟乙烷、2-氯一 1，1，1—三氟乙烷、1，1 ，1，2-四氟乙烷及氟化氫爲主之第1塔底餾出部份（53 )° 將第1塔底餾出部份（53 )導入第2蒸餾塔6，由第 2蒸餾塔6之塔頂餾出以五氟乙烷、1，1，1，2 —四氟乙 烷、2 —氯一 1，1，1，2-四氟乙烷及氟化氫爲主之第2 塔頂餾出部份（54 )。其次，將此第2塔頂餾出部份（54 )，供予精製系，分離出HFC— 134a/HFC— 1 25 ( 5 5 )、 HCFC — 1 24 (56)及氟化氫。精製系包含未在圖中表示之 第4蒸餾塔。HCFC - 124及氟化氫可循環各反應步驟再使 用。由第2蒸餾塔6之塔底，分離出以2，2-二氯一 1， 1一二氟乙院、2 —氯—1，1，1一二氟乙院及氟化氫爲 主之第2塔底餾出部份（57 )。將第2塔底餾出部份（57 (請先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CMS ) Α4規格（210Χ297公釐） -37- 534898 A7 ___B7 五、發明説明（35) )導入第3蒸餾塔7。 第3蒸I留塔7之塔頂分離出HCFC — 133a/HF爲第3 塔頂餾出部份（5 8 )。於反應器D中循環使用。在第3 蒸餾塔7之供給部上方部份設有分部，可提出HCFC -12 3/HF ( 59 )，於反應器B中循環使用。在第3蒸餾塔之 塔底回收氟化氫（60 )，可因應反應器A、B、C及D之 需要使之循環。 其次是使用圖2所示之裝置，依據上述方法之運轉例 如下所示。 合流生成物（51 )之流量爲100 ( kg/hr)時，關於步 驟流程（31)至（37) 、（ 40)至（47)以及（51)至（ 6〇)中，各成份之質量配合（質量％)如表3及表4所示 (請先閲讀背面之注意事項再填寫本頁) 丨·!. 訂 經濟部智慧財產局g(工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 -38- 534898 A7 B7 五、發明説明（36) 經濟部智慧財產苟員工消費合作社印製 寸 o o o ① CN d O o d CD 〇 d o o d CO t-H d o o d o o o o o d o o d LO 寸 d ◦ 〇 d rr o d CO o d r> O CO CM CO CN CO (M LO CO CO r-H o o d O o d L〇 CD d CO 寸 CD 〇 ^--V LO o o d o o o’ 卜 o d o o o 〇 o d 寸 (M cq CO o o o o o d o o d o o d f-H CO C^I CO 寸 ''—^ o o d rH o d r*H o d o o d i〇 00 o (M r-H ① CO o o d o o d o o d l〇 CD d CM rH — CO CO 3 o o d »-H o d r-H o d i〇 o d I> CO cq CO ϊ> i〇 CM c<i o q d o o d CO o d 10 (M CO /·*—V CM o q d o o 〇· O d o q d o o d o CN 1C o o d o o d o o d o d L〇 (M iri r-H o o d o o d o o d o o d o o d o o d o o d o o d (N 〇 o o d (N 〇 o o o o o o o o o o l> C5 o o o o o o o o 卜 Ο d d d d d CO d d d d CO s 卜 CO l〇 CO t-H o 寸’ CO (M d o d CO CO d 寸 r-H CD o lO o o o d o q 〇· o d ① cq rH CD CO o o d o o d o o d o o d o o d ΙΛ CO o o d o o d o o d o o d l〇 CO rH /^~V lO CO o o 〇· o o d o 00 d o o d o o d 寸 CD 寸· o o d o o d o o d o o d 10 寸 l〇 CO o o d o rH iC o o 〇· CO O d rH CO O ΙΟ 寸 d o o d o o 〇· o o d ¢0 0 d CO 0 10 CO CO l〇 CO d t> a> d l〇 CD d o o d 〇 o d 00 CO CO CD rH o q d o o d d r-H rH l> cq CO o o d o o d q o o o d o o d l> iO 呀 o o d o o d o q d 〇 〇 〇· 00 10 寸 rH CO o o d o o d o o d o o d o o d o o d o o 〇· CO l〇 cq o o d 0 0 d CO L〇 (N l〇 ΟΆ m (M Λ—V 寸 CN T—( Tf rH CO oa T—H CO (M rH «V cd 寸 CO rH d 寸 CO aS CO CO rH /0^ cd r-H 6 ό 1-H ό CO 妾 < 6 6 CO ^-4 o w W pCH o o P=H o rH a 〇 o ffi a ffi K ffi ffi ffi Pm 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 #1. -39- 534898(29) 0.00 0.00 0.10 0.00 0.00 43.35 0.00 0.00 0.00 0.0 0.03 43.49 (28) 0.00 0.00 0.80 0.00 0.00 4.64 1 0.00 0.00 0.00 0.00 5.45 (27) 0.00 0.01 0.01 0.00 ί 29.85 3.61 I 0.00 0.00 0.00 0.65 34.12 (26) 0.00 5.10 0.00 0.03 I 0.31 0.45 0.00 0.00 0.00 0.06 5.96 (25) 1.39 0.27 0.00 3.16 0.00 0.15 0.00 0.00 0.00 0.08 5.05 (24) 0.33 0.00 0.00 | 0.00 0.00 0.00 1 5.55 0.00 0.00 0.00 5.88 (23) 0.00 0.01 0.91 0.00 29.85 51.61 1 0.00 0.00 0.00 0.72 83.11 (22) 1.72 5.37 0.00 3.19 j 0.31 0.60 5.55 0.00 0.00 0.14 16.89 (21) 1.72 5.38 0.91 3.20 30.16 52.21 5.55 0.00 0.00 0.86 100.00 HFC-125 (F125) HCFC-124 (F124) HCFC- 123 (F123) HFC-I34a (Fl34a) HCFC-l33a (Fl33a) HF Hd ^ PCE TCE Other TOTAL (Please read the precautions on the back before filling out this page) The paper size of this paper applies the Chinese National Standard (CNS) Α4 specifications ( 210X297 mm) -34- 534898 A7 B7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperative, V. Description of Invention (32) Example 7 Use the device shown in Figure 2 to perform the following operations. The compounds shown in Figure 2 are shown below. Ethyl tetrachloride: PCE Ethylene trichloride: TCE 2,2-dichloro-1 '1,1-trifluoroethane: F123 2 —Chlorine-1,1' 1,2-tetrafluoroethane: F124 2-Chloro-1,1,1,1-trifluoroethane: F- 133a Pentafluoroethane: F125 1,1,1,2-tetrafluoroethane · F134a Hydrogen fluoride: HF Hydrogen chloride: HC1 Figure 2 outline of the device Four gas-phase reactors A, B, C, and D, each of which can be filled with different catalysts, and a first distillation column are refined, and pentafluoroethane and 1, which are contained in the top of the second distillation column, are separated. Refining system for 1,1,2-tetrafluoroethane gas and a third distillation column for separating intermediate compounds such as HCFC-133a and unreacted hydrogen fluoride from the bottom of the second distillation column. In Fig. 2, with respect to reactor A and reactor B, a reaction for producing pentafluoroethane is performed. Firstly, ethylene tetrachloride (PCE) (31), which is a raw material, is introduced into the reactor A. Reactor A is filled with the most suitable catalyst. At the same time, hydrogen fluoride (60) separated by the third distillation column is introduced into reactor A via the oxygen fluoride circulation pipe as (32). Hydrogen fluoride can be re-introduced as needed (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -35- 534898 Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative prints A7 B7 V. Description of the invention (33). Reactions shown in Formula 1 and Formula 2 and partial reactions shown in Formula 3 and Formula 4 occur in the reactor to produce HCFC containing hydrogen chloride and intermediates — 123, HCFC — 124, HFC — 125 and the first product (33) of unreacted hydrogen fluoride. Confluence of the first product (33) and the second product (37), the third product (43) described later and After the fourth product (46) becomes (51), it is introduced into the first distillation column 5. The HCFC-124 (56) separated by the purification