TWI243809B - Process for purifying octafluorocyclobutane, process for preparing the same, and use thereof - Google Patents

Abstract

A process for purifying octafluorocyclobutane according to the present invention is characterized by contacting a crude octafluorocyclobutane containing impurities with an impurity decomposing agent under elevated temperature and then with an adsorbent to substantially remove the impurities from the crude octafluorocyclobutane. According to the purification process or preparation process of octafluorocyclobutane of the present invention, the impurities such as fluorocarbon can be substantially removed and a high-purity octafluorocyclobutane can be easily obtained. The octafluorocyclobutane obtained by the purification process of the present invention is substantially free of impurities and therefore, can be used as an etching or cleaning gas for use in the production process of a semiconductor device or the like.

Description

經濟部智慧財產局8工消費合作社印製 1243809 A7 _ B7___ 五、發明説明（1) 發明之技術領域 本發明係有關八氟化環丁烷之精製方法，製造方法及 高純度八氟化環丁烷，以及其用途。 目前技術 目前，半導體裝置製造過程中，於構成半導體回路之 各種薄膜材料上形成回路圖型的方法之一爲，去除部分薄 膜材料之氣體蝕刻法。又，爲了去除薄膜形成過程中，附 著於反應容器內等之薄膜原料，而利用淸潔氣體等去除附 著物。目前適用於半導體裝置製造過程的鈾刻氣體或淸潔 氣體之一爲八氟化環丁烷（以下稱爲「F C - C 3 1 8」 )° 又，近年來隨著電器或電子機器的高性能化，小型化 ，高密度配線化等，而使回路基板之電極傾向微細化，爲 了使利用鈾刻等方法形成更高精準度之回路圖型，因此需 求能極力去除不純物之高純度蝕刻氣體。其因爲，蝕刻氣 體既使含微量之不純物，仍會成爲微細圖型產生寬幅線， 或增加具有高密度集成回路之製品缺陷的要因。 又，爲了使利用淸潔氣體去除附著物之過程能提供高 純度及品質之裝置，而需盡可能減小淸潔後半導體裝置製 造過程中殘留之不純物，因此需求實質不含不純物之高純 度淸潔氣體。 上述F C - C 3 1 8之製造方法如，將製造四氟化乙 烯（以下稱爲「FC - 1 1 1 4」或六氟化丙烯（以下稱 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐） ---------装------、訂------^ (請先閲讀背面之注意事項再填寫本頁) -4- 1243809 經濟部智慧財產局資工消费合作社印製 A7 _B7五、發明説明（i 爲「FC — 1216」）時所得之副產物FC — C318 精製而得。 但，如E P 4 5 1 7 9 3號公報所記載，將F C -1 1 1 4或FC - 1 2 1 6熱分解時，熱分解反應所生成 之物質種類多，且含多量未反應之HC F C - 2 2及含氯 化合物。 將厂（：一〇3 18及^^€?(：-2 2熱分解時所生成 之不純物中，所含化合物之沸點如表1所示。其中，幾乎 可利用蒸餾法將FC-1114或FC—1216之目的 生成物及未反應之HC F C - 2 2分離。 但，氯氟化碳，特別是2 —氯一 1，1，2，3，3 ，3 -七氟化丙烷（以下稱爲「CFC — 217ba」） ，1 一氯—1，1，2，2，3，3，3 —七氟化丙烷（ 以下稱爲「CFC — 217ca」），2 —氯一 1，1， 1，2 —四氟化乙烷（以下稱爲「HCFC— 124」） ，1 一氯—1，1，2 ’ 2 —四氟化乙烷（以下稱爲「 HCFC— 124a」），1，2 —二氯四氟化乙烷（以 下稱爲「CFC — 114」），FC— 1216 及 1H — 七氟化丙烷（以下稱爲「HFC — 227ca」）與FC - C 3 1 8之沸點相近，因此很難以蒸餾分離法使f c -C3 1 8之不純物濃度爲1質量ppm以下。 