經濟部中央標準局員工消費合作社印製 2^46^9 A7 _ B7 五、發明説明（1 ) 本發明係關於一種製備氩氟烷，特別是m 2·四氟乙 烷或五氟乙烷之方法。 數種已被提出的方法中，已知的其他方法如HFc 134a製 偏1，1，1,2-四氟乙烷，已知的其他方法如hfc 125製備五氟 乙坑，在許多引用氯氟碳之應用中，用來當做氯氟碳或當 作取代氯氟碳之组成。在此方法中，相對應之含氣起始物 質之氟化，通常在有氟化催化劑存在下，藉由在液相或氣 相中起始物質輿氟化氩反應而得。 在英國專利説明書號碼1，589,924中提出藉由氣相氟化本 身可由如英國專利説明書號碼1，307,224中所描述藉由氟 化三氣乙締所獲得之1，1，ϋ氣乙烷（HCFC 133a)製備HFC 134a 0 所形成的HFC 134a爲氟化三氟乙缔的一種副產品，則在 英國專利説明書號碼819,849，而主要反應產品爲HCFC 133a。 近來咸提出從三氣乙烯製備HFC 134a之方法，是基於三 氟乙烯輿氟化氩反應製備11€?(：133&和11(：1?(：133&與氟化 氩反應製備HFC 134a之結合。 在WO 90/08755中，該内容合併於參考文獻中，其描述 三氣乙埽轉化爲HFC 134a，其中在具有將一部分含有 HCFC 133a產物流再使用之單一反應區域中，有兩個反應 步驟進行。 在ΕΡ 0 449 614中，該内容合併於參考文獻中，其描述 一種製造HFA 134a之方法，包含以下步樣： -4- 本紙乐尺度適财關家標準（CNS ) A4規格（21GX297公釐)' " (請先閲讀背面之注意事項再填寫本頁) -59 經濟部中央樣準局員工消费合作社印製 A 7 ________B7_ 五、發明説明（2 ) (A)在超過大氣壓力下，溫度範圍從約2〇〇"C至約4〇〇 eC，在單一反應區域中，將含有一種三氣乙缔混合物和氟 化氯，在有氟化催化劑下，形成一種含有丨，^•三氟·2_氯 乙烷產物和氯化氩，以及未反應物質， (Β)在溫度範困從約280 °C至約450 °C，但是比在步樣 A中更高的溫度下，將步驟a之產物和氟化氩一起通至含 有氟化催化劑之第二反應區域中，形成一種含m•三氟_ 2·氯乙烷、1，1，1，2-四氟乙烷產物和氣化氣， (C) 處理步驟B之產物，從1，1，1-三氟-2_氣乙烷和未反 應的氟化氩分離出1，1，1，2-四氟乙烷和氣化氫，以及 (D) 將從步驟C所得之1，1，1-三氟-2-氣乙烷一起和三氯乙 烯和氟化氩加入該第一反應區域（步驟A)。 在ΕΡ 0 449 617中，該内容合併於參考文獻中，其描述 —種製備HFC 134a之方法，包含以下步樣： (A) 在溫度範圍從約280°C至約450°C，在第一反應區 域中’將含有一種1,1,1-三氣-2-氣乙故混合物和氟化氯， 在有氟化催化劑下，形成一種含有1，1，1，2_四氟乙燒產物 和氣化氩，以及未反應物質， (B) 在溫度範圓從約200°C至約40(TC，但是比在步樣 A中更低的溫度下，將步驟A之產物和三氣乙烯一起通至 含有氟化催化劑之第二反應區域中，形成一種含有151卜 二氣氣乙燒、1，1，1，2 -四氣乙坑、氣化氣產物，以及未 反應之三氣乙烯和氟化氩， (C) 處理步驟B之產物，從1，1，1-三氟-2-氣乙烷、未反 -5- 本紙張尺度適用中國國家標準（CNS ) A4規格（210'X 297公釐） ----- (請先閲讀背面之注意事項再填寫本頁) 、-° A7 2Q4649 ______ B7 五、發明説明（3 T — " 應之三氣乙埽和氟化氫分離出mi四氟乙烷和氣化氫 ，以及 (D)將從步驟C所得之1,1,1-三氟-2_氣乙烷—起和氟化氩 加入該第一反應區域（步驟A)。 然而，製備1，1，1，2·四氟乙烷之方法，爲基於1_氣·2 2 2· 三氟乙烷和/或三氣乙烯之氩氟化，其所遣遇的一個問題 是1 -氣-2,2,2-三氟乙坑轉化成l，l，i，2-四氟乙烷爲平衡所 限制，在典型的操作條件下之最大轉化只有約20%。 咸已提出藉由氣四氟乙烷（HCFC 124)和/或本身可藉由 過氣乙缔和氟化氩氟化獲得之二氯三氟乙烷（HCFC 123) 和氟化氩經氣化催化而製備五氟乙烷（HFC 125)。 本發明在於一種從至今尚未被使用過之起始物質製備氩 氟烷’特別是1，1，1，2-四氟乙烷和五氟乙坑之方法，其方 法在製備1，1，1，2-四氟乙烷情況下，不會遣遇如前述平衡 限制之問題。 根據本發明所提供一種製備氩氟烷之方法，其中包括含 有一種具有分子式CC1XYCFHZ之氫氯氟乙烷或一種具有 分子式CC1A=CFZ之氫氣氟乙缔，其中X和γ各自獨立爲 氣或氣’ Z爲氣或氩，而A爲氣或氟，假設其中每一個X 和Y爲氟，及Z爲氩，於氣相中與氟化氩和一種氟化催化 劑反應，以及從所得之產物中回收氫氟烷。 在一個特定製備1，1，1，2-珥氟乙烷之方法的實例中，該 氩氣氟乙烷具有分子式爲CC1XYCFH2，而該氩氯氟乙烯 具有分子式爲CC1Z=CFH » ~ 6 - 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) :衣. 訂---- 經濟部中央標準局員工消費合作社印裂 A7 B7 五、發明説明（4 ) 頃發現從製備1，1，1，2-四氟乙烷之方法所得之產物氣體 ，比當使用1-氣-2,2,2-三氟乙烷作爲起始物質時所獲得者 ，含有較大體積莫耳濃度比例之1，1，1，2-四氟乙烷》 該方法之起始物質爲CC13CFH2、CC12FCFH2、 CC1F2CFH2 ' CC12FCC1FH、CCI3CHFCI ' CC12=CFH、 CC1F=CFH、CC12 =CFC1、及CC1F=CFC1。我們較喜歡引用 CC12=CFH 或 CC12FCFH2，特別是以 CC12=CFH 製備 1，1，1，2-四氟乙烷，以及以CC12FCC1FH或CC1F=CFC1製備 五氟乙烷，因爲此類物質較爲方便取得。 本發明之起始物質之製備方法爲已知。因此例如CC12: CFH可從三氣乙烯製得，正如在日本化學期刊28,112 (1963)中所描述者，或從四氣乙烷製得，正如在EP 537560中所描述者。 經濟部中央標準局員工消費合作杜印製 ---------U ★—— (請先閏讀背面之注意事項再填寫本頁) 合適的氟化催化劑爲其可生產所要的氩氟烷產物之產率 大於20%，較佳地爲大於25%，其爲以製程中的起始物 質爲根據，以及包括催化劑以鉻氧化物或氟氧化鉻以及其 他金屬的氟化物或氟氧化物爲主，例如鎂和鋁。其他提高 活性量的金屬，例如鋅和鎳亦可以存在，我們特別喜歡引 用一種催化劑包含鋅加於鉻氧化物上，正如發表在歐洲專 利公告號碼502605中所詳細描述者，該内容合併於參考 文款中。 所引用之氟化氩對起始物質的比較比例是可以在寬泛的 界限，但是通常較佳地引用超過化學計量之氟化氫。所需 要之化學計量莫耳比例則視特定之起始物質而定。在較佳 本紙張尺度適用中國國家標準（CNS) A4規格（210x 297公釐） 經濟部中央標準局員工消費合作社印裝 A7 _________B7 五、發明説明（5 ) 的起始物質爲1，1-二氣·2·氟乙烷情沉下，~需要的氟化氩 對1，1-二氣-2-氟乙烯之化學計量莫耳比例爲3:1。氟化氫 對起始物質，例如1,1·二氣_2_氟乙烯，之莫耳比例，通常 至少爲2 : 1，較佳地爲至少爲4 : i，且特別至少爲6 :1，以 及若需要可以引用實質上大量超量之氟化氫，例如加至 50:1。 此方法操作的溫度，較佳地爲至少,及更佳地至 少爲200C或220C，但是可以大爲低於典型所引用將卜 氯-2,2,2-二氟乙燒轉化成1112·四氟乙故之溫度。較佳 的溫度爲不超過350°C，特別是不超過330。(3。 此方法可以在大氣愿力下進行，即使是超過大氣惠力， 較佳地高至約30巴。 在大氣要力下’較佳的接觸時間範圓從約〇1秒至約1〇 秒，較佳的時間範固從約0.5秒至約5秒。 如前所述’三氯乙烯之氳氟化，經由使用中間物質丨氣 -2,2,2-二氟乙坑來製備1，1，1，2_四氟乙坑。若需要，本發 明之方法可以與以三氣乙烯/丨-氣_2 2 2_三氟乙烷爲主之 製備1，1，1，2-四氟乙坑之方法相結合。 如此，根據本發明較佳的一個實例，如前述所定義之氩 氣氣燒和/或氫氣氟埽，例如M-二氣_2_氟乙烯，則加至 製程當做第二起始物質，用以製備引用三氣乙烯當作起始 物質之1，1，1，2·四氟乙坑。 該共同加入之三氣乙埽和第二起始物質，如1]l•二氯·2_ 氟乙烯可能會影響製程，其描述在我們發表在歐洲專利公 -8 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0 X 297公董） ϋϋ me · nn ^1^1] n^n T. d ^^、-。 (請先閲讀背面之注意事項再填寫本頁) 2d464d 經濟部中央標準局員工消費合作社印製 Μ B7 五、發明説明（6 ) 告號碼0 449 617和0 449 614，該内容則合併於參考文獻 中。 本發明藉由下列實例來舉例説明，但並不限制僅於此例 子。 在這些例子中所使用的1，1-二氯-2- 氟乙烯（HCFC 1121a)是經由乙繂氩氧化鉀將三氣氟乙烷（HCFC 131)脱籃 酸化所合成，正如J_ Am. Chem. Soc.，1936，58,402中所插 述者。將所得未經精製的產物用水清洗，以硫酸鍰乾揉， 然後以分段煮沸分餾，並收集在32°C和34eC之間的成分 ;此分率成份經分析，發現爲純的HCFC 1 12 1 a。 在這些例子中所使用的1，1-二氣-1，2-二氟乙烷（HCFC 132c)是經由使用氧化鉛（IV)於無水氟化氫中將1，1-二氣乙 坑（二氣乙缔）氧氟化所合成，正如J. Am. Chem. Soc.， 1945,67，1639中所描述者。此反應在一個HastalloyC高餍 反應器中進行，並可得相當可觀產量之共同產物1，1_二氣· 1-氟乙烷（HCFC 141b)。將所得之反應混合物分餾，且所 收集之分率且成份則包含60 0/。重量百分比之HCFC 141b和 40%重量百分比之HCFC 132c ;藉由蒸餚無法從HCFC 141b分 離出 HCFC 132c。 在這些例子中所使用的1，1，2-三氣-1,2-二氟乙烷（HCFC 122a)是在一個Hastalloy C高壓反應器中經由使用氧化鉛 (IV)於無水氟化氩中將三氯乙烯氧氟化所合成，正如j Am. Chem. Soc·，1945, 67，1639中所描述者。該含有未反 應的三氣乙烯反應混合物之去除則藉由以溴處理而形成 -9- 本纸張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） n I - - I II 11 II 士.oi. I I - i ..1-.1 -二·· Τ» 03 、τ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作杜印製 A7 B7 五、發明説明（7 ) 1,2-二溴-1，1,2-三氣乙烷，然後再經分餾》所收集之分率 成份含有HCFC 122a，經分析顯示其爲純的HCFC 122a。 實例1 將2毫升含有8%重量百分比鋅在鉻氧化物上之催化劑裝 在一個1/4"内徑的英高鎳反應管内，此催化劑之預氟化 則藉由在3 0 0 °C下將氟化氩通過催化劑2 4小時。經過這段 時間，在275 °C下將氟化氩和1，1-氣-2-氟乙烯（於乙醇中） 各別以流速爲25毫升/分鐘和6毫升/分鐘通過催化劑，其 给予與催化劑接觸的時間爲1.4秒。 在反應器中氣體消散後，進行採樣，並以氣相層析儀分 析該樣品。1，1-二氣_2·氟乙晞之轉化率爲55.8%，以及選 择性轉化成1，1，1，2_四氟乙烷之轉化率爲67.6%。 實例2 將2.5克含有8 %重量百分比鋅在鉻氧化物上之催化劑裝 在一個1/4”内徑的英高鎳反應管内，此催化剤於300°C下 在流速爲1 0毫升/分鐘氮氣流下乾燥1小時。然後此乾燥 後的催化劑之氟化則藉由在300 °C下，於一流速爲10毫升 /分鐘氟化氫流及氮氣流下，加熱2小時，該流速大約可每 分鐘可運送41毫莫耳之氟化氩。 事先製備一 1,1-二氣-2-氟乙烯（0·64克）於氟化氫之樣品 ，其藉由將1,1-二氣-2-氟乙烯加入一個經氟化氩清洗過之 Whitey金屬容器中，並將含有氟化氫：樣品之莫耳比例爲 8:1通過催化劑，藉由將氟化氩/氮氣流分流達成，而該催 化劑溫自始至終則維持在3 0 0 °C »在樣品流中氟化氩： -10- 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) 、-=s 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（8 ) 1，1-二氣-2-氟乙埽大約爲4:1。 在從將氟化氫/氮氣流分流達成以随流帶走丨，丨-二氣_2_氟 乙烯樣品、產物流之樣品5分鐘後，再以碳酸訥溶液洗滌 後’以氣相層析分析及〗尺光譜分析之。 經分析判斷該主要產物爲1，1，1,2-四氟乙烷[HFC 134a] '氣-2,2,2-三氟乙烷[HFC 133 a]及氣四氟乙烷[HCFC 124] 〇 結果顯示於表1中，而且也類 示加入 二氣-2_氟乙缔 取代三氣乙烯產生較高產率之1,1,1，2·四氟乙烷（HFC 134a) ，而且不會如加入三氣乙烯時所遭遇到平衡限制的問題。 實例3 重復在實例2中所描述之程序，除了將氟化氫/氮氣流減 少至5毫升/分鐘以取代原有的1〇毫升/分鐘，所以供應至 催化劑之氟化氫：1，1-二氫-2-氟乙烯莫耳比例則減半爲大 約 2 : 1。 經分析判斷該主要產物爲大約相當量之1，1,1，2_四氟乙 烷（HFC 13乜）和氣_2,2,2-三氡乙烷（HFC 133a)。結果顯示 於表1中。 實例4 重覆在實例2中所描述之程序，在不同的催化溫度下， 將1，1-二氣-2-氟乙烯（〇·32克）與氟化氫反應。供應至催化 劑之氟化氫：1，卜二氣-2-氟乙烯起始莫耳比例大約爲& 1 〇 复Printed 2 ^ 46 ^ 9 A7 _ B7 by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (1) The present invention relates to a preparation of argonine, especially m 2 · tetrafluoroethane or pentafluoroethane method. Among several methods that have been proposed, other known methods such as HFc 134a for partial 1,1,1,2-tetrafluoroethane, other known methods such as hfc 125 to prepare pentafluoroethane pits, in many cited chlorine In the application of fluorocarbon, it is used as chlorofluorocarbon or as a component to replace chlorofluorocarbon. In this method, the fluorination of the corresponding gas-containing starting material is usually obtained by reacting the starting material with argon fluoride in the liquid or gas phase in the presence of a fluorination catalyst. It is proposed in British Patent Specification No. 1,589,924 that gas phase fluorination itself can be obtained from 1,1, ϋ gas ethane obtained by fluorinating trigas ethylene as described in British Patent Specification No. 1,307,224 (HCFC 133a) Preparation of HFC 134a 0 The formed HFC 134a is a by-product of fluorinated trifluoroethylene, which is in British Patent Specification No. 819,849, and the main reaction product is HCFC 133a. Recently, Xian proposed a method of preparing HFC 134a from tri-gas ethylene, which is based on the reaction of trifluoroethylene and argon fluoride to prepare 11 €? (: 133 & and 11 (: 1? (: 133 & reacting with argon fluoride to prepare HFC 134a In WO 90/08755, this content is incorporated in the reference, which describes the