509666 A7 B7 _ 五、發明說明（，） [發明所屬之技術領域] (請先閱讀背&之注意事項再填寫本頁) 本發明關於一種在汽相中使氫氟化碳與氟氣體反應以 製造全氟化碳之方法，及關於一種製造全氟化碳之方 法，其特徵在於：在第一反應區中使氫氟化碳與氟氣體 於汽相中於高反應溫度進行接觸，將所生成之氣體作爲 稀釋性氣體導入第二反應區中，將不同於第一反應區所 反應者的氫氟化碳（若須要連同氟氣體）送至第二反應 區，以使在高反應溫度中接觸。在常溫下呈液態的全氟 化碳化合物例如可用於在半導體工業中當作蝕刻氣體、 淸洗氣體等，而在常溫下呈液態的化合物則可作爲冷卻 液體等，其用途極爲廣泛，在工業上堪稱爲一項有用之 化合物。 [既有技術1 經濟部智慧財產局員工消費合作社印製 關於全氟化碳的製法，在以往已提出各種方法。例如 具有1個碳原子之全氟化碳的四氟甲烷（以下稱作爲 「FC-14」或「CF4」）情況中，係爲使氯三氟甲烷（CC1F3) 在觸媒的存在下與HF反應之方法（特公昭62-1 02 1 1 號），二氯二氟甲烷（CC12F2)在觸媒之存在下與HF反應 之方法（特公昭42-3004號），使四氯化碳（CC丨4)與HF 反應之方法（特公昭43-10601號），使三氟甲烷（CHF3) 與F2反應之方法（GB-1 11 6920 ; 1 986年），在BrF3或 IFS中使碳（〇與F2反應之方法（特開昭58-162536號）， -3- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 509666 A7 一 ___B7__ 五、發明說明（2 ) 將四氟化乙烷（cf2 = cf2)與co2在高溫加以熱分解之方 法(US-4365 1 02 ； 1982 年）等。 (請先閱讀背¾之注意事項再填寫本頁) 又，例如在有2個碳原子之全氟化碳的六氟乙烷（以 下稱作爲「FC-116」或「CF3CF3」）之情況中，已知有 以乙烷及/或乙烯作爲原料之電解氟化法，將四氟乙烯 等予以熱分解之熱分解法，使用金屬氟化物來氟化乙 炔、乙烯及/或乙烷等之方法，使用氟化氫來氟化二氯 四氟乙烷或氯化五氟乙烷等之方法，使用氟氣體與乙烷 等反應而直接氟化之方法等。 再者，例如在已知有3個碳原子之全氟化碳的八氟丙 烷（以下稱作爲「FC-218」或「C3F8」）之情況中，已 知有使用氟氣體與丙烷反應之直接氟化法（EP-31519:1981 年）等 ° 經濟部智慧財產局員工消費合作社印製 使用氟氣體的直接氟化法，已知有（a)藉由噴射式反應 器使氟氣體與乙烷反應而得到FC-14或FC-116之方法 (美國化學學會雜誌77，3307(1955)，美國化學學會雜 誌82，5827(1 960)，（b)藉由一具有多孔質之氧化鋁管反 應器以氟氣體將C-H氟化之方法（EP-31519 (1981))， (〇藉由一具有多孔質金屬管的反應器（雙重管構造）， 於稀釋性氣體存在下，將直鏈烴氣體氟化之方法：該稀 釋性氣體爲 SF6、CF4、C2F6、C3F8(EP-33210(1981)) 等。 -4- 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐） \1/ \~/ 2 3 试 >严 耳 耳 莫莫 F^/F 卡 HfHHffH 4960 7 9 + 4 + 6 161 11 F 11 FH 2H ΟΔΟΔ r\ /fvv 經濟部智慧財產局員工消費合作社印製 509666 A7 B7 五、發明說明（3 ) 使用氟氣體的其它反應例，已知有（d)使飽和或不飽和 烴或部分被氟化之烴與氟氣體反應以製造氫氟化碳之方 法（US-54〇6008(1995))或從吸附有鏈烯與氟氣體之碳 製造氟化鏈烯之方法（特開平2-2 0 7 052 )等。 [發明所欲解決之問題】 如上述使用氟氣體之直接氟化法，因係使用富有極具 反應性之氟氣體，而使得作機基質的有機化合物與氟氣 體有爆炸及腐蝕之危險，此外有因爲發熱而導致之C-C 鍵斷裂或聚合，或是因爲碳（C)的形成或沈積等而導致 的急劇反應或爆炸等之危險。例如，在藉直鏈烴化合物 與氟氣體反應以合成全氣化碳的直接氟化法之情況中， 則伴隨有以下非常大的反應熱。 CKU + 4F2 C2 H6 + 6F2 依此，C-F鍵取代1個C-H鍵時，會發生約_11〇汗 卡/莫耳的反應熱。在丙院與氟氣體反應之直接氟化法 中，ΔΗ則爲約-880仟卡/莫耳。 以甲烷爲原料的情況（式2)中，則每一莫耳的甲院使 用4莫耳的氟，而以乙烷爲原料的情況（式3)中，則每 一莫耳的乙院需要使用6莫耳的氟。因此，反應的熱量 係與所用的氟之莫耳數成比例，氟量愈多數其反應熱愈 --—裝------**!訂·--------· (請先閱讀背a之注意事項再填寫本頁) -5- 509666 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（4 ) 大。該發熱容易引起C-C鍵的斷裂或爆炸等，而降低其 產率，並有工業上製造及操作上的問題。作爲抑制直接 氟化法中所急劇產生的熱量之方法，曾考慮：將氟以其 他情性氣體（氮或氯等）予以稀釋之方法，將作爲基質 的有機化合物事先溶解於一對氟呈惰性的溶劑中以降低 濃度之方法，在低溫範圍中進行反應之方法，在汽相中 進行反應之方法，用噴射式反應器等裝置使作爲基質的 有機化合物與數氟數小量逐漸接觸之方法。 本發明旨在於解決以上所述問題或課題，從而其目的 係在於提供一種藉由使用有機化合物當作基質，使其與 氟氣體進行直接氟化，而得以工業上安全地且有經濟上 有效益之全氟化碳的製造方法。 [解決問題所需之手段j 以上之問題或課題，有關於在汽相中使氫氟化碳與氟 氣體反應而製造全氟化碳的方法，其特徵在於：在第一 反應區中使氫氟化碳與氟氣體於汽相中於高反應溫度接 觸，將所生成之氣體作爲稀釋性氣體導入第二反應區 中，將不同於第一反應區所反應者的氫氟化碳（若須要 則連同氟氣體）送至第二反應區，以使在高反應溫度中 接觸，同時將第二反應區的生成氣體之至少一部分予以 循環作爲第一反應區的稀釋性氣體使用。 稀釋性氣體爲係四氟甲烷、六氟乙烷、八氟丙烷以及 -6 - 本紙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¾之注意事項再填寫本頁) 訂---------線0- ^666 ^666 經濟部智慧財產局員工消費合作社印製 A7 B7 $、發明說明（f ) 氟化氫，較佳爲四氟甲烷、六氟乙烷及氟化氫，且最佳 爲富有氟化氫成分者。 實施本反應之際，作爲原料之氫氟化碳有必要在彼此 之反應區入口濃度在8莫耳％以下實施反應。又，反應 溫度係在高溫範圍內實施，最好在彼此反應區於200-550 t之範圍者爲佳。反應壓力在各自之反應區宜以在0-5MPa範圍內實施。 以本反應所獲得之全氟化碳有2種類以上，爲FC-1 4、 FC-116以及FC-218，最好爲FC-14及FC-116。所供應 的氫氟化碳係以如下通式CxHyFZ(lSx^3，l^yS4, l$zS7 且 x 爲 1 時 y + z = 4，X 爲 2 時 y + z = 6，x 爲 3 時 y + z = 8所表示之整數）所代表的氫氟化碳類之2種以上， 宜由氟甲烷（CH3F)、二氟甲烷（CH2F2)、三氟甲烷 (CHF3)、三氣乙院（C2H3F3)、四氟乙烷（C2H2F4)、五氟 乙烷（c2hf5)、五氟丙烷（c3h3f5)、六氟丙烷（C3H2f6)以 及七氟丙烷（C3HF7)群所選取，較佳爲氟甲烷、二氟甲 烷、三氟甲烷、三氟乙烷、四氟乙烷及五氟乙烷，最佳 爲二氟甲烷、三氟甲烷、四氟乙烷及五氟乙烷。 又，在所供應的氫氟化碳中含有不純物氯化合物，最 好使用含有該氯化合物的濃度在2莫耳％以下之氫氟化i 碳。 [發明之實施形態1 -7 _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------------‘--訂---------線 (請先蘭讀背面之注意事項再填寫本頁) 509666 A7 ____Β7____五、發明說明（G ) 以下針對本發明之製造全氟化碳的方法作詳細說明。 本發明爲在第一反應區中使氫氟化碳與氟氣體於汽相 中於高反應溫度接觸，將所生成之氣體（全氟化碳及/ 或氟化氫）作爲稀釋性氣體導入第二反應區中，將不同 於第一反應區所反應者的氫氟化碳送至第二反應區，若 須要則連同氟氣體，以使在高反應溫度中接觸的全氟化 碳之製法，同時以第二反應區所生成之氣體（全氟化碳 及/或氟化氫）之至少一部分循環作爲第一反應區的稀 釋性氣體使用，如此得以克服以往直接氟化法所引起之 問題，得以工業上安全地及經濟上有效率地製造全氟化 碳者。 本發明的主要特點乃爲稀釋性氣體。 由本反應之氫氟化碳與氟氣體以製造全氟化碳時，其 反應式與反應熱則爲如下所示。 (請洗閱讀背，面之注意事項再填寫本頁) 裝 — — ill ·11111 經濟部智慧財產局員工消費合作社印製 CH2 F2 + 2F2 chf3 + f2 CFs CH2 F + 2F2 CF3 CHF2 + F2 CF4 + 2HF (式 4) (△H=- 2 5 9肝/莫耳) CF4 + HF (式 5) ^ CFs CFs + 2HF (式6) (△11=一2 3 1仟卡/_ CFs CFs + HF (式7) 作爲稀釋性氣體，一般雖可使用氮、氨或氬等惰性氣 體，惟考慮及於標的物之全氟化碳與此等惰性氣體以蒸 8- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 509666 A7 B7 五、發明說明（了） 餾步驟之分離、純化等，就成本面而言’實非有利之方 法，而作爲稀釋性氣體’所生成之氣體乃爲含有四氟甲 烷，六氟乙烷，八氟丙烷以及氟化氫之氣體，較好爲含 有四氟甲烷，六氟乙烷及氟化氫之氣體’而最好係含有 大量氟化氫成分者最具經濟。 本發明如以上式4至式7所示，皆生成有氟化氫（沸 點2 00 °C )之產物。例如使用二氟甲烷爲原料之有機化 合物時，會生成1莫耳之FC-14與2莫耳之氟化氫。 如係使用五氟乙烷時，則生成1莫耳之FC-116與1莫 耳之氟化氫，其標的物FC-14(沸點：-127.9°C)或FC-116 (沸點：-78.5°C )與副產物氟化氫之沸點差爲約l〇〇°C， 可藉蒸餾，純化步驟而容易分離氟化氫，又比較氦（沸 點：-2 86.9 °C)等均爲高沸點，對於分離、純化之能量 成本槪爲有利。 更且，可直接將反應之生成氣體稀釋使用，頗符成本 效益。又，氟化氫作爲稀釋性氣體可經由蒸餾、純化步 驟8回收氟化氫而供循環使用，而通常係使用於其他之 用途。至於使用氟氣體之直接氟化法因經由長期間反應 如前述由C-C鍵之斷裂或聚合物等而有碳的生成和沈積 等情形。此種碳的生成、沈積等雖有氟氣體之急激反應 或爆炸之危險性，但因使用富含有氟化氫作爲稀釋性氣 體，因此可抑制碳的生成和沈積。含有豐富氟化氫成分 -9 - 表紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 一 ------------裝-----L--訂--------- (請先閱讀背面之注意事項再填寫本頁) 509666 A7 B7_ 五、發明說明（S ) 係意味以氟化氫爲主要成分之意思。 (請先閱讀背S之注音3事項再填寫本頁) 雖在氫氟化碳（反應之基質），氟氣體以及稀釋性氣 體的存在下進行反應，但通常係將導入於反應器前無論 爲反應的基質，氟氣體的任何一種以稀釋性氣體稀釋 後，再將其導入於反應器。惟基於安全性的考量，最好 盡可能將反應之基質與氟氣體同時以稀釋性氣體使之形 成爲低濃度者爲佳。 經濟部智慧財產局員工消費合作社印製 本發明之第二特點爲，將反應基質之氫氟化碳在8莫 耳％以下之反應器入口濃度進行反應。如上述一般使用 氟氣體的直接氟化法，由於使用富有相當反應性的氟氣 體，因此屬於基質之有機化合物（特別是含有氫之化合 物），如拋露於氟中則有燃燒或爆炸之危險。本發明因 使用含有氫之氫氟化碳作爲基質化合物，故其主要特點 爲可防止氫氟化碳與氟的爆炸。如欲防止爆炸則需將混 合氣體之組成介於爆炸範圍內不可。本發明者針對氫氟 化碳與氟氣體之爆炸範圍檢討結果，發現依氫氟化碳的 種類而其範圍數値有差異，同時判明氫氟化碳爆炸範圍 的下限値在8莫耳％以下，因而可設定本反應有機化合 物入口濃度的安全範圍。 反應溫度亦爲使本發明有效率地進行反應的重要條件 之一，而反應溫度可依接觸時間或氫氟化碳原料之種類 而改變其最適範圍。例如，1，1，1，2-四氟乙烷與氟在稀 -1 0 _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 經濟部智慧財產局員工消費合作社印製 A7 B7___ $、發明說明（守） 釋性氣體的存在下反應時，接觸時間大時（接觸時間15 秒）反應溫度則自約5 0 °C開始反應，至約2 5 0。(：其轉化 率則達約1〇〇%。反應溫度在升高溫度範圍內，第一反 應區及第二反應區一起彼此宜在200-550 °C之範圍。 如反應溫度未滿2 0 0 °C時，則氫氟化碳的轉化率則會 下降，如超出550°C時則發生C-C鍵的斷裂或聚合等而 減低產率，同時有引起反應器等之腐蝕或提高能量成本 的問題故亦不宜適用。接觸時間雖無特別限制，惟宜在 0.1-120秒之範圍，如加長接觸時間時則反應器需加大 而不經濟，通常係在1-30秒之間，較佳則在3-30秒之 範圍，至於充分混合反應基質與氟氣體亦屬重要。 又，在反應系所供應氫氟化碳與氟氣體的莫耳比宜在 〇·5-5·0之範圍內，較佳係在1.0-3.0之範圍內。如所供 應氟氣體的莫耳比未滿0.5時則不會進行反應而效率 差，但如超越5.0時則會有過剩的氟氣體，因需有回收 所用之設備等，殊屬不經濟。關於供應氟氣體的方法雖 無特別限制，例如在第一反應區供應多餘量時，則殘餘 之未反應氟氣體雖可在第二反應區進行反應，通常在第 一反應區及第二反應區一起供應，就安全面考量較爲適 宜。 在進行本反應時反應壓力亦爲防止爆炸等危險的主要 因素。壓力愈高則產生爆炸範圍愈廣，故最好在愈低之 -11 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐)~^ ------------- I I I I ΙΓ I ^--------- (請先-閱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 A7 ---- —___Β7___ 五、發明說明（10 ) 壓力下進行反應爲佳’因此第一反應區及第二反應區之 反應壓力最好在O-SMPa之範圍內。 再者，反應器的材質以對腐蝕性氣體具有耐性者爲 佳，其例子包括有鎳、鎳鉻鐵耐熱合金、耐熱耐蝕鎳基 質合金等。 如前述作爲基質的有機化合物與氟氣體的直接氟化法 係伴隨有非常大的反應熱，反應熱與所使用氟氣體的莫 耳數成比例，由於氟量愈多反應熱愈大，如C-F鍵置換 C-H鍵之數目愈少時則愈容易控制反應熱的問題，因可 減少高價位氟氣體的使用量，故頗符經濟上效益。 