system is introduced into the reactor B as (34) (as shown in FIG. 1, ① indicates (56) (Continued with (34), the same ② means (58) and (44) and ③ means (59) and (35) connected). In addition, HCFC-123 / HF separated by the third distillation column 7 (59 ) Is introduced into (35), and a part of the hydrogen fluoride (HF) separated from the bottom of the third distillation column 7 is also introduced (60) is (36) so that Recycling. Reactor B is filled with the most suitable catalyst. In Reactor B, HFC-125 containing HC1, target substance, HCFC-123, and HCFC- The second product (37) of 124. The combined second product (37) and the gas (51) produced by other reactors are introduced into the first distillation column 5. On the other hand, for reactors C and D, Reaction to produce 1,1,1,2-tetrafluoroethane. In reactor C, ethylene tetrachloride (TCE) (41) as a raw material is introduced, and newly added hydrogen fluoride (40) and cyclic hydrogen fluoride (42) are introduced. In the reactor C, the reaction according to the above formula 5 'generates a third product (43) containing HC1, intermediate HCFC-133a and unreacted hydrogen fluoride, and the combined third product (43) and After the gas generated by other reaction devices is (51), it is introduced into the first distillation column at 5 °. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). -36- 534898 Printed by A7 B7, M Industrial Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs Description of the invention (34) In the reactor D, HCFC-133a / HF (58) separated by the third distillation column 7 is introduced as (44) and circulating hydrogen fluoride (60) is introduced as (45). According to the above formula 6 reaction to produce the fourth product (46) containing HC1 and the target HFC-134a and unreacted HCFC-133a and hydrogen fluoride, and the fourth product (46) merges with the gas produced by other reactors The component (51) is introduced into the first distillation column 5. After the first product (33), the second product (37), the third product (43), and the fourth product (46) are combined (51), they are introduced into the first distillation column 5. From the top of the first distillation column 5, a first top distillation section (52) mainly composed of HC1 is distilled. From the bottom of the first distillation column 5, distillate with 2,2-dichloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, pentafluoro Ethane, 2-chloro-1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane and hydrogen fluoride as the first bottom distillation part (53) ° The bottom distillation part (53) is introduced into the second distillation column 6, and from the top of the second distillation column 6, pentafluoroethane, 1,1,1,2, tetrafluoroethane, 2-chloro-1 The second overhead distillate (54) consisting mainly of 1,1,1,2-tetrafluoroethane and hydrogen fluoride. Next, the second column overhead part (54) was supplied to the refining system, and HFC-134a / HFC-1 25 (55), HCFC-1 24 (56), and hydrogen fluoride were separated. The purification system includes a fourth distillation column (not shown). HCFC-124 and hydrogen fluoride can be reused for each reaction step. From the bottom of the second distillation column 6, a second 2 mainly consisting of 2,2-dichloro-1, 1, 1-difluoroethane, 2-chloro-1, 1, 1, 1-difluoroethane, and hydrogen fluoride was separated. The bottom of the column was distilled off (57). Distill the bottom of the second column (57 (please read the precautions on the back before filling this page). The size of the paper is applicable to the Chinese National Standard (CMS) A4 specification (210 × 297 mm) -37- 534898 A7 ___B7 5. Description of the invention (35)) is introduced into the third distillation column 7. HCFC — 133a / HF is separated from the top of the third distillation column 7 leaving column 7 — 133a / HF is the third column top distillation section (5 8). Recycled in reactor D. A branch is provided at the upper part of the third distillation column 7 and the HCFC-12 3 / HF (59) can be provided for recycling in the reactor B. Hydrogen fluoride (60) is recovered at the bottom of the third distillation column, and can be circulated according to the needs of reactors A, B, C, and D. The second is to use the device shown in Fig. 2. An example of operation according to the above method is shown below. When the flow rate of the combined product (51) is 100 (kg / hr), the mass of each component in the steps (31) to (37), (40) to (47), and (51) to (60) The cooperation (mass%) is shown in Table 3 and Table 4 (Please read the precautions on the back before filling this page) (CNS) A4 specifications (210X297 mm) -38- 534898 A7 B7 V. Description of invention (36) Printed by the Intellectual Property Department of the Ministry of Economic Affairs and the Employees' Cooperative Cooperative Society ooo ① CN d O od CD 〇dood CO tH doodooooodood LO inch d 〇d rr od CO od r > O CO CM CO CN CO (M LO CO CO rH ood O od L〇CD d CO inch CD 〇 ^-V LO oodoo o 'Buodooo 〇od inch (M cq CO ooooodoodood fH CO C ^ I CO inch ''-^ ood rH odr * H odoodi〇00 o (M rH ① CO oodoodoodl〇CD d CM rH — CO CO 3 ood »-H od rH odi〇od I > CO cq CO ϊ > i〇CM c < ioqdood CO od 10 (M CO / · * —V CM oqdoo 〇 · O do qdoodo CN 1C oodoodoodod L〇 (M iri rH oodoodoodoodoodoodood ood (N 〇ood (N 〇oooooooooo l > C5 oooooooo) ddddd CO dddd CO s CO CO l〇CO tH o inch 'CO (M dod CO CO d inch rH CD o lO ooodoq 〇 · od ① cq rH CD CO oodoodoodoodood ΙΛ CO oodoodoodoodl〇CO rH / ^ ~ V lO CO oo 〇 · oodo 00 doodood inch CD inch oodoodoodood 10 inch l〇CO oodo rH iC oo 〇 CO O d rH CO O ΙΟ inch doodoo 〇 · ood ¢ 0 0 d CO 0 10 CO CO l〇CO d t > a > dl〇CD dood 〇od 00 CO CO CD rH oqdoodd rH rH l > cq CO oodoodqooodood l > iO 呀 odoodoqd 〇 〇〇 · 00 10 inch rH CO oodoodoodoodoodoodoo 〇 · CO l〇cq ood 0 0 d CO L〇 (N l〇〇Ά m (M Λ—V inch CN T— (Tf rH CO oa T—H CO (M rH « V cd inch CO rH d inch CO aS CO CO rH / 0 ^ cd rH 6 ό 1-H ό CO 妾 < 6 6 CO ^ -4 ow W pCH oo P = H o rH a 〇o ffi a ffi K ffi ffi ffi Pm This paper size is applicable to China National Standard (CNS) A4 size (210X297 mm) (Please read the note on the back first Matters need to be filled out on this page) Order # 1. -39- 534898