conversion of trifluoroethane to HFC 134a, where there are two reactions in a single reaction zone with a portion of the product stream containing HCFC 133a reused The steps are carried out. In EP 0 449 614, this content is incorporated in the reference, which describes a method of manufacturing HFA 134a, including the following steps: -4- Benzhi music standard suitable for financial standards (CNS) A4 specification (21GX297 (Mm) "(please read the precautions on the back before filling in this page) -59 Printed by the Central Sample Bureau of the Ministry of Economic Affairs Employee Consumer Cooperative A 7 ________B7_ V. Description of the invention (2) (A) Under atmospheric pressure The temperature range is from about 200 ° C to about 400eC. In a single reaction zone, it will contain a mixture of three-gas ethylene and chlorine fluoride. With the fluorination catalyst, a mixture containing • Trifluoro · 2_chloroethane product Argon chloride, as well as unreacted substances, (B) At a temperature range from about 280 ° C to about 450 ° C, but at a higher temperature than in step A, the product of step a is combined with argon fluoride Lead to the second reaction zone containing fluorination catalyst to form a product containing m · trifluoro_2 · chloroethane, 1,1,1,2-tetrafluoroethane and gasification gas, (C) Process Step B The product is separated from 1,1,1-trifluoro-2_gas ethane and unreacted argon fluoride by 1,1,1,2-tetrafluoroethane and gasified hydrogen, and (D) will be removed from the step The 1,1,1-trifluoro-2-gas ethane obtained from C is added to the first reaction zone together with trichloroethylene and argon fluoride (step A). In EP 0 449 617, this content is incorporated by reference In it, it describes a method for preparing HFC 134a, which includes the following steps: (A) At a temperature ranging from about 280 ° C to about 450 ° C, the first reaction zone will contain a 1,1,1- The mixture of trifluoro-2-gas ethyl and chlorine fluoride, in the presence of a fluorination catalyst, forms a product containing 1,1,1,2-tetrafluoroethane and vaporized argon, as well as unreacted substances, (B) in The temperature range is from about 200 ° C to 40 (TC, but at a lower temperature than in step A, the product of step A and the three-gas ethylene are passed into the second reaction zone containing the fluorination catalyst to form a ethane gas containing 151 b , 1,1,1,2-Four gas pits, gasification gas products, and unreacted three gas ethylene and argon fluoride, (C) treatment of the product of step B, from 1,1,1-trifluoro- 2-Gas ethane, non-reverse-5- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210'X 297mm) ----- (please read the precautions on the back before filling this page), -° A7 2Q4649 ______ B7 Fifth, the description of the invention (3 T — " should be three gas ethene and hydrogen fluoride to separate mi tetrafluoroethane and gasified hydrogen, and (D) 1,1,1 from step C -Trifluoro-2_gas ethane-and argon fluoride are added to the first reaction zone (step A). However, the method of preparing 1,1,1,2,2 · tetrafluoroethane is based on the argon fluorination of 1_gas · 2 2 2 · trifluoroethane and / or trigas ethylene. The conversion of 1-gas-2,2,2-trifluoroethane to l, l, i, 2-tetrafluoroethane is limited by equilibrium, and the maximum conversion under typical operating conditions is only about 20%. Xian has proposed gasification of dichlorotrifluoroethane (HCFC 123) and argon fluoride by gaseous tetrafluoroethane (HCFC 124) and / or itself which can be obtained by fluorination of gaseous ethylene and argon fluoride Catalytically prepare pentafluoroethane (HFC 125). The present invention resides in a method for preparing argonine from starting materials