本發明之次一特點爲，作爲基質的有機化合物如前述 不使用多數量C-F鍵置換C-H鍵的直鏈烴，部分藉用 已被氟化之氫氟化碳（HFC)，則C-F鍵置換C-H鍵之數 量變少而容易控制反應熱，更且供應2種類以上氫氟化 碳，而可製造2種類以上之全氟化碳。所用氫氟化碳， 係如以下通式509666 A7 B7 _ V. Description of the invention (,) [Technical field to which the invention belongs] (Please read the back & notes before filling out this page) The present invention relates to a method for reacting hydrofluorocarbon with fluorine gas in the vapor phase A method for manufacturing a perfluorocarbon and a method for manufacturing a perfluorocarbon are characterized in that: in a first reaction zone, a hydrofluorocarbon is brought into contact with a fluorine gas in a vapor phase at a high reaction temperature, and The generated gas is introduced into the second reaction zone as a diluent gas, and a hydrofluorocarbon (if necessary together with a fluorine gas) different from that reacted in the first reaction zone is sent to the second reaction zone, so that at a high reaction temperature中 contact. Perfluorocarbon compounds that are liquid at normal temperature can be used, for example, as etching gas and purge gas in the semiconductor industry, and compounds that are liquid at normal temperature can be used as cooling liquid. It can be called a useful compound. [Existing technology 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Various methods have been proposed for the production of perfluorocarbons in the past. For example, in the case of tetrafluoromethane (hereinafter referred to as "FC-14" or "CF4") having a perfluorocarbon with one carbon atom, chlorotrifluoromethane (CC1F3) is reacted with HF in the presence of a catalyst. The reaction method (Japanese Patent Publication No. 62-1 02 1 1), and the method of reacting dichlorodifluoromethane (CC12F2) with HF in the presence of a catalyst (Japanese Patent Publication No. 42-3004), makes carbon tetrachloride (CC丨 4) A method of reacting with HF (Special Publication No. 43-10601), a method of reacting trifluoromethane (CHF3) with F2 (GB-1 11 6920; 1986), and carbon (〇 in BrF3 or IFS). Method for reaction with F2 (Japanese Patent Application Laid-Open No. 58-162536), -3- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 509666 A7 _B7__ 5. Description of the invention (2) will Method for thermal decomposition of ethane tetrafluoride (cf2 = cf2) and co2 at high temperature (US-4365 1 02; 1982), etc. (Please read the precautions on the back before filling this page). In the case of 2-carbon hexafluoroethane (hereinafter referred to as "FC-116" or "CF3CF3"), it is known to use ethane and / or ethylene as the source. Electrolytic fluorination method, a thermal decomposition method that thermally decomposes tetrafluoroethylene, etc., uses a metal fluoride to fluorinate acetylene, ethylene and / or ethane, etc., and uses hydrogen fluoride to fluorinate dichlorotetrafluoroethane. Or a method such as pentafluoroethane chloride, a method of directly fluorinating by reacting a fluorine gas with ethane, etc. Further, for example, octafluoropropane (hereinafter referred to as perfluorocarbon having three carbon atoms) In the case of "FC-218" or "C3F8"), the direct fluorination method (EP-31519: 1981) using the reaction of fluorine gas with propane is known. As a direct fluorination method using a fluorine gas, (a) a method of obtaining FC-14 or FC-116 by reacting a fluorine gas with ethane through a jet reactor is known (Journal of the American Chemical Society 77, 3307 (1955) , Journal of the American Chemical Society 82, 5827 (1960), (b) A method of fluorinating CH with fluorine gas through a porous alumina tube reactor (EP-31519 (1981)), (0 by A reactor with a porous metal tube (dual tube structure) in the presence of a diluent gas Method for fluorinating linear hydrocarbon gas: The diluent gas is SF6, CF4, C2F6, C3F8 (EP-33210 (1981)), etc. -4- This paper standard is applicable to National Standard (CNS) A4 specification (210 X 297 mm) \ 1 / \ ~ / 2 3 Trial > Yan Ermo Mo F ^ / F Card HfHHffH 4960 7 9 + 4 + 6 161 11 F 11 FH 2H ΟΔΟΔ r \ / fvv Intellectual Property Bureau, Ministry of Economy Printed by the employee consumer cooperative 509666 A7 B7 V. Description of the invention (3) Other reaction examples using fluorine gas, known as (d) reacting saturated or unsaturated hydrocarbons or partially fluorinated hydrocarbons with fluorine gas to produce hydrofluoride A method of carbonizing (US-54,06008 (1995)) or a method of producing fluorinated alkenes from carbon in which olefins and fluorine gas are adsorbed (Japanese Patent Application Laid-Open No. 2-2 0 7 052). [Problems to be Solved by the Invention] As described above, the direct fluorination method using a fluorine gas uses a highly reactive fluorine gas, so that the organic compounds used as the organic matrix and the fluorine gas may explode and corrode. In addition, There is a danger of rupture or polymerization of the CC bond due to heat generation, or a sudden reaction or explosion due to the formation or deposition of carbon (C). For example, in the case of a direct fluorination method in which a linear hydrocarbon compound is reacted with a fluorine gas to synthesize a fully gasified carbon, the following very large reaction heat is accompanied. CKU + 4F2 C2 H6 + 6F2 According to this, when C-F bond replaces one C-H bond, a reaction heat of about -11 khan / mol is generated. In the direct fluorination method of the reaction between C and C and fluorine gas, ΔΗ is about -880 仟 cal / mol. In the case of methane (Equation 2), 4 moles of fluorine are used per mole of A-house, and in the case of ethane (Equation 3), each mole of B-house needs Use 6 moles of fluorine. Therefore, the heat of the reaction is proportional to the mole number of fluorine used. The larger the amount of fluorine, the more the heat of reaction ---------------! (Please read the precautions of the back a before filling out this page) -5- 509666 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (4) Large. This heat easily causes the C-C bond to be broken or exploded, thereby reducing its yield, and has industrial manufacturing and handling problems. As a method to suppress the rapid heat generation in the direct fluorination method, a method of diluting fluorine with other emotional gases (nitrogen or chlorine, etc.) has been considered, and an organic compound as a matrix is previously dissolved in a pair of fluorine to be inert. The method of reducing the concentration in the