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 1243809Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative 1243809 A7 _ B7___ V. Description of the Invention (1) Technical Field of the Invention The present invention relates to a purification method, a manufacturing method and a high-purity cyclobutyl octafluoride octafluoride. Alkane, and its uses. Current technology Currently, one of the methods for forming a circuit pattern on various thin film materials constituting a semiconductor circuit in the manufacturing process of a semiconductor device is a gas etching method that removes a part of the thin film material. In addition, in order to remove the thin film raw materials attached to the reaction vessel and the like during the film formation process, a cleaning gas or the like is used to remove the adherends. One of the uranium-engraved gases or plutonium gases currently suitable for the manufacturing process of semiconductor devices is cyclobutane octafluoride (hereinafter referred to as "FC-C 3 1 8"). In addition, in recent years, with the rise of electrical and electronic equipment, Performance, miniaturization, high-density wiring, etc., tend to miniaturize the electrodes of circuit substrates. In order to form circuit patterns with higher accuracy by uranium etching and other methods, high-purity etching gas that can remove impurities is required. . The reason is that, even if the etching gas contains a trace amount of impurities, it will still be the main reason for the fine pattern to generate wide lines or increase the defects of products with high-density integrated circuits. In addition, in order to provide a high-purity and high-quality device in the process of removing adherents by using cleaning gas, it is necessary to minimize impurities remaining in the manufacturing process of semiconductor devices after cleaning. Therefore, high purity that does not substantially include impurities is required. Clean gas. The manufacturing method of the above-mentioned FC-C 3 1 8 is, for example, the production of ethylene tetrafluoride (hereinafter referred to as "FC-1 1 1 4" or hexafluorinated propylene (hereinafter referred to as the paper standard applies to China National Standard (CNS) A4) (210 × 297 mm) --------- install ------, order ------ ^ (Please read the precautions on the back before filling in this page) -4- 1243809 Ministry of Economy Wisdom Printed by A7 _B7 of the Industrial and Commercial Assets Cooperatives V. Refined by-product FC-C318 obtained when the invention description (i is "FC-1216"). However, as described in EP 4 5 1 7 9 3, When FC-1 1 1 4 or FC-1 2 1 6 is thermally decomposed, there are many kinds of substances generated by the thermal decomposition reaction, and they contain a large amount of unreacted HC FC-2 2 and chlorine-containing compounds. 