that have not been used so far, especially 1,1,1,2-tetrafluoroethane and pentafluoroethane, the method of which is to prepare 1,1,1 In the case of 2-tetrafluoroethane, the problem of balance restrictions as described above will not be met. According to the present invention, there is provided a method for preparing argonine, which includes a hydrochlorofluoroethane having a molecular formula CC1XYCFHZ or a hydrogen fluoride having a molecular formula CC1A = CFZ, wherein X and γ are each independently gas or gas. Z is gas or argon, and A is gas or fluorine, assuming that each of X and Y is fluorine, and Z is argon, reacting with argon fluoride and a fluorination catalyst in the gas phase, and recovering from the resulting product Hydrofluorocarbon. In an example of a specific method for preparing 1,1,1,2-fluorofluoroethane, the argon fluoroethane has a molecular formula of CC1XYCFH2, and the chlorofluoroethylene has a molecular formula of CC1Z = CFH »~ 6-this The paper standard is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (please read the notes on the back before filling in this page): Clothing. Order ---- Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. 2. Description of the invention (4) It was found that the product gas obtained from the method for preparing 1,1,1,2-tetrafluoroethane uses 1-gas-2,2,2-trifluoroethane as the starting material. The obtained material contains 1,1,1,2-tetrafluoroethane with a larger molar ratio of moles. The starting materials of this method are CC13CFH2, CC12FCFH2, CC1F2CFH2 'CC12FCC1FH, CCI3CHFCI' CC12 = CFH, CC1F = CFH, CC12 = CFC1, and CC1F = CFC1. We prefer to quote CC12 = CFH or CC12FCFH2, especially CC12 = CFH for 1,1,1,2-tetrafluoroethane, and CC12FCC1FH or CC1F = CFC1 for pentafluoroethane, because such substances are more convenient Made. The preparation method of the starting material of the present invention is known. Thus, for example, CC12: CFH can be prepared from tri-gas ethylene, as described in Japanese Chemical Journal 28,112 (1963), or from tetra-gas ethane, as described in EP 537560. Du printed by the Ministry of Economic Affairs, Central Bureau of Standards and Staff Consumer Cooperation --------- U ★ —— (please read the notes on the back before filling this page) A suitable fluorination catalyst is the argon it can produce The yield of the halothane product is greater than 20%, preferably greater than 25%, which is based on the starting materials in the process, and includes catalysts based on chromium oxide or chromium oxyfluoride and fluoride or fluorine oxidation of other metals Mainly based on materials, such as magnesium and aluminum. Other metals that increase activity, such as zinc and nickel, can also be present. We particularly like to cite a catalyst containing zinc added to chromium oxide, as described in detail in European Patent Publication No. 502605, which is incorporated by reference In the paragraph. The cited ratio of argon fluoride to the starting material can be in a wide range, but it is generally preferred to quote hydrogen fluoride in excess of the stoichiometric amount. The required stoichiometric molar ratio depends on the specific starting material. At the preferred paper size, the Chinese National Standard (CNS) A4 specification (210x 297 mm) is applied. The A7 _________B7 is printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. The starting material for the invention description (5) is 1,1-II Gas · 2 · fluoroethane sinks, the required stoichiometric molar ratio of argon fluoride to 1,1-digas-2-fluoroethylene is 3: 1. The molar ratio of hydrogen fluoride to the starting material, such as 1,1 · digas-2-fluoroethylene, is usually at least 2: 1, preferably at least 4: i, and