solvent, the method of performing the reaction in the low temperature range, the method of performing the reaction in the vapor phase, and the method of gradually contacting the organic compound as a matrix with a small number of fluorine by using a device such as a jet reactor. . The present invention aims to solve the above-mentioned problems or problems, and an object thereof is to provide an industrial compound that is directly fluorinated with fluorine gas by using an organic compound as a substrate, thereby being industrially safe and economically beneficial. Manufacturing method of perfluorocarbon. [Means required for solving the problem j. The above problems or problems relate to a method for producing a perfluorocarbon by reacting a hydrofluorocarbon with a fluorine gas in a vapor phase, which is characterized in that hydrogen is made in a first reaction zone Carbon fluoride and fluorine gas are contacted in the vapor phase at a high reaction temperature, and the generated gas is introduced as a diluent gas into the second reaction zone, and a hydrofluorocarbon different from the one reacted in the first reaction zone (if required) Then it is sent to the second reaction zone together with fluorine gas) to be contacted at a high reaction temperature, and at least a part of the gas generated in the second reaction zone is recycled as a diluent gas in the first reaction zone. The diluent gas is tetrafluoromethane, hexafluoroethane, octafluoropropane, and -6-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions at the back of the paper before reading) (Fill in this page) Order --------- line 0- ^ 666 ^ 666 Printed by A7 B7 $, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economy, Invention Note (f) Hydrogen fluoride, preferably tetrafluoromethane, six Fluoroethane and hydrogen fluoride, and preferably those rich in hydrogen fluoride. In carrying out this reaction, it is necessary to carry out the reaction at a concentration of 8 mol% or less at the entrance of each reaction zone. The reaction temperature is carried out in a high temperature range, and it is preferable that the reaction temperature is within a range of 200 to 550 t. The reaction pressure is preferably implemented in the range of 0-5 MPa in the respective reaction zone. There are two or more types of perfluorocarbons obtained by this reaction, which are FC-1 4, FC-116, and FC-218, and preferably FC-14 and FC-116. The supplied hydrofluorocarbon is based on the following general formula CxHyFZ (lSx ^ 3, l ^ yS4, l $ zS7 and y + z = 4 when x is 1, y + z = 6 when X is 2, and x when 3 is y + z = an integer represented by 8) 2 or more types of hydrofluorocarbons, preferably from fluoromethane (CH3F), difluoromethane (CH2F2), trifluoromethane (CHF3), Sanqiyiyuan ( C2H3F3), Tetrafluoroethane (C2H2F4), Pentafluoroethane (c2hf5), Pentafluoropropane (c3h3f5), Hexafluoropropane (C3H2f6) and Heptafluoropropane (C3HF7). It is preferably fluoromethane, difluoromethane , Trifluoromethane, trifluoroethane, tetrafluoroethane and pentafluoroethane, the most preferred are difluoromethane, trifluoromethane, tetrafluoroethane and pentafluoroethane. In addition, since the supplied hydrofluorocarbon contains an impure chlorine compound, it is preferable to use a hydrofluorinated i-carbon having a concentration of 2 mol% or less of the chlorine compound. [Inventive Embodiment 1 -7 _ This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------------------'-- Order --------- Line (please read the precautions on the back before filling out this page) 509666 A7 ____ Β7 ____ V. Description of the invention (G) The following is a detailed description of the method for manufacturing perfluorocarbon according to the present invention. . In the present invention, in a first reaction zone, a hydrofluorocarbon and a fluorine gas are brought into contact in a vapor phase at a high reaction temperature, and the generated gas (perfluorocarbon and / or hydrogen fluoride) is introduced into the second reaction as a diluent gas. In the zone, a hydrofluorocarbon different from the one reacted in the first reaction zone is sent to the second reaction zone, if necessary, together with a fluorine gas to make a perfluorocarbon contacted at a high reaction temperature, and at the same time, At least a part of the gas (perfluorocarbon and / or hydrogen fluoride) generated in the second reaction zone is recycled as a diluent gas in the first reaction zone, so that the problems caused by the previous direct fluorination method can be overcome, and industrial safety can be achieved. Those who produce PFCs locally and economically efficiently. The main feature of the present invention is a diluent gas. When the perfluorocarbon is produced from the hydrofluorocarbon and fluorine gas in this reaction, the reaction formula and heat of reaction are as follows. (Please read the back and fill out the precautions before filling out this page.) Packing — ill · 11111 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs CH2 F2 + 2F2 chf3 + f2 CFs CH2 F + 2F2 CF3 CHF2 + F2 CF4 + 2HF (Equation 4) (△ H =-2 5 9 liver / mole) CF4 + HF (Equation 5) ^ CFs CFs + 2HF (Equation 6) (△ 11 = One 2 3 1 仟 Card / _ CFs CFs + HF ( (Formula 7) As a diluent gas, although inert gases such as nitrogen, ammonia, or argon can generally be used, the perfluorocarbons of the subject matter and these inert gases are considered for steaming. 8- This paper applies Chinese national standards (CNS ) A4 size (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 509666 A7 B7 V. Description of the invention (I) The separation and purification of distillation steps, in terms of cost, 'is not a beneficial method, As the diluent gas, the gas generated is a gas containing tetrafluoromethane, hexafluoroethane, octafluoropropane and hydrogen fluoride, preferably a gas containing tetrafluoromethane, hexafluoroethane and hydrogen fluoride. It is the most economical if it contains a large amount of hydrogen fluoride. It is a product with hydrogen fluoride (boiling point 200 ° C). For example, when using difluoromethane as an organic compound, 1 mole of FC-14 and 2 mole of hydrogen fluoride will be generated. If pentafluoroethane is used, One mole of FC-116 and one mole of hydrogen fluoride are produced. The difference between the boiling point of the subject matter FC-14 (boiling point: -127.9 ° C) or FC-116 (boiling point: -78.5 ° C) and the by-product hydrogen fluoride is At about 100 ° C, hydrogen fluoride can be easily separated by distillation and purification steps. Compared with helium (boiling point: -2 86.9 ° C), all have high boiling points, which is advantageous for the energy cost of separation and purification. Moreover, The reaction generated gas can be directly diluted and used, which is quite cost-effective. In addition, as a diluent gas, hydrogen fluoride can be recovered through distillation and purification step 8 for recycling, and is usually used for other purposes. As for the use of fluorine gas The direct fluorination method has the formation and deposition of carbon due to the long-term reaction such as the rupture of the CC bond or the polymer, etc. Although such carbon generation and deposition have the violent reaction or explosion danger of fluorine gas , But because it is rich in fluorine Hydrogen is a diluent gas, so it can suppress the generation and deposition of carbon. Rich in hydrogen fluoride content -9-The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) One ------- ----- Equipment ----- L--Order --------- (Please read the notes on the back before filling in this page) 509666 A7 B7_ V. Description of the invention (S) means to The meaning of hydrogen fluoride as the main component. (Please read Note 3 of Note S before filling out this page.) Although the reaction is performed in the presence of hydrofluorocarbon (the substrate of the reaction), fluorine gas and diluent gas, it is usually carried out before introduction into the reactor. Any of the reaction substrate, fluorine gas, is diluted with a diluent gas and then introduced into the reactor. However, based on safety considerations, it is best to use a diluent gas to make the reaction matrix and fluorine gas as low concentration as possible. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The second feature of the present invention is to react the hydrofluorocarbon of the reaction substrate at a reactor inlet concentration of 8 mol% or less. The direct fluorination method that generally uses fluorine gas as described above, due to the use of quite reactive fluorine gas, organic compounds (especially compounds containing hydrogen) that belong to the matrix, if exposed to fluorine, there is a danger of burning or explosion . Since the present invention uses hydrogen-containing hydrofluorocarbon as a matrix compound, its main feature is that it can prevent the explosion of hydrofluorocarbon and fluorine. To prevent explosion, the composition of the mixed gas must be within the scope of the explosion. The inventor reviewed the explosion range of HFC and fluorine gas and found that the range number varies depending on the type of HFC and the lower limit of the range of HFC explosion was determined to be below 8 mole%. Therefore, it is possible to set a safe range of the inlet concentration of the organic compound in the reaction. The reaction temperature is also one of the important conditions for efficiently carrying out the reaction of the present invention, and the reaction temperature can be changed to its optimum range depending on the contact time or the type of the hydrofluorocarbon raw material. For example, 1,1,1,2-tetrafluoroethane and fluorine in dilute -1 0 _ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative Preparing A7 B7___ $, Description of Invention (Preservation) When reacting in the presence of a release gas, when the contact time is large (contact time 15 seconds), the reaction temperature starts from about 50 ° C to about 250. (: Its The conversion rate is about 100%. The reaction temperature is within the elevated temperature range, and the first reaction zone and the second reaction zone together should be in the range of 200-550 ° C. If the reaction temperature is less than 200 ° C If it exceeds 550 ° C, the CC bond will break or polymerize to reduce the yield. At the same time, it will cause corrosion of the reactor or increase the energy cost. Not applicable. Although the contact time is not particularly limited, it should be in the range of 0.1-120 seconds. If the contact time is increased, the reactor needs to be enlarged and uneconomical, usually between 1-30 seconds, preferably 3- In the range of 30 seconds, it is also important to sufficiently mix the reaction matrix and the fluorine gas. The molar ratio of the supplied hydrofluorocarbon and fluorine gas should be in the range of 0.5-5. 0, and preferably in the range of 1.0-3.0. If the molar ratio of the supplied fluorine gas is less than At 0.5, the reaction does not proceed and the efficiency is poor, but if it exceeds 5.0, there will be excess fluorine gas, which is uneconomical because of the equipment required for recovery. Although there are no special restrictions on the method of supplying fluorine gas, for example When the excess amount is supplied in the first reaction zone, although the remaining unreacted fluorine gas can be reacted in the second reaction zone, it is usually supplied together in the first reaction zone and the second reaction zone, and it is appropriate to consider the safety aspect. The reaction pressure during the reaction is also the main factor to prevent dangers such as explosion. The higher the pressure, the wider the explosion range, so it is better to be lower -11-This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) ~ ^ ------------- IIII ΙΓ I ^ --------- (please read the notes on the back before filling this page) Ministry of Economy Wisdom A7 printed by the Consumer Cooperative of the Property Bureau ---- —___ Β7 ___ V. Description of Invention (10) It ’s better. Therefore, the reaction pressure of the first reaction zone and the second reaction zone is preferably in the range of O-SMPa. Furthermore, the material of the reactor is preferably resistant to corrosive gases. Examples include nickel, Nickel-chromium heat-resistant alloy, heat-resistant and corrosion-resistant nickel matrix alloy, etc. As mentioned above, the direct fluorination method of organic compounds and fluorine gas as a matrix is accompanied by a very large reaction heat, which is proportional to the mole number of the fluorine gas used. As the amount of fluorine increases, the reaction heat increases. For example, the smaller the number of CF bonds replacing the CH bonds, the easier it is to control the reaction heat. The use of high-priced fluorine gas can be reduced, which is quite economical. A second feature of the present invention is that, as the organic compound as a matrix, as described above, the straight chain hydrocarbons that do not use a large number of CF bonds to replace the CH bonds are partially borrowed from fluorinated hydrogen fluoride (HFC), and the CF bonds replace the CH The number of bonds is reduced, which makes it easier to control the heat of reaction, and more than two types of hydrofluorocarbons can be supplied to produce two or more types of perfluorocarbons. The hydrofluorocarbon used is as follows