3 18 and ^^ €? (: -2 2 The boiling points of the compounds contained in the impurities generated during thermal decomposition are shown in Table 1. Among them, the distillation method can be used to produce FC-1114 or FC-1216 for the purpose. And unreacted HC FC-2 2. However, chlorofluorocarbons, especially 2-chloro-1,1,2,3,3,3-propane heptafluoride (hereinafter referred to as "CFC-217ba" ) 1 monochloro-1,1,2,2,3,3,3-propane heptafluoride (hereinafter referred to as "CFC-217ca"), 2-chloro-1,1,1,2,2-ethane tetrafluoride (Hereinafter referred to as "HCFC-124"), 1-chloro-1,1,2,2'2-tetrafluoroethane (hereinafter referred to as "HCFC-124a"), 1,2-dichlorotetrafluoroethane (Hereinafter referred to as "CFC-114"), FC-1216 and 1H-propane heptafluoride (hereinafter referred to as "HFC-227ca") have similar boiling points as FC-C 3 1 8 and it is difficult to make fc by distillation. -C3 1 8 The impurity concentration is 1 mass ppm or less. (Please read the precautions on the back before filling in this page.) Binding and binding The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 1243809

7 B 五、發明説明（i 經濟部智惡財產局員工消費合作社印^ 表1 化合物名 構造式 沸點（t ) 八氟化環丁烷（FC -C 3 1 8 ) C-CF2CF2CF2CF2 -6 氯二氟化甲烷（HCFC — 2 2) CHC1F2 -41 六氟化丙烯（FC -12 16) CF3CF = CF2 -31 2 -氯—1，1，1，2， 3，3，3 -七氟化丙烷（ CFC-217ba) CF3CCIFCF3 -2 1-氯-1，1，，2，2 ，3，3，3 -七氟化丙烷 (CFC-217ca) CCIF2CF2F3 -2--1 2 —氯-1，1，1，2 — 四氟化乙烷（HCFC — 12 4) CFsCHClF -12 1 一氯-1，1，2，2-四氟化乙烷（HCFC — 12 4a) CCIF2CHF2 -10.2 1H -七氟化丙烷（HFC -2 2 7 c a ) CHF2CF2CF3 -19 1 ，2 —二氯四氟化乙烷（ C F C - 1 1 4 ) CCIF2CCIF2 -3.8 (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（210X297公釐） 碎 -6- -柒·7 B V. Description of the invention (i Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs ^ Table 1 Compound name Structural formula Boiling point (t) Cyclofluorobutane (FC -C 3 1 8) C-CF2CF2CF2CF2 -6 Chlorine Methane fluoride (HCFC — 2 2) CHC1F2 -41 Propylene hexafluoride (FC -12 16) CF3CF = CF2 -31 2 -Chloro-1,1,1,2,3,3,3 -propane heptafluoride ( CFC-217ba) CF3CCIFCF3 -2 1-chloro-1,1,1,2,2,3,3,3 -propane heptafluoride (CFC-217ca) CCIF2CF2F3 -2--1 2 -chloro-1,1,1 ， 2 — ethane tetrafluoride (HCFC — 12 4) CFsCHClF -12 1 monochloro-1,1,2,2-tetrafluoroethane (HCFC — 12 4a) CCIF2CHF2 -10.2 1H-propane hexafluoride ( HFC -2 2 7 ca) CHF2CF2CF3 -19 1 ， 2-Dichlorotetrafluoroethane (CFC-1 1 4) CCIF2CCIF2 -3.8 (Please read the precautions on the back before filling this page) This paper size is applicable to China Standard (CNS) A4 size (210X297 mm) broken -6--柒 ·