particularly at least 6: 1, and If necessary, a substantial amount of excess hydrogen fluoride can be cited, for example to 50: 1. The operating temperature of this method is preferably at least, and more preferably at least 200C or 220C, but it can be much lower than the typical cited conversion of chloro-2,2,2-difluoroethane to 1112 · 4 The temperature of fluoroethylene. The preferred temperature is not more than 350 ° C, especially not more than 330. (3. This method can be carried out under atmospheric pressure, even if it exceeds the atmospheric power, preferably as high as about 30 bar. Under atmospheric pressure, the preferred range of contact time is from about 0.01 second to about 1. 〇 seconds, the preferred time range is from about 0.5 seconds to about 5 seconds. As mentioned above, the 'trifluoroethylene trifluoride fluorination, prepared by using the intermediate material 丨 gas-2,2,2-difluoroethane pit 1,1,1,2-tetrafluoroethane pit. If necessary, the method of the present invention can be used to prepare 1,1,1,2 for trifluoroethylene / 丨 -gas_2 2 2_trifluoroethane -The method of combining tetrafluoroethane pits. Thus, according to a preferred example of the present invention, argon gas burning and / or hydrogen fluoride as defined above, such as M-digas_2_fluoroethylene, add The process is used as the second starting material to prepare 1,1,1,2, tetrafluoroethane pits that use trigas ethylene as the starting material. Such as 1] l • Dichloro · 2_ vinyl fluoride may affect the process, which is described in the European Patent Publication-8 we published-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0 X 297 Gongdong) ϋϋ me · nn ^ 1 ^ 1] n ^ n T. d ^^,-. (Please read the precautions on the back before filling out this page) 2d464d Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs BM7. Invention description (6) Report numbers 0 449 617 and 0 449 614, the contents of which are incorporated in the reference. The present invention is illustrated by the following examples, but is not limited to this example. The 1, used in these examples, 1-Dichloro-2-fluoroethylene (HCFC 1121a) is synthesized by debasification of trifluorofluoroethane (HCFC 131) by potassium oxyhydroxide, as in J_Am. Chem. Soc., 1936, 58,402 Interpolator: Wash the resulting unrefined product with water, dry knead with sulphuric acid, then fractionate by boiling in stages, and collect the components between 32 ° C and 34eC; this fractional component is analyzed and found to be pure HCFC 1 12 1 a. The 1,1-digas-1,2-difluoroethane (HCFC 132c) used in these examples is the use of lead (IV) oxide in anhydrous hydrogen fluoride to convert 1,1- Two gas pits (two gas ethene) oxyfluorination synthesis, as described in J. Am. Chem. Soc., 1945,67,1639. This reaction is in In a HastalloyC reactor, and a considerable yield of the common product 1,1_2 gas · 1-fluoroethane (HCFC 141b) can be obtained. The resulting reaction mixture is fractionated, and the fractions and components collected It contains 60% / wt HCFC 141b and 40% wt HCFC 132c; HCFC 132c cannot be separated from HCFC 141b by steaming. The 1,1,2-trigas-1,2-difluoroethane (HCFC 122a) used in these examples was used in a Hastalloy C high-pressure reactor through the use of lead (IV) oxide in anhydrous argon fluoride The oxyfluorination of trichloroethylene is synthesized as described in j Am. Chem. Soc., 1945, 67, 1639. The removal of the unreacted tri-gas ethylene reaction mixture is formed by treatment with bromine-9- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specifications (210Χ 297 mm) n I--I II 11 II士 .oi. II-i ..1-.1-二 ·· Τ »03, τ (please read the precautions on the back before filling in this page) Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 