CxHyFz (通式） (式中，X、y、Z 各爲 1SxS3，l$yS4，lgzS7，且 X 爲 1時y + z = 4，X爲2 時y + z = 6，X爲3時y + z = 8所示之 整數）所代表之氫氟化碳。 宜爲選自C-F鍵置換C-H鍵之數在3以內之氟甲烷、 二氟甲烷、三氟甲烷、三氟乙烷、四氟乙烷、五氟乙烷、 -12- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) _ — — — — — — — — — — — I I I I 舊靈 I (請先閱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 509666 A7 __B7 ___ 五、發明說明（"） 五氟丙烷、六氟丙烷及七氟丙烷之群，較佳爲易於採購 之原料如氟甲烷、二氟甲烷、三氟甲烷、三氟乙烷、四 氟乙烷及五氟乙烷，而最佳爲C-F鍵置換C-H鍵之數 在2以內之二氟甲烷、三氟甲烷、三氟乙烷、四氟乙烷 及五氟乙烷，此等氫氟化碳類例如可作爲氯氟化碳（CFC) 或氫氯氟化碳（HCFC)的替代品，或作爲冷媒而工業化 生產，因容易獲得純度亦高達99.9 %以上故宜於適用。 因此，如與直鏈的烴化合物和氟氣體所製造的全氟化 碳（式2及式3)比較時，由於因使用上述之氫氟化碳 故可將反應熱抑制約1/2-1/6(式4至式7)。 此等氫氟化碳可單獨或以混合物之形態使用，從其所 獲得標的物之全氟化碳爲2種類以上，宜爲四氟甲烷、 六氟乙烷及/或八氟丙烷，而最佳爲四氟甲烷及六氟乙 烷。 再者，此等作爲反應原料之氫氟化碳最好不含有氯化 合物者爲佳，如含有氯化合物時在反應之際會生成氯或 氟化氯，對於裝置材質或蒸餾操作上均不適宜。含氯化 合物之混合濃度宜在2莫耳％以下，較佳爲1莫耳％以 下，而最佳爲〇 · 1莫耳％以下。 本發明之另一重要之特點爲，提供以上三種特點與反 應條件相加而成之安全且有效率之經濟性製造方法，以 汽相在第一反應區使氫氟化碳與氟氣體在高之反應溫度 -13- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱) ' - -----------裝-----r--訂-------- (請先閱讀背面之注意事項再填寫本頁) 509666 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（u) 中接觸生成全氟化碳與氟氣體，將其部分或全部作爲稀 釋性氣體而導入於第二反應區，如有必要供應以不同於 第一反應區所供應之氫氟化碳與氟氣體，在高反應溫度 中接觸生成第二之全氟化碳與氟化氫，將其部分作爲稀 釋性氣體再循環使用於第一反應區及/或第二反應區之 製造方法。 例如，在汽相以1，1，1，2-四氟乙烷作爲氫氟化碳以富 有氟化氫之氟氣體作爲稀釋性氣體一起供應於高溫的第 一反應區，在第一反應區生成FC-116爲全氟化碳與氟 化氫。反應器出口氣體可將其一部分直接使用作爲稀釋 性氣體，而有可能導入於蒸餾步驟，一般係導入於第二 反應器。在第二反應器的入口，例如有必要時則以二氟 甲烷作爲不同之氫氟化碳而氟氣體則與第一反應區的出 口氣體混合供應在提高反應溫度的第二反應區，生成 FC-14全氟化碳與氟化氫。 第二反應區的出口氣體則爲FC-116與FC-14之全氟 化碳，並獲得對含有過剩氟化氫之全氟化碳混合物之副 產物。此第二反應區出口氣體的混合物係將其一部分直 接作爲稀釋性氣體而循環使用於第一反應區及/或第二 反應區，殘餘物則經由蒸餾、純化步驟分離爲全氟化碳 與氟化氫。 依此，從2種類以上之全氟化碳製造2種類以上全氟 -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------------Ρ 丨訂----------線· (請先閱讀背面之注意事項再填寫本頁) A7 B7 經濟部智慧財產局員工消費合作社印製 i、發明說明（1¾ ) 化碳之本製造方法，比較一般之從一種氫氟化碳製造一 種全氟化碳方法而言，可簡化蒸餾步驟等設備或能源成 本等故深具有經濟上效益。 反應區係由一種反應器而可區隔成區，通常基於操作 性或安全性的考量宜使用二種以上反應器。反應器的組 合方式可選用並列或直列，而通常以採用直列者爲宜。 又，2種以上之氫氟化碳，例如由二氟甲烷與三氟甲 烷有可能製造1種類的全氟化合物，如FC-14，更且， 1種氫氟化碳，例如將二氟甲烷分割供應於第一反應區 與第二反應區，而有可能緩和反應。 依此，本製法確屬一種具有工業上安全及富有經濟效 率之全氟化碳的製法。 [實施例] 以下表示本發明之實施例。 首先，將本反應所用原料之氫氟化碳表示如下。 [二氟甲烷] 使用目前當作HCFC-22(CHCIF2)之替代品供應的二氟 甲烷（CH2F2).Eco丨oace 32(商品名：昭和電工製）。其 之純度在99.95%以上，含有1，1，1-三氟乙烷（CF3CH3) 及氟甲烷（CH3F)當作不純物，而其內沒有檢測出氯化合 物。 [三氟甲烷1 -15- (請先閱讀背面之注意事項再填寫本頁) 一裝 I l· ---訂 ---- # 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） j^666 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（κ) 使用目前當作爲冷媒供應的三氟甲烷（chf3) · Ec〇I〇ace23(商品名：昭和電工製）。其之純度在99.95% 以上，含有氯二氟甲烷（CHC〖F2)或氯三氟甲烷（CC1F3) 等含氯化合物當作不純物。 [1，1，1，2-四氟乙烷] 使用目前當作 CFC-12(CC1F2)之替代品供應的 1，1，1，2 -四氟乙烷（CF3CH2F).Eco 丨 oace 134a (商品名： 昭和電工產製）。其之純度爲99.99 %以上，含有異構物 之1，1，2,2-四氟乙烷，沒有檢測出含氯化合物。 [五氟乙烷] 使用目前當作HCFC-22(CHCIF2)之替代品供應的五氟 乙烷（CF3CHF2)*Ecoloace 125(商品名：昭和電工公司 產製）。其之純度爲99.95%以上，含有當作不純物的 CF3CH2F、CF3CH3以及當作含氯化合物的氯五氣乙院 (CF3CC1F2)、1-氯-1，2,2,2·四氟乙烷（CHC1FCF3)。 [實例1] 第1圖顯示本發明全氟化碳製法之流程圖。將上述三 氟甲烷當作氫氟化碳（圖中符號I2)，將其與氟氣體（圖 中符號11)和稀釋性氣體（圖中符號19)之混合而成的混 合氣（圖中符號13)導入第一反應區（圖中符號1)內。 在第一反應區中，於反應壓力爲0.15MPa，反應溫度爲 400°C，F2/三氟甲烷的莫耳比爲1.51，三氟甲烷之入口 -16- 本紙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) 華- 509666 經濟部智慧財產局員工消費合作社印製 A7 •--------B7___ 五、發明說明（G ) 濃度爲2·1莫耳％的條件下反應，而獲得第一反應區的 出口氣體（圖中符號14)。 該出口氣體與作爲新氫氟化碳（圖中符號16)的 1，1，1，2-四氟乙烷和氟氣體（圖中符號ls)進行混合。 將所獲得的混合氣導入於第二反應區（圖中符號2)內。 在第二反應區中，於反應壓力爲0el5]Vlpa，反應溫度爲 3 7(TC，F2/l，l，l，2-四氟乙烷之莫耳比爲 2.06，1，1，1，2- 四氟乙烷之入口濃度爲1.35莫耳％的條件下反應，而獲 得第二反應區之出口氣體（圖中符號18)。將此出口氣體 分離成一稀釋性氣體（圖中符號19)及一將導入於蒸餾 純化步驟內之氣體（圖中符號20)。結果示於表i中。 表1中上段之數値係對應於第1圖中符號。 [實例2] 以相同於實例1之製法流程，使作爲氫氟化碳（圖中 符號12)的上述五氟乙烷與氟氣體（圖中符號u)和 稀釋性氣體（圖中符號19)進行混合，及將所獲得的混 合氣（圖中符號13)導入於第一反應區（圖中符號1) 內。在第一反應區中，於反應壓力爲O.lSMPa，反應溫 度爲370°C，F2/五氟乙烷之莫耳比爲1.47，五氟乙烷之 入口濃度爲3·2莫耳％的條件下反應，而獲得第一反應 區的出口氣體（圖中符號14)。 該出口氣體與作爲新氫氟化碳（圖中符號16)的二氟 -17- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------1---1*!訂------丨 (請先蘭讀背面之注意事項再填寫本頁) A7 ^〜----- —_B7__ 五、發明說明（丨G ) 甲烷和氟氣體（圖中符號15)進行混合，將所獲得的混 合氣（圖中符號I7)導入於第二反應區（圖中符號2) 內。在第一反應區中，於反應壓力爲〇.15MPa,反應溫 度爲3S0C’ F"二氟甲烷之莫耳比爲2·〇ι，二氟甲烷之 入口濃度爲2.05莫耳％的條件下反應，而獲得第二反應 區的出口氣體（圖中符號18)。將此出口氣體分離成一 稀釋性氣體（圖中符號19)及一將導入於蒸餾純化步驟 內之氣體（圖中符號20)。結果示於表2中。 (請先閱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 • 18- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 509666 A7B7 明說 明發 表 D>; β Φ HF?134a- KFC_K H F EF225 F?116 F?14 >H彦 經濟部智慧財產局員工消費合作社印製 姗丑胗St姻 fiaKmol/hr a)<il>m-*^HFC'34aMr 1,1,2-13 »(N钸 * HFC 丨 23l®lll»-ffl爾-HFC 丨 125M£»(Na。 1.013 polo LQ03 11 0·666 31koo9 3L489 PS2 P462 32k5 32· 365 29b2 2.733 0.OQ1 0.665 1·2 13 1.012 0.02 068 17.288 0·0〇〇0 4.983 S5 0.031 0.047 1033 P015 5· 002 7.916 0·031 P367 14 0·00? 0k5 15 0· 038 7.916 5.S2 015 17b3CxHyFz (general formula) (where X, y, and Z are each 1SxS3, l $ yS4, lgzS7, and X is 1 when y + z = 4, X is 2 when y + z = 6, and X is 3 when y + z = integer represented by 8). Preferably, it is selected from the group consisting of fluoromethane, difluoromethane, trifluoromethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, pentafluoroethane, within the number of 3 that the CF bond replaces the CH bond. Standard (CNS) A4 Specification (210 X 297 mm) _ — — — — — — — — — — — — IIII Jiuling I (Please read the precautions on the back before filling this page) Intellectual Property Bureau Staff Consumer Cooperatives Print 509666 A7 __B7 ___ 5. Description of the invention (Pentafluoropropane, hexafluoropropane and heptafluoropropane groups, preferably raw materials such as fluoromethane, difluoromethane, trifluoromethane, trifluoroethane, Tetrafluoroethane and pentafluoroethane, with difluoromethane, trifluoromethane, trifluoroethane, tetrafluoroethane and pentafluoroethane being the most preferred CF bonds replacing the number of CH bonds within two, etc. Hydrofluorocarbons can be used as substitutes for chlorofluorocarbons (CFCs) or hydrochlorofluorocarbons (HCFCs), or as industrial refrigerants. They are suitable for use because they are easy to obtain and have a purity of 99.9% or more. Therefore, when compared with perfluorocarbons (formulas 2 and 3) produced by linear hydrocarbon compounds and fluorine gas, the heat of reaction can be suppressed by about 1 / 2-1 because of the use of the above-mentioned hydrofluorocarbons. / 6 (Equation 4 to Equation 7). These hydrofluorocarbons can be used singly or in the form of a mixture. The target substance obtained from them has 2 or more types of perfluorocarbons, preferably tetrafluoromethane, hexafluoroethane and / or octafluoropropane. Preferred are tetrafluoromethane and hexafluoroethane. In addition, it is preferable that the hydrofluorocarbons used as a reaction raw material do not contain a chloride compound. If a chlorine compound is contained in the reaction, chlorine or chlorine fluoride is generated, which is not suitable for the device material or distillation operation. The mixed concentration of the chloride-containing compound is preferably 2 mol% or less, preferably 1 mol% or less, and most preferably 0.1 mol% or less. Another important feature of the present invention is to provide a safe and efficient economical manufacturing method obtained by adding the above three characteristics and reaction conditions. The vapor phase in the first reaction zone makes the hydrofluorocarbon and fluorine gas at a high level. Reaction temperature -13- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public love) '------------ install ----- r--order- ------ (Please read the notes on the back before filling this page) 509666 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. The invention description (u) generates perfluorocarbon and fluorine gas through contact, Part or all of it is introduced into the second reaction zone as a diluent gas. If necessary, it is supplied with a hydrofluorocarbon and a fluorine gas different from those supplied in the first reaction zone, and is contacted at a high reaction temperature to form a second whole. A method for producing carbon fluoride and hydrogen fluoride by recycling a part of them as a diluent gas in the first reaction zone and / or the second reaction zone. For example, in the vapor phase, 1,1,1,2-tetrafluoroethane is used as hydrofluorocarbon, and hydrogen fluoride-rich fluorine gas is used as a diluent gas to be supplied to a high-temperature first reaction zone, and FC is generated in the first reaction zone. -116 is perfluorocarbon and hydrogen fluoride. A part of the reactor outlet gas can be directly used as a diluent gas, and may be introduced into a distillation step, and is generally introduced into a second reactor. At the inlet of the second reactor, for example, if necessary, difluoromethane is used as a different hydrofluorocarbon, and the fluorine gas is mixed with the outlet gas of the first reaction zone and supplied in the second reaction zone to increase the reaction temperature to generate FC. -14Perfluorocarbon and hydrogen fluoride. The outlet gas of the second reaction zone is the perfluorocarbons of FC-116 and FC-14, and a by-product of a perfluorocarbon mixture containing excess hydrogen fluoride is obtained. A part of the mixture of the gas at the outlet of the second reaction zone is directly reused as a diluent gas in the first reaction zone and / or the second reaction zone, and the residue is separated into perfluorocarbon and hydrogen fluoride through distillation and purification steps. . Based on this, two or more types of perfluoro-14 are manufactured from more than two types of perfluorocarbons. 14- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------- ------- Ρ 丨 Order ---------- Line · (Please read the notes on the back before filling in this page) A7 B7 Printed by i, inventions by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs (1¾) The method for producing carbonized carbon is more economical than the general method for producing a perfluorocarbon from a hydrofluorocarbon, which can simplify the equipment such as distillation steps or energy costs. The reaction zone is divided into one type by one type of reactor. Generally, two or more types of reactors should be used based on operability or safety considerations. The combination of reactors can be parallel or in-line, and usually it is better to use in-line. In addition, two or more types of hydrofluorocarbons, such as difluoromethane and trifluoromethane, may produce one type of perfluoro compound, such as FC-14, and one type of hydrofluorocarbon, for example, difluoromethane The supply is divided into the first reaction zone and the second reaction zone, and the reaction may be moderated. Based on this, this method is indeed a method of making industrially safe and economically efficient perfluorocarbons. [Examples] Examples of the present invention are shown below. First, the hydrofluorocarbons of the raw materials used in this reaction are shown below. [Difluoromethane] Uses difluoromethane (CH2F2). Eco 丨 oace 32 (trade name: manufactured by Showa Denko), which is currently supplied as a substitute for HCFC-22 (CHCIF2). Its purity is above 99.95%, and it contains 1,1,1-trifluoroethane (CF3CH3) and fluoromethane (CH3F) as impurities, and no chloride is detected therein. [Trifluoromethane 1 -15- (Please read the precautions on the back before filling out this page) One pack I l · --- Order ---- # This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) j ^ 666 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (κ) Uses trifluoromethane (chf3) · Ec〇I〇ace23 (trade name: Showa) Electrician). Its purity is above 99.95%, and it contains chlorine-containing compounds such as chlorodifluoromethane (CHC 〖F2) or chlorotrifluoromethane (CC1F3) as impurities. [1,1,1,2-tetrafluoroethane] Use 1,1,1,2-tetrafluoroethane (CF3CH2F), which is currently supplied as a substitute for CFC-12 (CC1F2). Eco 丨 oace 134a ( Product name: manufactured by Showa Denko). Its purity is more than 99.99%, it contains 1,1,2,2-tetrafluoroethane with isomers, and no chlorine-containing compound is detected. [Pentafluoroethane] Pentafluoroethane (CF3CHF2) * Ecoloace 125 (trade name: manufactured by Showa Denko Corporation), which is currently supplied as a substitute for HCFC-22 (CHCIF2), is used. Its purity is 99.95% or more. It contains CF3CH2F, CF3CH3 as impurities, and Chlorine Pentoxide (CF3CC1F2), which is a chlorine-containing compound, 1-chloro-1,2,2,2, tetrafluoroethane (CHC1FCF3). ). [Example 1] Fig. 1 shows a flowchart of the perfluorocarbon