A B 經濟部智慧財產^7員工消費合作社印製 五、發明説明（37) (60) 0.00 0.00 0.10 0.00 I 0.00 43.35 0.00 0.00 0.00 0.03 43.49 (59) 0.00 0.00 0.80 0.00 0.00 4.64 1 0.00 0.00 0.00 0.00 5.45 (58) 0.00 0.01 0.01 0.00 29.85 j 3.61 1 0.00 0.00 0.00 0.65 34.12 (57) 0.00 0.01 0.91 0.00 29.85 [ 51.61 0.00 0.00 0.00 0.68 83.06 (56) 0.00 5.10 0.00 0.03 0.31 0.45 0.00 0.00 0.00 0.06 5.96 (55) 1.39 0.01 0.00 3.10 j 0.00 0.01 0.00 0.00 0.00 0.13 4.64 (54) 1.39 5.37 0.00 3.19 0.31 0.60 0.00 0.00 0.00 0.19 11.06 (53) 〇 CO 5.38 0.91 3.20 | 30.16 52.21 0.00 0.00 0.86 94.12 (52) 0.33 0.00 0.00 0.00 0.00 0.00 5.55 0.00 0.00 0.00 5.88 (51) 1.72 5.38 0.91 3.20 30.16 52.21 5.55 0.00 0.00 0.86 100.00 LO 寸 ✓—s CO a 寸 2 CO CO (Μ rH οα rH 寸 (N CO CO t-H ci ?—) a CO LC οα (N τ-Η (M r—H 1 寸 00 CO 1-H J rH 6 〇 rH 1 ό •a C 6 Ph o w w o 〇 o o o o o K E Oh (請先閱讀背面之注意事項再填寫本頁) 訂 #1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -40- 534898 A7 B7 五、發明説明（38) 產業上利用之可能性 如上述之說明，由於使用本發明之精製方法，可減低 四氯化乙烯中所含之安定劑。本發明之精製方法，特別適 用於含有如苯酚及甲酚等之具有羥基之芳香族化合物之四 氯化乙烯，但亦可使用於含有具有胺基之芳香族化合物之 四氯化乙烯。以已減低具有羥基之芳香族化合物之四氯化 乙烯爲原料，製造五氟乙烷時，可達成提高製造步驟中所 使用之催化劑之壽命，並且可有效率地，經濟地製造五氟 乙烷。 依據關於本發明中氫氟化碳之製造方法，無須在各反 應裝置中，設置生成物之分離步驟，合流這些反應裝置之 生成物後於蒸餾塔蒸餾，回收目的物之HFC- 134a、HFC 一 125及副生成物之HC1爲製品，因爲其他中間體及未反 應原料可再循環於各步驟使用，所以有關連續運轉之步驟 條件安定，步驟管理變容易，且設備亦單純化，而且與以 往之方法相比較，可降低單位能量源。 (請先閱讀背面之注意事項再填寫本頁) · ^•-t» 經濟部智慧財產局員工消費合作社印製 可 ，烷之 時甲等 法氟烷 方二乙 ti及氟 製烷三 之乙1-碳氟， 化四 1 氟-卜 2 氫，， 之 1 院 明卜乙 發，氟 本1二 於或-關烷 2 用乙卜 使氟、 ， 五院 。 外造甲碳 另製氟化 時三氟 同、氫 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -41 -AB Intellectual Property of the Ministry of Economic Affairs ^ 7 Printed by Employee Consumer Cooperatives V. Invention Description (37) (60) 0.00 0.00 0.10 0.00 I 0.00 43.35 0.00 0.00 0.00 0.03 43.49 (59) 0.00 0.00 0.80 0.00 0.00 4.64 1 0.00 0.00 0.00 0.00 5.45 ( 58) 0.00 0.01 0.01 0.00 29.85 j 3.61 1 0.00 0.00 0.00 0.65 34.12 (57) 0.00 0.01 0.91 0.00 29.85 [51.61 0.00 0.00 0.00 0.68 83.06 (56) 0.00 5.10 0.00 0.03 0.31 0.45 0.00 0.00 0.00 0.06 5.96 (55) 1.39 0.01 0.00 3.10 j 0.00 0.01 0.00 0.00 0.00 0.13 4.64 (54) 1.39 5.37 0.00 3.19 0.31 0.60 0.00 0.00 0.00 0.19 11.06 (53) 〇CO 5.38 0.91 3.20 | 30.16 52.21 0.00 0.00 0.86 94.12 (52) 0.33 0.00 0.00 0.00 0.00 5.5 5.5 0.00 0.00 0.00 5.88 (51) 1.72 5.38 0.91 3.20 30.16 52.21 5.55 0.00 0.00 0.86 100.00 LO inch ✓—s CO a inch 2 CO CO (Μ rH οα rH inch (N CO CO tH ci? —) A CO LC οα (N τ- Η (M r—H 1 inch 00 CO 1-HJ rH 6 〇rH 1 aa C 6 Ph owwo 〇ooooo KE Oh (Please read the precautions on the back before filling this page) # 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -40- 534898 A7 B7 V. Description of the invention (38) The possibility of industrial utilization is as described above, due to the refined use of the present invention This method can reduce the stabilizer contained in ethylene tetrachloride. The purification method of the present invention is particularly suitable for ethylene tetrachloride containing an aromatic compound having a hydroxyl group such as phenol and cresol, but it can also be used for ethylene tetrachloride containing an aromatic compound having an amine group. When ethylene tetrachloride, which has been reduced from aromatic compounds having a hydroxyl group, is used as a raw material, the life of the catalyst used in the production step can be improved, and pentafluoroethane can be efficiently and economically produced. . According to the method for producing hydrofluorocarbon in the present invention, there is no need to set up product separation steps in each reaction device. The products from these reaction devices are combined and distilled in a distillation column to recover the target HFC-134a and HFC. 125 and by-product HC1 are products. Because other intermediates and unreacted raw materials can be recycled in each step, the conditions of the continuous operation steps are stable, step management becomes easier, and the equipment is simplistic. Compared with the method, the unit energy source can be reduced. (Please read the notes on the back before filling in this page) · ^ • -t »Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 1-fluorocarbon, fluorinated tetrafluoride, 1-fluorine, 2 hydrogen, and 1 of the hospital, Ming Bu Yifa, fluorinated 1 2 or -guanane 2 with Ebu, fluorine, 5th house. Externally produced formazan carbon, separately fluorinated, trifluoride, and hydrogen. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -41-

Claims (1)