L 1243809 A7 B7 五、發明説明（4 因此出現蒸餾分離以外之精製方法，例如萃取蒸餾法 ’膜分離法，吸附分離法等。 但，萃取蒸餾法含有設備成本高，過程複雜等問題， 膜分離法會因尙無適當且實用之具有分離F C - C 3 1 8 及不純物時所需特性的膜，而難精製以使例如F C -C 3 1 8中不純物含量爲1質量p pm以下之高純度。又 ’如表2所示般F C - C 3 1 8與不純物化合物之分子徑 (安定型構造時之計算値）幾乎無差別，且如上述般F C 一 C 3 1 8與不純物化合物之沸點差較小及，F C -C 3 1 8與不純物之構造，物性類似，因此，利用既存之 吸附劑，例如活性碳，矽膠，沸石（分子篩），分子篩分 離碳（以下稱爲「MS C」）等之吸附分離法，將難分離 F C - C 3 1 8及不純物化合物而得高純度F C -C 3 1 8 〇 I 裝 訂線 (請先閲讀背面之注意事項再填寫本頁) 絰濟郎智慧財產局S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（210X 297公釐） 1243809 A7 B7 五、發明説明（9 經濟部智慧財產局員工消費合作社印災 表2 化合物名 __ 分子徑（計算値） 八氟化環丁烷（FC - C318) 5 · 2 - 5 . 8 A 2 -氯-1，1，1，2，3，3 ，3 —b氟化丙院（CFC — 2 1 7 b a ) 4 . 0 〜6 · 2 A 1-氯-1，1，2，2，3，3 ，3 —七氟化丙烷（CFC — 2 1 7 c a ) 3 · 9 〜6 · 1 A 2 —氯—1，1，1，2 —四氟化 乙烷（HCFC — 124) 4 . 3 〜5 · 6 A 1—氯一 1，1，2，2 —四氟化 乙烷（HCFC - 124a) 4 · 3 〜5 · 6 A 1，2 —二氯四氟乙烷（CFC — 114) 4 . 8 〜5 · 6 A 六氟化丙烯（FC— 1216) 4 . 9 〜5 · 9 A 1H —七氟化丙烷（HFC -2 2 7 c a ) 4 . 3 〜6 · 2 A 其中，活性碳能有效吸附去除不純物之- F c 一 1 2 1 6，但難分離含氯化合物之其他全部的不純物。 因此，以目前之精製方法很難得到氟化碳所形成之不 純物，特別是CFC - 2 1 76 a濃度爲1質量p pm以 下的 FC — C318。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I 裝 訂 線 (請先閲讀背面之注意事項再填寫本頁) -8- l2438〇9 經濟部智慧財產局工消费合作社印裝 A7 B7 五、發明説明（Θ 0 0至9 0 0°C而對原料碳進行賦活化處理之步驟（ φ _ 4 )所構成之方法而得的賦活碳爲佳。 原料碳較佳爲，將椰子殼碳，石碳，木碳及焦瀝青中 選出至少1種加熱至4 0 0至6 0 0°C而進行碳化處理所 得之物。 酸爲無機酸，且酸濃度較佳爲1至1 0 0 0莫耳/m 〇 該酸又以鹽酸及/或硫酸爲佳。 又，實施步驟2後移行到步驟3時較佳爲，不活性氣 流下，以3 0 0至5 0 0。(： / h r速度將經步驟2之原料 碳升溫至700至900 °C。 上述混合氣體中，對全部混合氣體之體積又以不活性 氣體5 0至89體積％，二氧化碳1 0至30體積％，以 蒸氣1至2 0體積％爲佳。 結束步驟4後較佳爲，不活性氣流下，以2 0 0至 3 0 〇 °C / h r之速度將經步驟4之賦活碳降溫至常溫。 該賦活碳之碘吸附量較佳爲7 0 0至1 0 0 Omg/ g 〇 又，賦活碳所含鹼金屬之總含量較佳爲1 0 0 〇 p p m以下。 鹼金屬爲鉀時，賦活碳所含總含量較佳爲5 0 0 pm 以下。 粗八氟化環丁烷又以不純物含量爲1 〇至 10，000質量ppm爲佳。 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） 裝 訂 線 (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费合作社印製 1243809 A7 B7 五、發明説明（9 該不純物較佳爲，2 —氯—1，1，1，2，3，3 ，3 —七氟化丙烷，1 一氯—1，1，2，2，3，3, 3，一七氟化丙烷，1—氯—1，2，2，2 —四氟化乙 烷，1—氯—1 ，1，2，2 —四氟化乙烷，1 ，2 -二 氯—1，1，2，2 —四氟化乙烷，六氟化丙烯及1H — 七氟化丙烷中所選出至少一種之氟化碳。 實質去除不純物後，八氟化環丁烷中殘留之不純物濃 度較佳爲低於1質量P pm。 本發明之八氟化環丁烷製造方法的特徵爲，製造含不 純物之粗八氟化環丁烷後，加熱下將粗八氟化環丁烷接觸 不純物分解劑，再接觸吸附劑，而得實質去除不純物之八 氟化環丁烷。 該含不純物之粗八氟化環丁烷的製造步驟可爲，將氯 二氟化甲烷熱分解。又，不純物可爲2-氯一1， 1 ， 1 ，2，3，3，3_七氟化丙烷，1 一氯—1，1，2, 2，3，3，3 —七氟化丙烷，1—氯—1，2，2，2 —四氟化乙烷，1—氯—1，1，2，2 —四氟化乙烷， 1，2 —二氯—1，1，2，2 —四氟化乙烷，六氟化丙 烯及1 Η -七氟化丙烷中所選出至少一種之氟化碳。 本發明之八氟化環丁烷的特徵爲，氟化碳所形成之不 純物含量低於0.0001質量％，且純度爲 99 · 9999質量％以上。 該氟化碳可爲2 -氯-1，1，1，2，3，3，3 —七戴化丙院，1—氯—1，1，2，2’3’3，3 — 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 辦衣1Τ^ (請先閲讀背面之注意事項再填寫本頁) -12- 瞍齊郎智慧財產局員工消費合作社印製 1243809 A7 B7 五、發明説明（如 七氟化丙烷，1 一氯—1，2，2，2 -四氟化乙烷，1 —氯—1 ，1，2，2 —四氟化乙烷，1，2 -二氯—1 ，1，2 ’ 2 -四氟化乙烷，六氟化丙烯及1H —七氟化 丙烷中所選出至少1種之氟化碳。 