production method of the present invention. A mixture of the above trifluoromethane as hydrofluorocarbon (symbol I2 in the figure) and a mixture of a fluorine gas (symbol 11 in the figure) and a diluent gas (symbol 19 in the figure) (symbol in the figure) 13) Introduction into the first reaction zone (symbol 1 in the figure). In the first reaction zone, the reaction pressure is 0.15 MPa, the reaction temperature is 400 ° C, the molar ratio of F2 / trifluoromethane is 1.51, and the inlet of trifluoromethane is -16- This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm) ---------------------- ^ ----- (Please read the precautions on the back before filling this page ) Hua-509666 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 • -------- B7___ 5. Description of the Invention (G) The reaction was performed at a concentration of 2.1 mol%, and the first response was obtained. Zone outlet gas (symbol 14 in the figure). This outlet gas is mixed with 1,1,1,2-tetrafluoroethane and fluorine gas (symbol ls in the figure) as neohydrofluorocarbon (symbol 16 in the figure). The obtained mixed gas is introduced into a second reaction zone (symbol 2 in the figure). In the second reaction zone, the reaction pressure is 0el5] Vlpa, and the reaction temperature is 37 (TC, F2 / l, 1, 1, 2-tetrafluoroethane with a molar ratio of 2.06, 1, 1, 1, 2- Tetrafluoroethane reacts at an inlet concentration of 1.35 mole% to obtain an outlet gas from the second reaction zone (symbol 18 in the figure). This outlet gas is separated into a diluent gas (symbol 19 in the figure) And a gas to be introduced into the distillation purification step (symbol 20 in the figure). The results are shown in Table i. The numbers in the upper section of Table 1 correspond to the symbols in Figure 1. [Example 2] Same as Example 1 The manufacturing method flow is to mix the above-mentioned pentafluoroethane as a hydrofluorocarbon (symbol 12 in the figure) with a fluorine gas (symbol u in the figure) and a diluent gas (symbol 19 in the figure), and mix the obtained mixture The gas (symbol 13 in the figure) is introduced into the first reaction zone (symbol 1 in the figure). In the first reaction zone, the reaction pressure is 0.1 SMPa and the reaction temperature is 370 ° C. The molar ratio is 1.47, and the inlet concentration of pentafluoroethane is 3.2 mole%. The outlet gas of the first reaction zone is obtained (symbol 1 in the figure). 4). The outlet gas and difluoro-17 as new hydrofluorocarbon (symbol 16 in the figure)-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------ ------- 1 --- 1 *! Order ------ 丨 (Please read the notes on the back before filling out this page) A7 ^ ~ ----- —_B7__ 5. Description of the invention (丨 G) Methane and fluorine gas (symbol 15 in the figure) are mixed, and the obtained mixed gas (symbol I7 in the figure) is introduced into the second reaction zone (symbol 2 in the figure). In the first reaction zone, The reaction was performed under the conditions of a reaction pressure of 0.15 MPa, a reaction temperature of 3S0C 'F " a molar ratio of difluoromethane of 2.0, and an inlet concentration of difluoromethane of 2.05 mole% to obtain a second reaction zone. The outlet gas (symbol 18 in the figure). This outlet gas is separated into a diluent gas (symbol 19 in the figure) and a gas to be introduced into the distillation purification step (symbol 20 in the figure). The results are shown in Table 2. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs • 18- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 509666 A7B7 Explanatory Note D > β Φ HF? 134a- KFC_K HF EF225 F? 116 F? 14 > Printed by Hyan ’s Intellectual Property Office Employee Consumer Cooperatives hr a) < il > m-* ^ HFC'34aMr 1,1,2-13 »(N 钸 * HFC 丨 23l®lll» -ffl1r-HFC 丨 125M £ »(Na. 1.013 polo LQ03 11 0 · 666 31koo9 3L489 PS2 P462 32k5 32 · 365 29b2 2.733 0.OQ1 0.665 1.2 · 1.03 0.02 068 17.288 0 · 0〇〇0 4.983 S5 0.031 0.047 1033 P015 5 · 002 7.916 0 · 031 P367 14 0 · 00? 0k5 15 0 · 038 7.916 5.S2 015 17b3
Qk7 0.462 P462 P952 0· 0300 7· 964 5.440Qk7 0.462 P462 P952 0 0 300 7.964 5.440
Gb3 18.873 003 0,004 0.010Gb3 18.873 003 0,004 0.010
P02Q 7U95 4.9003 P030 oboo P669 P457 P003 17· 20000rc-noocn o.os 0.02 009 0· 001 16 17 --—---------------'--訂 —-------- (請先閱讀背面之注意事項再填寫本頁) 18 19 2 0 -19- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 509666 A7B7 五、發明說明（丨8 )表2 •id 〇P02Q 7U95 4.9003 P030 oboo P669 P457 P003 17 · 20000rc-noocn o.os 0.02 009 0 · 001 16 17 ---------------------'-- Order ------ ---- (Please read the notes on the back before filling this page) 18 19 2 0 -19- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 509666 A7B7 V. Description of the invention (丨 8) Table 2 • id 〇
滴-4 11 φ 費热 -ffl φ 游ΜUS ο |il m -β ° 嫌 經濟部智慧財產局員工消費合作社印製 Ιυδ wSI (N 講 0 1 rr 〇> 1 其他 FC-14 F〇-ns HFC-23 HFC-32 HFC-125 "TJ K> a Φ 1.519 1.505 1 0.014 h-1 l·-1 1.000 <z> CD Ο C<3 0,9980 h-A to 32· 174 0. 036 7.295 4.983 0.030 17.288 CD CO OO 1.514 CO 32.174 ! 0.036 1 1 7.310 5.966 0.015 18.286 0.045 0.516 H^· 办 0.885 0.007 0. 878 丨 cn 0.693 I 0.693 CD 33.752 0. 043 7.310 5.966 1 0.015 1 18.286 0.693 0.045 1.394 1 33.752 0.043 ! 7.985 5.977' 0.033 19.665 0. 034 i 0.015 ' 00 29.655 1 0.020 7. 295 4.983 0.030 17.288 0.030 0.009 CD 4.097 C3 CD . to 0.690 0.994 0.003 2.377 0-004 0.006 ro o -20- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------ ----l·---------—^_^— (請先閱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 509666 A7 _ B7_ 五、發明說明（Η ) [發明之功效] 本發明提供一種工業上安全地以及經濟上有效率之全 氟化碳的製造方法。 [圖式之簡單說明1 第1 圖係 本發明實 施 例 之 流 程 面 〇 [符號說明] 1 第 一反應區 2 第 一反應區 3 蒸 館純化步 驟 11 供 應於第一 反 應 之 氟 氣 體 12 供 應於第一 反 應 區 之 氫 氟 化 碳 13 供 應於第一 反 應 區 之 氣 體 成 分 14 第 一反應區 出 □ 氣 體 成 分 15 供 應於第二 反 應 區 之 氟 氣 體 16 供 應於第二 反 應 區 之 氫 氟 化 碳 17 供 應於第二 反 應 之 氣 體 成 分 18 第 二反應區 出 □ 氣 體 成 分 19 稀 釋性氣體 20 導 入於蒸餾 純 化 步 驟 之 氣 體 -21- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------1----------,--tT---1----- (請先♦閱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 A7 B7 五、發明說明（2〇 ) [補充的實例] t氟丙烷（起始原料） 使用由六氟丙烷（cf3cf = cf2)與氟化氫之反應所獲得 七氟丙烷（CF3CHFCF3)。其之純度爲 99.98 %以上，含 有當作不純物的 1，1，1，2-四氟乙烷（CF3CH2F)、五氟乙 烷（CF3CHF2)以及當作含氯化合物的氯五氟乙院 (CF3CC1F2)、1-氯-1，2,2,2-四氟乙烷（CHC1FCF3)。 ZL氟丙烷之製造例 , 以相同於實例1之製法流程，使作爲氫氟化碳（圖中 符號12)的上述三氟甲烷與氟氣體（圖中符號11)和 稀釋性氣體（圖中符號19)進行混合，及將所獲得的混 合氣（圖中符號13)導入於第一反應區（圖中符號1) 內。在第一反應區中，於反應壓力爲1.5MPa，反應溫 度爲40 0°C，F2/三氟甲烷之莫耳比爲1.51，三氟乙烷之 入口濃度爲2.1莫耳％的條件下反應，而獲得第一反應 區的出口氣體（圖中符號14)。 