Description of the invention (7) 1,2-dibromo-1,1,2-trigas ethane, and then fractionated by fractionation. The fractional component collected contains HCFC 122a, and analysis shows that it is pure HCFC 122a. Example 1 2 ml of a catalyst containing 8% by weight of zinc on chromium oxide was placed in a 1/4 "inner diameter nickel high nickel reaction tube. The pre-fluorination of this catalyst was performed at 300 ° C Argon fluoride was passed through the catalyst for 24 hours. After this period of time, argon fluoride and 1,1-gas-2-fluoroethylene (in ethanol) were passed through the catalyst at a flow rate of 25 ml / min and 6 ml / min at 275 ° C, which was given The catalyst contact time was 1.4 seconds. After the gas dissipated in the reactor, a sample was taken and the sample was analyzed with a gas chromatograph. The conversion rate of 1,1-digas_2 · fluoroethane is 55.8%, and the conversion rate of selective conversion to 1,1,1,2-tetrafluoroethane is 67.6%. Example 2 2.5 g of a catalyst containing 8% by weight of zinc on chromium oxide was packed in a 1/4 "ID English high nickel reaction tube. The catalyst was at 300 ° C at a flow rate of 10 ml / min Dry for 1 hour under nitrogen flow. Then the fluorination of the dried catalyst is carried out at 300 ° C under a flow of 10 ml / min hydrogen fluoride flow and nitrogen flow for 2 hours, the flow rate can be transported per minute 41 millimoles of argon fluoride. Prepare a sample of 1,1-digas-2-fluoroethylene (0.64 g) in hydrogen fluoride in advance by adding 1,1-digas-2-fluoroethylene In a Whitey metal container cleaned with argon fluoride, a hydrogen fluoride: sample molar ratio of 8: 1 was passed through the catalyst by dividing the argon fluoride / nitrogen flow, and the catalyst temperature was maintained at 3 0 0 ° C »Argon fluoride in the sample stream: -10- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page),-= s A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (8 ) 1,1-Digas-2-Fluoroethane is about 4: 1. After splitting the hydrogen fluoride / nitrogen flow to follow the flow away, the sample of the 2-fluo-2-fluoroethylene sample, product stream After 5 minutes, wash with carbonic acid solution and then analyze it by gas chromatography and spectroscopic analysis. The main product is 1,1,1,2-tetrafluoroethane [HFC 134a] after analysis. -2,2,2-trifluoroethane [HFC 133 a] and gas tetrafluoroethane [HCFC 124] 〇The results are shown in Table 1, and also the addition of two gas -2_fluoroethylene to replace three gas Ethylene produces a higher yield of 1,1,1,2, tetrafluoroethane (HFC 134a), and it does not suffer from the equilibrium limitation problems encountered when adding trigas ethylene. Example 3 Repeat the description in Example 2 In addition to reducing the flow of hydrogen fluoride / nitrogen to 5 ml / min to replace the original 10 ml / min, the ratio of hydrogen fluoride supplied to the catalyst: 1,1-dihydro-2-fluoroethylene molar is halved to About 2: 1. After analysis, the main products are about 1,1,1,2-tetrafluoroethane (HFC 13 乜) and gas _2,2,2-tridonethane (HFC 133a). The results are shown in Table 1 Example 4 The procedure described in Example 2 was repeated. At different catalytic temperatures, 1,1-difluoro-2-fluoroethylene (〇.32 g) was reacted with hydrogen fluoride. Hydrogen fluoride supplied to the catalyst: 1 , The initial molar ratio of Budiqi-2-fluoroethylene is approximately & 1 〇 复