534898 V A8 B8 C8 D8 六、申請專利範ΐ Ί (請先閱讀背面之注意事項再填寫本頁) 1·一種四氯化乙烯之精製方法，其特徵爲，包含將作 爲安定劑含具有羥基之芳香族化合物之四氯化乙烯，以液 相與3.4至1 1Α之平均細孔徑之沸石及/或3.4至11Α之 平均細孔徑之碳質吸著劑相接觸，以減低上述之安定劑。 2. 如申請專利範圍第1項之方法，其中沸石之Si/Al 之比率爲2以下。 3. 如申請專利範圍第1項或第2項之方法，其中沸石 爲至少一種選自分子篩4A，分子篩5A，分子篩10X以及 分子篩1 3 X所成群。 4. 如申請專利範圍第1項之方法，其中碳質吸著劑爲 分子篩碳4A及/或分子篩碳5A。 5. 如申請專利範圍第1項之方法，其中使作爲安定劑 含具有羥基之芳香族化合物之四氯化乙烯與沸石及/或碳 質吸著劑接觸時之溫度爲- 20°C至+ 80°C。 6 ·如申請專利範圍第1項之方法，其中使作爲安定劑 含具有羥基之芳香族化合物之四氯化乙烯與沸石及/或碳 質吸著劑接觸時之壓力爲〇至3MPa。 經濟部智慧財產局員工消費合作社印製 7·—種四氯化乙烯之製造方法，其特徵爲，包含使用 如申請專利範圍第1項之精製方法，以減低作爲安定劑含 於具有羥基之芳香族化合物。 8.—種五氟乙烷之製造方法，其特徵爲，包含以下3 個步驟：（1 )使用如申請專利範圍第1項之精製方法， 減低四氯化乙烯中所含有具有羥基之芳香族化合物之步驟 ，（2 )依據步驟（1 )，使上述之已減低含有具有羥基之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 534898 經濟部智慧財產局員工消費合作社印製 A8 Β8 C8 D8六、申請專利範圍 2 " 芳香族化合物之四氯化乙儲，於氧化鋁一氧化鉻催化劑之 存在下’以氣相與氟化氫進行反應，而得到含有1，i _ 二氯—2，2，2 —三氟乙烷以及1—氯—1，2，2，2 —四 氟乙烷之混合氣體之步驟，（3 )使上述之步驟（2 )中所 得到之含有1，1一二氯一 2，2，2-三氟乙烷以及1—氯 一 1，2，2，2 -四氟乙烷之混合氣體，於氧化鋁一氧化鉻 催化劑之存在下，以氣相與氟化氫進行反應，製成五氟乙 院之步驟。 9·如申請專利範圍第8項之方法，其中使用步驟·（ 1 )中之已減低具有羥基之芳香族化合物至30質量ppm以 下之四氯化乙烯，進行步驟（2 )。 1 〇.如申請專利範圍第8項或第9項之方法，其中具 有羥基之芳香族化合物爲至少一種選自苯酚、甲酚、2，6 一二一叔-丁基-對-甲酚及胺基甲基苯酚所成群。 11. 一種氫氟化碳之製造方法，其特徵爲，包含（A) 使鹵化鏈烯及/或鹵化鏈烷與氟化氫，於氟化催化劑之存 在下進行反應，生成第1個氫氟化碳之步驟，（B)使鹵 .化鏈烯及/或鹵化鏈烷與氟化氫，於氟化催化劑之存在下 進行反應，生成第2個氫氟化碳之步驟，以及（C )合流 步驟（A )及步驟（B )所得之生成物後，蒸餾製成第1 個氫氟化碳及第2個氫氟化碳之步驟。 12. 如申請專利範圍第11項之方法，其中步驟（A ) 爲至少一種選自自四氯化乙烯、2，2 —二氯一 1，1，1一 三氟乙烷及2 —氯一 1，1，1，2 —四氟乙烷所成群’與氟 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -43- 534898 A8 Β8 C8 D8 七、申請專利範圍 3 化氫於氟化催化劑之存在下進行反應，生成作爲第1個氫 氟化碳之五氟乙烷。 13. 如申請專利範圍第11項或第12項之方法，其中 步驟（A )包含使四氯化乙烯與氟化氫於氟化催化劑之存 在下，在第1反應帶進行反應，生成含有2，2-二氯一 1 ，1，1—三氟乙烷及/或2 —氯—1，1，1，2 —四氟乙烷之 氣體之步驟（1)，以及使含有2，2-二氯一1，1，1一 三氟乙烷及/或2-氯—1，1，1，2-四氟乙烷之氣體與氟 化氫於氟化催化劑之存在下，在第2反應帶進行反應·，生 成含有五氟乙烷之氣體之步驟（2)。 14. 如申請專利範圍第11項之方法，其中步驟（B ) 爲使三氯化乙烯及/或2-氯一 1，1，1—三氟乙烷與氟化 氫於氟化催化劑之存在下進行反應，生成作爲第2個氫氟 化碳之1，1，1，2 —四氛乙院。 15. 如申請專利範圍第11項之方法，其中步驟（B ) 包含使三氯化乙烯與氟化氫於氟化催化劑之存在下，在第 3反應帶進行反應，生成含有2-氯一 1，1，1一三氟乙烷 之氣體之步驟（3)，以及使含有2-氯一 1，1，1一三氟 乙烷之氣體與氟化氫於氟化催化劑之存在下，在第4反應 帶進行反應，生成含有1，1，1，2-四氟乙烷之氣體之 步驟（4 )。 16. 如申請專利範圍第11項之方法，其中步驟（C ) 是合流步驟（A )所得到之含有五氟乙烷之氣體以及步驟 (B)所得到之含有1，1，1，2-四氟乙烷之氣體後進行 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ~ -44 - —^ϋ ·111 mu In —^ϋ ·ϋί ϋϋ am —m.^— n (請先閲讀背面之注意事項再填寫本頁) 訂 ... 經濟部智慧財產局員工消費合作社印製 534898 A8 B8 C8 D8 々、申請專利範圍 4 菡餾。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1 7·如申請專利範圍第1 1項之方法，其中步驟（a ) 包含（1 )使四氯化乙烯與氟化氫於氟化催化劑之存在下 ，在第1反應帶進行反應，得到含有氯化氫、2，2 -二氯 —1，1，1—三氟乙烷、2 —氯—1，1，1，2 —四氟乙烷、 五氟乙烷及氟化氫之氣體之步驟，以及（2)使含有2，2 —二氯一 1，1，1一三氟乙烷及/或2-氯—1，1，1，2 — 四氟乙烷之氣體與氟化氫於氟化催化劑之存在下，在第2 反應帶進行反應，得到含有氯化氫、五氟乙烷、2，2-二 氯一 1，1，1—三氟乙烷、2 —氯—1，1，1，2 —四氟乙烷 及/或氟化氫之氣體之步驟，步驟（B )包含（3 )使三氯 化乙烯與氟化氫於氟化催化劑之存在下，在第3反應帶進 行反應，得到含有氯化氫、2-氯一 1，1，1一三氟乙烷及 氟化氫之氣體之步驟，以及（4)使含有2-氯一 1，1，1 -三氟乙烷之氣體與氟化氫於氟化催化劑之存在下，在第 4反應帶進行反應，得到含有氯化氫、1，1，1，2 -四氟 乙烷、2-氯—1，1，1—三氟乙烷及氟化氫之氣體之步驟 ，步驟（C )是（5 )合流上述步驟（1 )至（4 )所得到之 氣體後，導入蒸餾塔中蒸餾而得到五氟乙烷及1，1，1， 2—四氟乙烷之步驟。 18.如申請專利範圍第11項之方法，其中氟化催化劑 是以三價之氧化鉻爲主成份之載體型或塊狀型催化劑。 1 9 .如申請專利範圍第1 7項或第1 8項中任一項之方 法，其中第丨反應帶至第4反應帶之任一反應帶之反應壓 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -45 - 534898 A8 Β8 C8 D8 々、申請專利範圍 5 力爲大氣壓力至〇.9Mpa之範圍內。 20.如申請專利範圍第17項之方法，其中第2反應帶 之壓力比第1反應帶之壓力高，第4反應帶之壓力比第3 反應帶之壓力高。 2 1.如申請專利範圍第1 7項之方法，其中步驟（5 ) 合流上述之步驟（1 )至（4 )所得到氣體導入第1蒸餾塔 ，關於此蒸餾塔，由塔頂分離出氯化氫、2 —氯一 1，1，1 —三氟乙烷、2—氯—1，1，1，2—四氟乙烷，五氟乙烷 及/或1，1，1，2-四氟乙烷，由塔底分離出氟化氫、 2-二氯—1，1，1一三氟乙烷及/或2 —氯—1，1，1—三 氟乙烷。 22. 如申請專利範圍第21項之方法，其中使第1蒸餾 塔之塔底所分離出之氟化氫、2，2 —二氯一 1，1，1—三 氟乙烷及/或2-氯—1，1，1—三氟乙烷於反應步驟中循 •fpq. 土展。 23. 如申請專利範圍第21項或第22項中任一項之方 法’其中將第丨蒸餾塔之塔底所分離出之氟化氫、2，2 一 二氯—1，1，1一三氟乙烷及/或2 —氯—1，1，1一三氟乙 烷導入第2蒸餾塔，分離純化後，循環至反應步驟中。 24. 如申請專利範圍第23項之方法，其中使第2蒸餾 塔所分離出之氟化氫，循環於至少一種之第1反應帶至第 4反應帶中。 25·如申請專利範圍第23項或第24項之方法，其中 使第2蒸餾塔所分離出之含有2，2 —二氯一 1，1，1一三 本紙張尺度適用中國國家樣準（CNS ) A4規格（210X297公嫠） (請先閲讀背面之注意Ϋ項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -46- 534898 A8 B8 C8 D8 六、申請專利範圍 6 氟乙烷之氣體於第2反應帶中循環。 2 6.如申請專利範圍第23項或第24項之方法，其中 使第2蒸餾塔所分離出之含有2 -氯一 1，1，1-三氟乙 烷之氣體於第4反應帶中循環。 27.如申請專利範圍第21項之方法，其中將第1蒸餾 塔之塔頂所分離出之氯化氫、2-氯—1，1，1一三氟乙烷 、2-氯—1，1，1，2 —四氟乙院，五氟乙焼及/或1，1， 1，2-四氟乙烷導入第3蒸餾塔，由塔頂得到五氟乙烷及 1，1，1，2—四氟乙烷。 2 8.如申請專利範圍第27項之方法，其中由第3蒸餾 塔之塔頂所得到之氣體中含有多量之1，1，1，2 -四氟 乙烷。 29.如申請專利範圍第17項之方法，其中蒸餾塔之塔 內壓力爲大氣壓力至3Mpa之範圍內。 3 0.如申請專利範圍第11項之方法，其中包含（A) 由至少一種選自四氯化乙烯、2，2 —二氯—1，1，1—三 氟乙烷及2-氯一 1，1，1，2 —四氟乙烷之成群與氟化氫 於氟化催化劑之存在下進行反應，生成五氟乙烷之步驟， (B)三氯化乙烯及/或2-氯一 1，1，1一三氟乙烷與氟 化氫於氟化催化劑之存在下進行反應，生成1，1，1，2 一四氟乙烷之步驟，以及（C )合流步驟（A )及步驟（B )所得到之生成物後導入蒸餾塔，由塔頂分離出以氯化氫 爲主要成份之氣體，由塔底分離出含有五氟乙烷及1，1 ，1，2-四氟乙烷之氣體，蒸餾由塔底所得到之氣體，而 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -47- 534898 A8 B8 C8 D8 六、申請專利範圍 Ί 得到五氟乙烷及1，1，1，2-四氟乙烷之步驟。 31. 如申請專利範圍第30項之方法，其中步驟（A ) 包含使四氯化乙烯與氟化氫於氟化催化劑之存在下，在第 1反應帶進行反應，生成含有2，2-二氯—1，1，1一三 氟乙烷及/或2 —氯—1，1，1，2-四氟乙烷之氣體之步驟 (1)，以及使含有2，2—二氯一1，1，1—三氟乙烷及/ 或2-氯一 1，1，1，2-四氟乙烷之氣體與氟化氫於氟化 催化劑之存在下，在第2反應帶進行反應，生成含有五氟 乙烷之氣體之步驟（2 )。 32. 如申請專利範圍第30項或第31項中任一項之方 法，其中步驟（B )包含使三氯化乙烯與氟化氫於氟化催 化劑之存在下，在第3反應帶進行反應，生成含有2-氯 一1，1，1一三氟乙烷之氣體之步驟（3)，以及使含有2 -氯- 1，1，1-三氟乙烷之氣體與氟化氫於氟化催化劑 之存在下，在第4反應帶進行反應，生成含有1，1，1， 2—四氟乙烷之氣體之步驟（4)。 33. 如申請專利範圍第32項之方法，其中步驟（A) 包含（1 )使四氯化乙烯與氟化氫於氟化催化劑之存在下 ，在第1反應帶進行反應，得到含有氯化氫、2，2 -二氯 —1，1，1—二氟乙院、2 —氯—1，1，1，2 —四氟乙焼、 五氟乙烷及氟化氫之氣體之步驟，以及（2)使含有2，2 —二氯—1，1，1—三氟乙烷及/或2 —氯—1，1，1，2-四氟乙烷之氣體、與氟化氫於氟化催化劑之存在下，在第 2反應帶進行反應，得到含有氯化氫、五氟乙烷、2，2- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 、1T 經濟部智慧財產局員工消費合作社印製 -48- 534898 A8 B8 C8 D8 六、申請專利範圍 8 (請先閲讀背面之注意事項再填寫本頁) 二氯—1，1，1—三氟乙烷、2 —氯一1，1，1，2 —四氟乙 烷及氟化氫之氣體之步驟，步驟（B)包含（3)使三氯 化乙烯與氟化氫於氟化催化劑之存在下，在第3反應帶進 行反應，得到含有氯化氫、2-氯一 1，1，1一三氟乙烷及 氟化氫之氣體之步驟，以及（4)使含有2-氯一 1，1，1 -三氟乙烷之氣體與氟化氫於氟化催化劑之存在下，在第 4反應帶進行反應，得到含有氯化氫、1，1，1，2 -四氟 乙烷、2-氯一 1，1，1-三氟乙烷及氟化氫之氣體之步驟 ，步驟（C )是（5 )合流上述步驟（1 )至（4 )所得到之 氣體後導入蒸餾塔中，由塔頂分離出以氯化氫爲主要成份 之氣體，由塔底分離出含有五氟乙烷及1，1，1，2 —四 氟乙烷之氣體，蒸餾由塔底所得到之氣體，而得到五氟乙 烷及1，1，1，2-四氟乙烷之步驟。 34.如申請專利範圍第30項之方法，其中氟化催化劑· 是以三價之氧化鉻爲主要成份之載體型或塊狀型催化劑。 經濟部智慧財產局員工消費合作社印製 3 5.