該出口氣體與作爲新氫氟化碳（圖中符號16)的上述 七氟丙烷和氟氣體（圖中符號15)進行混合，將所獲得 的混合氣（圖中符號I7)導入於第二反應區（圖中符號 2)內。在第二反應區中，於反應壓力爲1.5MPa，反應 溫度爲400°C，F2/七氟丙烷之莫耳比爲le03，七氟丙院 之入口濃度爲2·0莫耳％的條件下反應，而獲得第二反 應區的出口氣體（圖中符號18)。將此出口氣體分離成 一稀釋性氣體（圖中符號19)及一將導入於蒸餾純化步 驟內之氣體（圖中符號20)。結果示於表3中。 -2 2 _ 表紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） ------------,—訂--------- (請¾.閱讀背ώ之注咅？事項再填寫本頁) 509666 A7 __B7 五、發明說明（W) 表3 成分 11 12 13 14 15 F2 1. 003 1. 006 0. 364 0. 320 HFC — 227 0. 024 0. 001 HFC-23 0. 665 0. 666 0. 047 HF 17. 325 17. 967 FC-218 6. 274 6. 297 FC-14 6. 340 6. 959 其他 0. 010 0. 001 0. 032 0. 032 0. 004 合計 1. 013 0. 666 31. 667 31. 667 0. 324 表3之續 成分 16 17 18 19 20 F2 0. 684 0. 003 0. 002 0. 001 HFC-227 0. 660 0. 661 0. 026 0. 024 0. 002 HFC-23 0. 047 0. 001 0. 001 HF 17. 967 18. 748 17. 325 1. 423 FC-218 6. 297 6. 832 6. 274 0. 558 FC— 1 4 6. 959 7. 005 6. 340 0. 665 其他 0. 036 0. 036 0. 022 0. 014 合計 0. 660 32. 651 32. 651 29. 988 2. 663 -----------裝------r--訂---------- (請先閱讀背•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 表中各成分之單位爲Kmol/hr。又，表中之HFC-：227 爲七氟丙烷，HFC-23爲三氟甲烷，FC-218爲八氟丙烷， FC-14爲四氟甲烷。 -23- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Drop-4 11 φ Ferre-ffl φ You MUS ο | il m -β ° Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Ιυδ wSI (N speak 0 0 rr 〇 > 1 other FC-14 F〇-ns HFC-23 HFC-32 HFC-125 " TJ K > a Φ 1.519 1.505 1 0.014 h-1 l-1 1.000 < z > CD Ο C < 3 0,9980 hA to 32 · 174 0. 036 7.295 4.983 0.030 17.288 CD CO OO 1.514 CO 32.174! 0.036 1 1 7.310 5.966 0.015 18.286 0.045 0.516 H ^ · Office 0.885 0.007 0. 878 丨 cn 0.693 I 0.693 CD 33.752 0. 043 7.310 5.966 1 0.015 1 18.286 0.693 0.045 1.394 1 33.752 0.043! 7.985 5.977 '0.033 19.665 0. 034 i 0.015' 00 29.655 1 0.020 7. 295 4.983 0.030 17.288 0.030 0.009 CD 4.097 C3 CD. To 0.690 0.994 0.003 2.377 0-004 0.006 ro o -20- This paper size applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) ------ ---- l · ---------— ^ _ ^ — (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 509666 A7 _ B7_ V. Description of the invention (Η) [Effect of the invention] The present invention Provide a method for manufacturing industrially safe and economically efficient perfluorocarbon. [Simplified description of the diagram 1 The first diagram is a flow chart of the embodiment of the present invention 0 [Description of symbols] 1 First reaction zone 2 A reaction zone 3 Purification step of the steaming hall 11 Fluorine gas supplied to the first reaction 12 Hydrocarbon fluoride supplied to the first reaction zone 13 Gas component supplied to the first reaction zone 14 Out of the first reaction zone □ Gas component 15 supplied Fluorine gas in the second reaction zone 16 Hydrofluorocarbon supplied to the second reaction zone 17 Gas component supplied to the second reaction 18 Out of the second reaction zone □ Gas component 19 Diluent gas 20 Gas introduced into the distillation purification step -21- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------- 1 ----------, --tT --- 1-- --- (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention (2〇) [Supplementary Examples] t-fluoro-propane (starting material) by the use of the reaction hexafluoropropane (cf3cf = cf2) with hydrogen of the obtained heptafluoropropane (CF3CHFCF3). Its purity is above 99.98%, and it contains 1,1,1,2-tetrafluoroethane (CF3CH2F), pentafluoroethane (CF3CHF2) as impurities, and chloropentafluoroethane (CF3CC1F2) as chlorine-containing compounds. ), 1-chloro-1,2,2,2-tetrafluoroethane (CHC1FCF3). In the production example of ZL fluoropropane, the same procedure as in Example 1 is used to make the above trifluoromethane, a fluorine gas (reference number 11 in the figure), and a diluent gas (reference number in the figure) as hydrofluorocarbons (reference numeral 12 in the figure). 19) Mixing, and introducing the obtained mixed gas (symbol 13 in the figure) into the first reaction zone (symbol 1 in the figure). In the first reaction zone, the reaction was performed under the conditions of a reaction pressure of 1.5 MPa, a reaction temperature of 40 ° C, a molar ratio of F2 / trifluoromethane of 1.51, and an inlet concentration of trifluoroethane of 2.1 mol%. , And the outlet gas of the first reaction zone is obtained (symbol 14 in the figure). This outlet gas is mixed with the above-mentioned heptafluoropropane and fluorine gas (reference numeral 15 in the figure) as the new hydrofluorocarbon (reference numeral 16 in the figure), and the obtained mixed gas (reference numeral I7 in the figure) is introduced into the second reaction zone ( Symbol 2) in the figure. In the second reaction zone, the reaction is performed under the conditions of a reaction pressure of 1.5 MPa, a reaction temperature of 400 ° C, a molar ratio of F2 / heptafluoropropane to le03, and an inlet concentration of heptafluoropropane hospital at 2.0 mole%. The outlet gas of the second reaction zone is obtained (symbol 18 in the figure). This outlet gas is separated into a diluent gas (symbol 19 in the figure) and a gas to be introduced into the distillation purification step (symbol 20 in the figure). The results are shown in Table 3. -2 2 _ The paper size of the table is applicable to China National Standard (CNS) A4 (21〇X 297 mm) ------------,-Order --------- (Please ¾. Read the note on the back page? Matters need to fill in this page) 509666 A7 __B7 V. Description of the invention (W) Table 3 Ingredients 11 12 13 14 15 F2 1. 003 1. 006 0. 364 0. 320 HFC — 227 0 . 024 0. 001 HFC-23 0. 665 0. 666 0. 047 HF 17. 325 17. 967 FC-218 6. 274 6. 297 FC-14 6. 340 6. 959 Others 0. 010 0. 001 0 032 0. 032 0. 004 Total 1. 013 0. 666 31. 667 31. 667 0. 324 Continuation of Table 3 16 17 18 19 20 F2 0. 684 0. 003 0. 002 0. 001 HFC-227 0. 660 0. 661 0. 026 0. 024 0. 002 HFC-23 0. 047 0. 001 0. 001 HF 17. 967 18. 748 17. 325 1. 423 FC-218 6. 297 6. 832 6 274 0. 558 FC— 1 4 6. 959 7. 005 6. 340 0. 665 Other 0. 036 0. 036 0. 022 0. 014 Total 0. 660 32. 651 32. 651 29. 988 2. 663 ----------- Install ------ r--Order ---------- (Please read the notes on the back and front before filling this page) Wisdom of the Ministry of Economic Affairs The unit of each component in the printed table of the employee's consumer cooperative of the property bureau is Kmol / h r. In the table, HFC-: 227 is heptafluoropropane, HFC-23 is trifluoromethane, FC-218 is octafluoropropane, and FC-14 is tetrafluoromethane. -23- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)