在樣品供應期間，在催化溫、爲25(TC、300°C和350eC -11 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝. '-° A7 發明説明（9 ) --- 下進行三個試脍》用以分析之產物流樣品則在從轉換氣化 氟/氮氣流随流帶走樣品4分鐘後取得。分析結果顆示於表 1中。 ' 在250 (3下，1，1-二氣-2-氟乙烯轉化率爲42.9%，而且 1，1，1，2 -四氣乙坑爲唯一的主產物。 在3〇〇C下，1,1-二氣-2-氟乙缔轉化率爲而且主 產物也是1，1，1，2-四氟乙烷，雖然也得到相當量之氣· 2,2,2_三氟乙坑[HCFC 133a]。 ‘裝-- f請先閲讀背面之注意事項再填寫本頁} 表1 經濟部中央標準局員工消费合作社印製 在3 5 0 C下’ 1,1-二氣-2-氟乙缔轉化率爲98.5%’而且主 產物爲一大約比例爲1:2之1，1，1，2-四氟乙烷和氯_2又2_三 氟乙燒。 樣品編號 溫度（°C) 轉化率（％ ) 選擇性（％) 134a 133a 2 300 93.7 54.8 37.2 3 300 86.6 48.2 46.0 4 250 42.9 76.5 5.3 300 81.6 69.3 25.3 350 98.5 32.8 65.5 實例5 此實例爲描述1,1-二氣-1,2-二氟乙烷（HCFC 132c)轉化成 1,1，1，2-四氟乙烷。 使用在實例2中所描述之程序，催化溫度範圍從200 °C 至3 3 3°C下，將1，1-二氱·1，2-二氟乙烷（〇·3克）與氟化氫反 -12- 、-0 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（10 ) 應。用以分析之樣品則在4分鐘後取得。試驗則在催化溫 度爲 200°C、250°C、29(TC 和 33(TC 下進行。la•二氣 _12·二 氟乙烷爲如前述所製備，且含有6〇 %重量百分比之i丨_二 氣-1-氟乙坑（HCFC 141b)及40%重量百分比之hcfc 132c。 在每一試驗中所觀察到的主產物爲三氣乙烷（HFC 1呼3a) ^以假設來解釋此結果（a)主產物爲唯—衍生來自於 起始物質中之ι，ΐ-二氣-1-氟乙烷，而（Β)11-二氣小氟乙烷 在其他部分沒有作用，所以除了 i，M_三氣乙烷以外，所 有其他的產物爲衍生來自1,1-二氣_12_二氟乙燒。 分析結果顯示於表2。 在330°C下，1，1-二氣-二氟乙烷轉化率爲1〇〇%，且 主產物爲1，1，1，2-四氟乙故和氣_2,2,2-三氟乙烷。 在下，其轉化率爲1〇0。/0,且主產物爲i，1，1，2·四 氟乙坑λ-2,2,2-三氟乙烷。 在2 50°C下，其轉化率爲100%，且主要產物爲1112· 四氟乙烷和氣-2,2,2-三氟乙烷。 在2O0eC下，其轉化率爲100%，且主要產物爲1112_ 四氟乙烷。 在這些試驗中’頃觀察到所得之^-二氣·2·氟乙烯 (1^?0：1121&)爲副產品且其選择性百分比爲162%(在33() 0：下）、2.9°/〇(在 290 (：下）、31.7%(在250。(：下）和55.6<%(在 200 C下）。也發現到可在25〇°c下（51%)及2〇〇.c 下（23.6%) 獲得。 表2 -13-During the sample supply period, at a catalytic temperature of 25 (TC, 300 ° C and 350eC -11-this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the precautions on the back (Fill in this page again) Install. '-° A7 Description of the invention (9) --- Three samples are carried out under "" The product stream samples for analysis are taken away from the converted gaseous fluorine / nitrogen stream for 4 minutes. The results are shown in Table 1. At 250 (3, the conversion rate of 1,1-digas-2-fluoroethylene is 42.9%, and the 1,1,1,2-tetrafluoroethane pit is The only main product. At 300 ° C, the conversion rate of 1,1-digas-2-fluoroethylene and the main product are also 1,1,1,2-tetrafluoroethane, although a considerable amount of Gas 2,2,2_trifluoroethane pit [HCFC 133a]. 'Install-f Please read the precautions on the back before filling in this page} Table 1 Printed on 3 5 0 by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Under C, the conversion rate of 1,1-digas-2-fluoroethylene is 98.5% 'and the main product is a ratio of approximately 1,2: 1,1,1,2-tetrafluoroethane and chlorine_2. 2_Trifluoroethane. Sample number temperature (° C) Conversion rate ( ) Selectivity (%) 134a 133a 2 300 93.7 54.8 37.2 3 300 86.6 48.2 46.0 4 250 42.9 76.5 5.3 300 81.6 69.3 25.3 350 98.5 32.8 65.5 Example 5 This example describes 1,1-difluoro-1,2-difluoro Ethane (HCFC 132c) is converted to 1,1,1,2-tetrafluoroethane. Using the procedure described in Example 2, the catalytic temperature range is from 200 ° C to 3 3 3 ° C. -Di-1,2,2-difluoroethane (0.3g) and hydrogen fluoride reverse -12-, -0 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative A7 B7 V. The description of the invention (10) should be. The sample for analysis is obtained after 4 minutes. The test is carried out at a catalytic temperature of 200 ° C, 250 ° C, 29 (TC and 33 (TC .La • Diqi_12 · difluoroethane is prepared as described above, and contains 60% by weight of i 丨 _diqi-1-fluoroethane pit (HCFC 141b) and 40% by weight of hcfc 132c. The main product observed in each experiment was tri-gas ethane (HFC 1H 3a). ^ Explain this result with assumptions. (A) The main product is only—the derivation comes from the start Among the substances, ι, l-digas-1-fluoroethane, and (B) 11-digas small fluorine ethane has no effect in other parts, so all products except i, M_trifluoroethane Derived from 1,1-digas_12_difluoroethane. The analysis results are shown in Table 2. At 330 ° C, the conversion rate of 1,1-digas-difluoroethane is 100%, and the main product is 1,1,1,2-tetrafluoroethane, and gas_2,2,2-tri Fluoroethane. Below, its conversion rate is 100. / 0, and the main product is i, 1,1,2, tetrafluoroethane λ-2,2,2-trifluoroethane. At 2 50 ° C, the conversion rate is 100%, and the main products are 1112 · tetrafluoroethane and gas-2,2,2-trifluoroethane. At 2O0eC, the conversion rate is 100%, and the main product is 1112_tetrafluoroethane. In these experiments, it was observed that the resulting ^ -digas · 2 · vinyl fluoride (1 ^? 