如申請專利範圍第33項或第34項中任一項之方 法，其中第1反應帶至第4反應帶之任一反應帶之反應壓 力爲大氣壓力至0.9Mpa之範圍內。 36.如申請專利範圍第33項之方法，其中第2反應帶 之壓力比第1反應帶之壓力高，第4反應帶之壓力比第3 反應帶之壓力高。 3 7.如申請專利範圍第3 7項之方法，其中步驟（5 ) 爲，合流上述之步驟（1)至（4 )所得到氣體導入第1蒸 餾塔，由塔頂分離出氯化氫，由塔底分離出含有以2 -氯 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -49- 534898 A8 B8 C8 D8 六、申請專利範圍 9 —1，1，1—三·乙院、2，2 —二氯—1，1，1—二氟乙院 、2—氯—1，1，1，2-四氟乙烷、五氟乙烷、1，1，1 ，2-四氟乙烷及/或氟化氫爲主之氣體。 3 8.如申請專利範圍第37項之方法，其中將第1蒸餾 塔之塔底所分離出含有以2-氯一 1，1，1—三氟乙烷、2 ，2 —二氯—1，1，1—三氟乙烷、2 —氯—1，1，1，2 — 四氟乙烷、五氟乙烷、1，1，1，2—四氟乙烷及/或氟化 氫爲主之氣體，導入第2蒸餾塔，由塔頂分離出五氟乙烷 、1，1，1，2—四氟乙烷及/或2 —氯—1，1，1，2 —四 氟乙烷，由塔底分離出2 —氯一 1，1，1—三氟乙烷、2， 2 —二氯—1，1，1一三氟乙烷及/或氟化氫。 39. 如申請專利範圍第38項之方法，其中第2蒸餾塔 之塔底分離出含有以2-氯一 1，·1，1—三氟乙烷、2，2 一二氯一 1，1，1一三氟乙烷及/或氟化氫爲主之氣體，導 入第3蒸餾塔，分離精製各成份後，使之循環於反應步驟 〇 40. 如申請專利範圍第39項之方法，其中使第3蒸餾 塔所分離出之氟化氫於至少1種之第1反應帶至第4反應 帶中循環。 4 1.如申請專利範圍第39項或第40項中任一項之方 法，其中使第3蒸餾塔所分離出以含有2，2 -二氯- 1， 1，1-三氟乙烷爲主之氣體於第2反應帶循環。 42.如申請專利範圍第39項或第40項中任一項之方 法，其中使第3蒸餾塔所分離出以含有2 -氯一 1，1，1 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X29*7公釐） ：II 4—, (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -50- 534898 A8 B8 C8 D8 六、申請專利範圍 10 -三氟乙烷爲主之氣體於第4反應帶中循環。 43. 如申請專利範圍第38項之方法，其中由第2蒸餾 塔之塔頂所得到之氣體中含有多量之1，1，1，2 -四氟 乙烷。 44. 如申請專利範圍第38項之方法，其中將第2蒸餾 塔之塔頂所分離出之含有五氟乙烷、1，1，1，2 -四氟乙 烷及/或2 —氯—1，1，1，2 —四氟乙烷之氣體，導入第4 蒸餾塔，由塔頂分離出五氟乙烷及1，1，1，2—四氟乙 烷，由塔底分離出2 —氯—1，1，1,2 —四氟乙烷，便2 一氯一 1，1，1，2 —四氟乙烷於第2反應帶中循環。 45. 如申請專利範圍第30項之方法，其中各蒸餾塔之 塔內壓力爲大氣壓力至3Mpa之範圍內。 (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） -51 -534898 V A8 B8 C8 D8 6. Application for patent application Ί (Please read the precautions on the back before filling this page) 1. A method for refining ethylene tetrachloride, which is characterized in that The ethylene tetrachloride of the aromatic compound is brought into contact with a zeolite having an average pore diameter of 3.4 to 11 A and / or a carbonaceous adsorbent having an average pore diameter of 3.4 to 11 A in a liquid phase to reduce the aforementioned stabilizer. 2. The method according to item 1 of the patent application scope, wherein the Si / Al ratio of the zeolite is 2 or less. 3. The method of claim 1 or 2, wherein the zeolite is at least one group selected from the group consisting of molecular sieve 4A, molecular sieve 5A, molecular sieve 10X, and molecular sieve 1 3 X. 4. The method according to item 1 of the patent application scope, wherein the carbonaceous sorbent is molecular sieve carbon 4A and / or molecular sieve carbon 5A. 5. The method according to item 1 of the patent application range, wherein the temperature at which the ethylene tetrachloride containing an aromatic compound having a hydroxyl group as a stabilizer is brought into contact with a zeolite and / or a carbonaceous sorbent is -20 ° C to + 80 ° C. 6. The method according to item 1 of the scope of patent application, wherein the pressure when the ethylene tetrachloride containing an aromatic compound having a hydroxyl group as a stabilizer is contacted with a zeolite and / or a carbonaceous adsorbent is 0 to 3 MPa. A method for manufacturing 7 · -tetrachloroethylene produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which includes the use of a refining method such as the one in the scope of patent application to reduce the content of aromatics with hydroxyl groups as a stabilizer Family of compounds. 8. A method for producing pentafluoroethane, which is characterized by comprising the following 3 steps: (1) using the refining method as described in item 1 of the scope of patent application, reducing the aromaticity of hydroxyl groups contained in ethylene tetrachloride Step of the compound, (2) According to step (1), the above-mentioned reduced paper size containing hydroxyl groups is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 534898 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8, B8, C8, D8 6. Scope of patent application 2 " Ethyl tetrachloride storage of aromatic compounds, in the presence of alumina and chromium oxide catalysts, 'react in the gas phase with hydrogen fluoride to obtain 1, i_ dichloride -2,2,2-trifluoroethane and chloro-1,2,2,2,2-tetrafluoroethane mixed gas, (3) so that the obtained in step (2) contains 1 A mixed gas of 1,2-dichloro-2,2,2-trifluoroethane and 1-chloro-1,2,2,2-tetrafluoroethane in the presence of alumina and chromium oxide catalyst The phase is reacted with hydrogen fluoride to make pentafluoroethane. 9. The method according to item 8 of the scope of patent application, wherein step (2) is performed using ethylene tetrachloride in which the aromatic compound having a hydroxyl group has been reduced in step (1) to 30 mass ppm or less. 10. The method of claim 8 or claim 9, wherein the aromatic compound having a hydroxyl group is at least one member selected from the group consisting of phenol, cresol, 2,6 t-butyl-p-cresol, and Groups of aminomethylphenols. 11. A method for producing hydrofluorocarbon, which comprises (A) reacting a halogenated alkene and / or a halogenated alkane with hydrogen fluoride in the presence of a fluorination catalyst to generate a first hydrofluorocarbon (B) a step of reacting halogenated alkenes and / or halogenated alkanes with hydrogen fluoride in the presence of a fluorination catalyst to form a second hydrofluorocarbon, and (C) a confluence step (A ) And the product obtained in step (B), and then distilled to produce the first hydrofluorocarbon and the second hydrofluorocarbon. 