本發明之氣體的特徵爲，含有上述八氟化環丁烷。 本發明之蝕刻氣體的特徵爲，由上述氣體形成。 本發明之淸潔氣體的特徵爲，由上述氣體形成。 發明具體說明 〔八氟化環丁烷之精製方法〕 本發明之八氟化環丁烷精製方法爲，加熱下將含不純 物之粗八氟化環丁烷接觸不純物分解劑後，再接觸吸附劑 ，而由粗八氟化環丁烷中實質去除不純物之方法。下面將 先詳細說明該精製方法。又，本說明書中，粗八氟化環丁 烷係指未經本發明精製步驟之含不純物的八氟化環丁烷。 實質去除係指完全不含或幾乎不含不純物。 不純物分解劑 本發明又以使用氧化鐵及鹼土類金屬化合物所形成之 不純物分解劑爲佳。 該氧化鐵如，氧化亞鐵，三氧化二鐵等，其中又以三 氧化二鐵爲佳。三氧化二鐵中又以r — Fe〇〇H (r-氫氧化氧化鐵），r — Fe2〇3 (r —三氧化二鐵）爲佳 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------批衣------、玎------線、 (請先閲讀背面之注意事項再填寫本頁) -13- 經濟部智慧財產局員工消費合作社印製 1243809 A7 B7 五、發明説明（1)1 ，更佳爲r — Fe〇〇H。 該氧化鐵可單獨使用或複數倂用。 推測7* — F e〇〇H或t — F e2〇3比7 — F e2〇3 適用係與氧化鐵活性有關。r 一 FeOOH或r 一 F e 2 0 3之反應性較高，且對氯化合物之活性依序爲，r —F e〇〇H〉7 — F e2〇3〉7* — F〇〇H>F e2〇3 > > r 一 F e 2〇3。又，推測該對氯化合物之活性差異係 因，r — F e〇OH或r_F e2〇3中鐵原子與氧原子之 鍵結能比r 一 F e〇〇Η等小。 本發明所使用之鹼土類金屬化合物較佳爲，鹼土類金 屬之氫氧化物，氧化物或碳酸鹽。該鹼土類金屬如，鎂， 鈣，緦或鋇。 該鹼土類金屬化合物中又以鈣之氫氧化物或氧化物爲 佳，更佳爲氫氧化鈣。又，該鹼土類金屬化合物可單獨使 用或複數倂用。 本發明所使用之不純物分解劑中，對不純物分解劑之 全質量又以氧化鐵含量5至5 0質量％，鹼土類金屬化合 物含量6 0至9 5質量％爲佳，更佳爲氧化鐵2 0至3 0 質量％，鹼土類金屬化合物7 0至8 0質量％。 不純物分解劑中氧化鐵及鹼土類金屬化合物含量爲上 述範圍時，如後述般，推測可有效進行不純物分解及，去 除不純物分解所生成之分解生成物，且極限活用氧化鐵及 鹼土類金屬化合物特性而有效率進行精製。 構成不純物分解劑之氧化鐵及鹼土類金屬化合物的形 本紙張尺度適用中國國家標準（CNS) Α4規格（210Χ297公釐） 辦衣 訂 I線 (請先閲讀背面之注意事項再填寫本頁) -14- 經濟部智慧財產局員工消費合作社印髮 1243809 A7 ___B7_ 五、發明説明（也 狀並無限定，但以粒子狀爲佳。又，氧化鐵及鹼土類金屬 形狀爲粒子狀時，添加前，即未形成不純物分解劑之前的 平均粒徑較佳爲1 〇 〇 /zm以下，更佳爲1 0 /zm以下， 特佳爲1/zm以下，其下限値較佳爲〇 · 〇1至1〇〇 //m，更佳爲〇 . 〇1至lo^zm，特佳爲〇 . 〇1至1 β m 〇 氧化鐵及鹼土類金屬化合物粒子之平均粒徑爲1 0 0 /zm以下時，可得純度更高之八氟化環丁烷及有效率進行 精製。推測其因爲，當不純物分解劑接觸不純物時，氧化 鐵及鹼土類金屬化合物爲微粉狀，因此可增加比表面積及 易使氧化鐵，鹼土類金屬化合物相互分散，故可增加含不 純物之粗八氟化環丁烷與氧化鐵及鹼土類金屬之接觸面積 及機會。 不影響粗八氟化環丁烷中不純物之分解能力下，氧化 鐵及鹼土類金屬化合物中不純物濃度及種類並無特別限制 〇 該不純物分解劑之形狀並無限定，可爲適用於精製之 任何形狀，但以粒子狀粒劑爲佳。該粒劑之具體形狀如， 顆粒徑，球狀等。又，粒劑之平均粒徑較佳爲0 . 5至 1 Omm，更佳爲1至5mm。 平均粒徑爲上述範圍時，可增加粗八氟化環丁烷所含 氟化碳等不純物與不純物分解劑之接觸機會，而有效率進 行不純物分解及去除。不純物分解劑之平均粒徑大於1 0 m m時，相對地會減少有關氣體吸附擴散之表面積，而減 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X297公釐1 ---------^------、訂------0 (請先閲讀背面之注意事項再填寫本頁) -15- 經濟部智慧財產局員工消费合作TI印奴 1243809 A7 B7 五、發明説明（h 緩擴散速度，又，平均粒徑小於0 · 5 m m時，相對地會 增加有關吸附擴散之表面積，而加速擴散速度，但會增力α 處理氣體量而擴大差壓。 由氧化鐵及鹼土類金屬化合物製造不純物分解劑之方 法並無限定，可爲添加氧化鐵及鹼土類金屬化合物粉末後 混合。依上述添加比率製造粒劑時，加水後可充分造粒。 又，氧化鐵或鹼土類金屬化合物之粒徑較粗時，可添加水 及粘合劑造粒。不影響所得不純物分解劑之性能下，粘合 劑種類及使用量並無限定，可爲無機系粘合劑，例如粘土 ’石膏等，或有機系粘合劑，例如甲基纖維素，聚乙烯醇 ，澱粉等已知之物。 粒狀不純物分解劑之粒劑的製法可爲，混合氧化鐵及 鹼土類金屬化合物後加入適量的水混煉，再將混煉物造粒 而得。