0: 1121 &) was a by-product and its selectivity percentage was 162% (at 33 () 0: below), 2.9 ° / 〇 (at 290 (: below), 31.7% (at 250. (: below) and 55.6 <% (at 200 C). It was also found to be at 25 ° C (51%) and 2〇 Obtained under 〇.c (23.6%). Table 2 -13-
本紙张尺度適用中國國家標準（CMS ) A4^m (TT〇^297^tT I--^-----装------1T------^ (請先閱讀背面之注意事項再填寫本頁) 2^4649 A7 B7 五、發明説明（h 樣品编號 溫度（°c) 轉化率（％ ) 選擇性（％) ------—-- ----- 134a 133a 5 200 100 17.2 1.3 250 100 54.8 6.2 290 100 26.9 65.0 330 100 22.5 52.6 爲了比較之目的，使用在實例2中所描述之程序，在催 化溪度爲29(TC下（試驗i)和330。〇下（試驗2)，將氣_ 2,2,2-三氟乙烷（HCFC 133a)(0.3克）舆氟化氩反應。 在試撿1中，在29(TC下，HCFC 133a轉化率只有約7% ，而1，1，1，2-四氟乙烷之產率爲6.5%。 在試驗2中，在HCFC之轉化率爲約20%，而ι，ι，ι，2-四 氟乙烷之產率爲18.7%。 結果則顯示於表3。 表3 樣品編號 溫度（°c) 轉化率（％) 『1 33al 選擇性（％) 『13 4a] 比對樣品 290 7.2 9 0^ 330 19.8 94.4 實例6 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 此實例爲舉例説明1，1，2-三氯-1,2-二氟乙烷（HCFC 122a) 轉化成五氟乙烷（HFC 125)。 使用在實例2中所描述之程序，在催化溫度爲34〇<>(：下 -14- 本紙乐尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（12 ) ，除了將催化劑過夜氟化取代2小時氟化，而將1，1，2-三氣 -1，2-二氟乙烷（0.47克）與氟化氫反應。結果則顯示於表4 --------批衣------1T------\ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 表4 樣品編號 溫度(°c) 轉化率〇) 選擇性(％) 125 12聆 124k 1111 6 340 100 33.2 2.1 29.6 7.4 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（2!0X 297公釐）This paper scale is applicable to Chinese National Standard (CMS) A4 ^ m (TT〇 ^ 297 ^ tT I-^ ----- installed ------ 1T ------ ^ (please read the back Matters needing attention and then fill out this page) 2 ^ 4649 A7 B7 5. Description of the invention (h Sample number temperature (° c) Conversion rate (%) Selectivity (%) ---------- ----- 134a 133a 5 200 100 17.2 1.3 250 100 54.8 6.2 290 100 26.9 65.0 330 100 22.5 52.6 For the purpose of comparison, the procedure described in Example 2 was used at a catalytic flux of 29 (TC (test i) and 330). 〇 next (test 2), the gas _ 2,2,2-trifluoroethane (HCFC 133a) (0.3 g) and argon fluoride reaction. In the test 1 at 29 (TC, HCFC 133a conversion rate Only about 7%, and the yield of 1,1,1,2-tetrafluoroethane is 6.5%. In Test 2, the conversion rate in HCFC was about 20%, while ι, ι, ι, 2-tetra The yield of fluoroethane is 18.7%. The results are shown in Table 3. Table 3 Sample number temperature (° c) Conversion rate (%) 『1 33al selectivity (%)『 13 4a] Comparison sample 290 7.2 9 0 ^ 330 19.8 94.4 Example 6 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the back Please pay attention to this page and fill out this page) This example is used to illustrate the conversion of 1,1,2-trichloro-1,2-difluoroethane (HCFC 122a) to pentafluoroethane (HFC 125). Used in Example 2 The described procedure, at a catalytic temperature of 34〇 < > (: Lower -14- This paper music standard is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) A7 B7 V. Invention description (12), except for The catalyst was fluorinated overnight instead of fluorination for 2 hours, and 1,1,2-trifluoro-1,2-difluoroethane (0.47 g) was reacted with hydrogen fluoride. The results are shown in Table 4 ------- -Approved clothing ------ 1T ------ \ (please read the precautions on the back before filling in this page) Printed form 4 Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 4 Sample number Temperature (° c) Conversion Rate 〇) Selectivity (%) 125 12 Listen 124k 1111 6 340 100 33.2 2.1 29.6 7.4 -15- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2! 0X 297 mm)