12. The method according to item 11 of the application, wherein step (A) is at least one selected from the group consisting of ethylene tetrachloride, 2,2-dichloro-1,1,1,1-trifluoroethane, and 2-chloro-1 1,1,1,2, —Tetrafluoroethane clusters' and fluorine (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) -43 -534898 A8 B8 C8 D8 VII. Application for patent scope 3 Hydrogen is reacted in the presence of a fluorination catalyst to form pentafluoroethane as the first hydrofluorocarbon. 13. The method of claim 11 or claim 12, wherein step (A) comprises reacting ethylene tetrachloride and hydrogen fluoride in the presence of a fluorination catalyst in a first reaction zone to produce a compound containing 2, 2 -Step (1) of dichloro-1,1,1,1-trifluoroethane and / or 2-chloro-1,1,1,2-tetrafluoroethane, and 2,2-dichloro -1,1,1-trifluoroethane and / or 2-chloro-1,1,1,2-tetrafluoroethane gas and hydrogen fluoride are reacted in the presence of a fluorination catalyst in a second reaction zone. Step (2) of generating a gas containing pentafluoroethane. 14. The method according to item 11 of the patent application, wherein step (B) is performed by using ethylene trichloride and / or 2-chloro-1,1,1-trifluoroethane and hydrogen fluoride in the presence of a fluorination catalyst. The reaction produces 1,1,1,2,4-difluoromethane, the second hydrofluorocarbon. 15. The method according to item 11 of the scope of patent application, wherein step (B) comprises reacting ethylene trichloride and hydrogen fluoride in the presence of a fluorination catalyst in a third reaction zone to produce a solution containing 2-chloro-1,1 The step (3) of 1,1-trifluoroethane gas, and the gas containing 2-chloro-1,1,1,1-trifluoroethane and hydrogen fluoride are carried out in the fourth reaction zone in the presence of a fluorination catalyst. Step (4) of reacting to generate a gas containing 1,1,1,2-tetrafluoroethane. 16. The method according to item 11 of the scope of patent application, wherein step (C) is the confluent gas obtained in step (A) and the gas contained in step (B) contains 1,1,1,2- Tetrafluoroethane gas is applied to this paper after applying Chinese National Standard (CNS) A4 size (210X297 mm) ~ -44-— ^ ϋ · 111 mu In — ^ ϋ · ϋί ϋϋ am —m. ^ — N ( Please read the notes on the back before filling out this page) Order ... Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 534898 A8 B8 C8 D8 々, patent application scope 4 菡 distillation. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 17 · If the method of applying for the scope of patent No. 11 is applied, step (a) includes (1) the tetrachloride Ethylene and hydrogen fluoride are reacted in the first reaction zone in the presence of a fluorination catalyst to obtain hydrogen chloride, 2,2-dichloro-1,1,1-trifluoroethane, and 2-chloro-1,1,1. Steps of 2,2-tetrafluoroethane, pentafluoroethane and hydrogen fluoride, and (2) making 2,2-dichloro-1,1,1,1-trifluoroethane and / or 2-chloro-1 1,1,2 — Tetrafluoroethane gas and hydrogen fluoride in the presence of a fluorination catalyst are reacted in a second reaction zone to obtain hydrogen chloride, pentafluoroethane, 2,2-dichloro-1,1 Step of 1,1-trifluoroethane, 2-chloro-1,1,1,2,2-tetrafluoroethane and / or hydrogen fluoride gas, step (B) includes (3) bringing ethylene trichloride and hydrogen fluoride to fluorine A step of obtaining a gas containing hydrogen chloride, 2-chloro-1,1,1,1-trifluoroethane and hydrogen fluoride in the third reaction zone in the presence of a catalyst And (4) reacting a gas containing 2-chloro-1,1,1-trifluoroethane with hydrogen fluoride in the presence of a fluorination catalyst in a fourth reaction zone to obtain hydrogen chloride-containing, 1,1,1, 2-tetrafluoroethane, 2-chloro-1,1,1-trifluoroethane and hydrogen fluoride gas step, step (C) is (5) confluence of the gas obtained in the above steps (1) to (4) After that, it is introduced into a distillation column and distilled to obtain pentafluoroethane and 1,1,1,2-tetrafluoroethane. 18. The method according to item 11 of the application, wherein the fluorination catalyst is a carrier-type or block-type catalyst mainly composed of trivalent chromium oxide. 19. The method according to any one of item 17 or item 18 in the scope of patent application, wherein the reaction pressure of any of the reaction bands from reaction bands 4 to 4 is in accordance with Chinese national standards (CNS ) A4 specification (210X297mm) -45-534898 A8 B8 C8 D8 々, patent application scope 5 Force is in the range of atmospheric pressure to 0.9Mpa. 20. The method according to item 17 of the patent application scope, wherein the pressure of the second reaction zone is higher than the pressure of the first reaction zone, and the pressure of the fourth reaction zone is higher than the pressure of the third reaction zone. 2 1. The method according to item 17 of the scope of patent application, wherein step (5) combines the gas obtained in steps (1) to (4) above into the first distillation column, and regarding this distillation column, hydrogen chloride is separated from the top of the column , 2-chloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,1,2-tetrafluoroethane, pentafluoroethane and / or 1,1,1,2-tetrafluoroethane For ethane, hydrogen fluoride, 2-dichloro-1,1,1-trifluoroethane and / or 2-chloro-1,1,1-trifluoroethane are separated from the bottom of the column. 