L 1243809 A7 B7 V. Explanation of the invention (4 Therefore, purification methods other than distillation and separation, such as extractive distillation method, membrane separation method, adsorption separation method, etc. have appeared. However, the extraction distillation method contains problems such as high equipment costs, complicated processes, and membrane separation. The method is difficult to purify due to the lack of a suitable and practical membrane having the characteristics required for the separation of FC-C 3 1 8 and impurities, for example, FC-C 3 1 8 has a high purity of 1 mass p pm or less. . Also 'as shown in Table 2, there is almost no difference between the molecular diameter of FC-C 3 1 8 and the impurity compound (calculated in the stable structure), and the boiling point difference between FC-C 3 1 8 and the impurity compound is as above. Smaller, FC-C 3 1 8 has similar structure and properties to the impurities. Therefore, existing adsorbents such as activated carbon, silica gel, zeolite (molecular sieve), molecular sieve to separate carbon (hereinafter referred to as "MS C"), etc. Adsorption separation method will separate FC-C 3 1 8 and impurities from high purity FC-C 3 1 8 〇I binding line (please read the precautions on the back before filling this page) S Industry Consumption The paper size printed by the company applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1243809 A7 B7 V. Description of the invention (9 Disaster Printing Form for Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 2 Compound name __ Molecular path (calculation Ii) Cyclobutane octafluoride (FC-C318) 5 · 2-5. 8 A 2 -Chloro-1,1,1,2,3,3,3 —b Propane fluoride (CFC — 2 1 7 ba) 4. 0 to 6 · 2 A 1-chloro-1,1,2,2,3,3,3-propane heptafluoride (CFC — 2 1 7 ca) 3 · 9 to 6 · 1 A 2 — Chlorine-1,1,1,2-tetrafluoroethane (HCFC-124) 4. 3 to 5 · 6 A 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124a) 4 · 3 ~ 5 · 6 A 1,2-dichlorotetrafluoroethane (CFC — 114) 4. 8 ~ 5 · 6 A Propylene hexafluoride (FC-1216) 4. 9 ~ 5 · 9 A 1H — Propane heptafluoride (HFC -2 2 7 ca) 4. 3 ~ 6 · 2 A Among them, activated carbon can effectively adsorb and remove impurities-F c-1 2 1 6, but it is difficult to separate all other impurities containing chlorine compounds Therefore, it is difficult to obtain the impurities formed by carbon fluoride with the current refining methods. In particular CFC - 2 1 76 a mass concentration of 1 to p pm under FC - C318. This paper size applies to China National Standard (CNS) A4 (210X297 mm) I binding line (please read the precautions on the back before filling this page) -8- l2438〇9 printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives B7 V. Description of the invention The activated carbon obtained by the method constituted by the step (φ_4) of activating the raw carbon by Θ 0 