22. The method according to item 21 of the patent application, wherein hydrogen fluoride, 2,2-dichloro-1,1,1-trifluoroethane, and / or 2-chloro separated from the bottom of the first distillation column is used. —1,1,1-trifluoroethane follows the reaction step • fpq. 土 展. 23. The method according to any one of the scope of patent application No. 21 or No. 22, wherein the hydrogen fluoride, 2,2 dichloro-1,1,1,1 trifluoro separated from the bottom of the distillation tower 丨Ethane and / or 2-chloro-1,1,1-trifluoroethane are introduced into a second distillation column, separated and purified, and then recycled to the reaction step. 24. The method of claim 23, wherein the hydrogen fluoride separated from the second distillation column is circulated in at least one of the first reaction zone to the fourth reaction zone. 25. If the method of the 23rd or 24th in the scope of the patent application is applied, the separation of the second distillation column contains 2,2-dichloro-1,1,1,13 This paper standard applies Chinese national standards ( CNS) A4 specification (210X297 public money) (Please read the note on the back before filling this page) Order printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economics-46- 534898 A8 B8 C8 D8 VI. Patent application scope 6 Fluoroethane The alkane gas is circulated in the second reaction zone. 2 6. The method of claim 23 or 24, wherein the gas containing 2-chloro-1,1,1-trifluoroethane separated from the second distillation column is placed in the fourth reaction zone. cycle. 27. The method of claim 21 in the scope of patent application, wherein hydrogen chloride, 2-chloro-1,1,1, trifluoroethane, 2-chloro-1,1, separated from the top of the first distillation column, 1,2 —Tetrafluoroethane Institute, pentafluoroacetamidine and / or 1,1,1,2-tetrafluoroethane are introduced into the third distillation column, and pentafluoroethane and 1,1,1,2 are obtained from the top of the column. -Tetrafluoroethane. 2 8. The method according to item 27 of the scope of patent application, wherein the gas obtained from the top of the third distillation column contains a large amount of 1,1,1,2-tetrafluoroethane. 29. The method of claim 17 in the scope of patent application, wherein the pressure in the distillation column is in the range of atmospheric pressure to 3 MPa. 30. The method according to item 11 of the patent application scope, comprising (A) at least one selected from the group consisting of ethylene tetrachloride, 2,2-dichloro-1,1,1-trifluoroethane and 2-chloro- 1,1,1,2,2-Tetrafluoroethane group reacts with hydrogen fluoride in the presence of a fluorination catalyst to form pentafluoroethane, (B) ethylene trichloride and / or 2-chloro-1 1,1,1-trifluoroethane and hydrogen fluoride are reacted in the presence of a fluorination catalyst to produce 1,1,1,2,4-tetrafluoroethane, and (C) the confluent steps (A) and (B) ) The obtained product is introduced into a distillation column, and a gas containing hydrogen chloride as a main component is separated from the top of the column, and a gas containing pentafluoroethane and 1,1,1,2-tetrafluoroethane is separated from the bottom of the column. Distill the gas obtained from the bottom of the tower, and this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page). -47- 534898 A8 B8 C8 D8 6. Application scope of patent Ί Obtain pentafluoroethane and 1,1,1,2-tetrafluoroethyl The step of alkane. 31. The method of claim 30, wherein step (A) comprises reacting ethylene tetrachloride and hydrogen fluoride in the presence of a fluorination catalyst in a first reaction zone to produce a compound containing 2,2-dichloro- Step (1) of 1,1,1-trifluoroethane and / or 2-chloro-1,1,1,2-tetrafluoroethane, and making 2,2-dichloro-1,1 The gas of 1,1-trifluoroethane and / or 2-chloro-1,1,1,2-tetrafluoroethane and hydrogen fluoride in the presence of a fluorination catalyst are reacted in a second reaction zone to generate pentafluoro Step (2) of ethane gas. 32. The method of claim 30 or 31, wherein step (B) comprises reacting ethylene trichloride and hydrogen fluoride in the presence of a fluorination catalyst in a third reaction zone to produce Step (3) of a gas containing 2-chloro-1,1,1, trifluoroethane, and the presence of a gas containing 2-chloro-1,1,1-trifluoroethane and hydrogen fluoride in the presence of a fluorination catalyst Next, a reaction (4) is performed in a fourth reaction zone to generate a gas containing 1,1,1,2-tetrafluoroethane. 33. The method of claim 32, wherein step (A) includes (1) reacting ethylene tetrachloride and hydrogen fluoride in the presence of a fluorination catalyst in a first reaction zone to obtain hydrogen chloride, 2, A process of 2-dichloro-1,1,1,1-difluoroethane, 2-chloro-1,1,1,2-tetrafluoroacetamidine, pentafluoroethane and hydrogen fluoride gas, and (2) making 2,2-Dichloro-1,1,1-trifluoroethane and / or 2-chloro-1,1,1,2-tetrafluoroethane gas, and hydrogen fluoride in the presence of a fluorination catalyst, The second reaction zone is reacted to obtain hydrogen chloride, pentafluoroethane, 2,2- This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T-48- 534898 A8 B8 C8 D8 6. Scope of patent application 8 (Please read the precautions on the back before filling this page) Dichloro-1,1,1-trifluoro Steps of ethane, 2-chloro-1,1,1,2-tetrafluoroethane and hydrogen fluoride gas, step (B) includes (3) A step of reacting ethylene trichloride and hydrogen fluoride in the presence of a fluorination catalyst in a third reaction zone to obtain a gas containing hydrogen chloride, 2-chloro-1,1,1, trifluoroethane and hydrogen fluoride, and (4 ) Reacting a gas containing 2-chloro-1,1,1-trifluoroethane with hydrogen fluoride in the presence of a fluorination catalyst in a fourth reaction zone to obtain hydrogen chloride containing 1,1,1,2,4 Steps of gas of fluoroethane, 2-chloro-1,1,1-trifluoroethane and hydrogen fluoride, step (C) is (5) confluence of the gas obtained in the above steps (1) to (4), and then introduced into the distillation In the column, the gas containing hydrogen chloride as the main component is separated from the top of the column, and the gas containing pentafluoroethane and 1,1,1,2-tetrafluoroethane is separated from the bottom of the column, and the gas obtained from the bottom of the column is distilled. To obtain pentafluoroethane and 1,1,1,2-tetrafluoroethane. 34. The method of claim 30, wherein the fluorination catalyst is a carrier-type or block-type catalyst with trivalent chromium oxide as the main component. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 5. If the method of applying for any of the items 33 or 34 in the scope of the patent application, the reaction pressure of any of the first reaction zone to the fourth reaction zone is Atmospheric pressure in the range of 0.9Mpa. 36. The method of claim 33, wherein the pressure in the second reaction zone is higher than the pressure in the first reaction zone, and the pressure in the fourth reaction zone is higher than the pressure in the third reaction zone. 37. The method according to item 37 of the scope of patent application, wherein step (5) is to combine the gas obtained in the above steps (1) to (4) to introduce into the first distillation column, separate hydrogen chloride from the top of the column, and The bottom of the paper contains 2-chlorine paper which is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -49- 534898 A8 B8 C8 D8 6. Application scope of patents 9-1, 1, 1-III · Yiyuan , 2,2-dichloro-1,1,1,1-difluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane Gases based on fluoroethane and / or hydrogen fluoride. 3 8. The method according to item 37 of the scope of patent application, wherein the bottom of the first distillation column is separated and contains 2-chloro-1,1,1-trifluoroethane, 2,2-dichloro-1 1,1,1-trifluoroethane, 2-chloro-1,1,1,1,2-tetrafluoroethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane and / or hydrogen fluoride The gas is introduced into the second distillation column, and pentafluoroethane, 1,1,1,2-tetrafluoroethane and / or 2-chloro-1,1,1,2, tetrafluoroethane are separated from the top of the column. From the bottom of the column, 2-chloro-1,1,1-trifluoroethane, 2,2-dichloro-1,1,1,1-trifluoroethane and / or hydrogen fluoride were separated. 39. The method according to item 38 of the scope of patent application, wherein the bottom of the second distillation column contains a mixture containing 2-chloro-1, · 1,1-trifluoroethane, 2,2 dichloro-1,1 1, 1 trifluoroethane and / or hydrogen fluoride-based gas is introduced into the third distillation column, after separating and refining each component, it is recycled in the reaction step 040. For example, the method of the 39th scope of the patent application, wherein the first 3 The hydrogen fluoride separated from the distillation column is circulated in at least one of the first reaction zone to the fourth reaction zone. 4 1. The method of claim 39 or 40, wherein the third distillation column is separated to contain 2,2-dichloro-1,1,1-trifluoroethane as The main gas is circulated in the second reaction zone. 42. The method of claim 39 or 40, wherein the third distillation column is separated to contain 2-chloro-1,1,1. The Chinese paper standard (CNS) Α4 specification (210X29 * 7mm): II 4—, (Please read the notes on the back before filling this page) Order printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs -50- 534898 A8 B8 C8 D8 VI. Patent Application A gas ranging from 10 -trifluoroethane is circulated in the fourth reaction zone. 43. The method of claim 38, wherein the gas obtained from the top of the second distillation column contains a large amount of 1,1,1,2-tetrafluoroethane. 44. The method according to item 38 of the application, wherein the top of the second distillation column contains pentafluoroethane, 1,1,1,2-tetrafluoroethane and / or 2-chloro- The gas of 1,1,1,2, tetrafluoroethane is introduced into the fourth distillation column, and pentafluoroethane and 1,1,1,2-tetrafluoroethane are separated from the top of the column, and 2 is separated from the bottom of the column. —Chloro-1,1,1,2—tetrafluoroethane, then 2—chloro-1,1,1,1,2—tetrafluoroethane is circulated in the second reaction zone. 45. The method of claim 30, wherein the pressure in each distillation column is in the range of atmospheric pressure to 3 MPa. (Please read the precautions on the back before filling out this page) Order Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X29 * 7mm) -51-
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JP2001206882A JP5105672B2 (en) 2001-07-06 2001-07-06 Method for purifying tetrachloroethylene and method for producing pentafluoroethane using the method
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