0 to 900 ° C is preferred. The raw carbon is preferably coconut. Shell carbon, stone carbon, lignin, and coke pitch are selected from at least one carbonized by heating to 400 to 600 ° C. The acid is an inorganic acid, and the acid concentration is preferably 1 to 10 0 mol / m 〇 The acid is preferably hydrochloric acid and / or sulfuric acid. In addition, it is more preferable to move to step 3 after performing step 2 under the inert gas flow, from 300 to 500. (: / hr speed to raise the raw carbon through step 2 to 700 to 900 ° C. In the above mixed gas, the volume of the entire mixed gas is again 50 to 89% by volume of inert gas and 10 to 30% by volume of carbon dioxide. The steam is preferably from 1 to 20% by volume. After the end of step 4, it is more preferable to use from 200 to 300 under an inert gas stream. The rate of C / hr will be reduced to normal temperature through the activated carbon in step 4. The iodine adsorption amount of the activated carbon is preferably 700 to 100 mg / g, and the total content of alkali metals contained in the activated carbon is better. It is 100 ppm or less. When the alkali metal is potassium, the total content of activated carbon is preferably 500 pm or less. The crude cyclobutane octafluoride has an impurity content of 10 to 10,000 mass ppm. This paper size applies to Chinese National Standard (CNS) A4 (210x297 mm) gutter (please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 1243809 A7 B7 V. Invention Explanation (9 The impurity is preferably 2-chloro-1,1,1,2,3,3,3-propanefluoride, 1-chloro-1,1,2,2,3,3,3, Propane heptafluoride, 1-chloro-1,2,2,2-tetrafluoroethane, 1-chloro-1,1,2,2-tetrafluoroethane, 1,2-dichloro-1 1,2,2—tetrafluoroethane, propylene hexafluoride and 1H—propane heptafluoride selected from at least one kind of carbon fluoride. After substantially removing the impurities, residual cyclobutane octafluoride remains The impurity concentration is preferably less than 1 mass P pm. The manufacturing method of the octafluorocyclobutane of the present invention is characterized in that after the crude octafluorocyclobutane containing the impurities is produced, the crude octafluorocyclobutane is heated under heating. The alkane is contacted with an impure substance decomposing agent, and then is contacted with an adsorbent, so as to substantially remove the impure octafluorocyclobutane. The crude octafluorocyclobutane containing the impure substance may be prepared by thermally decomposing chlorodifluoromethane. The impurity may be 2-chloro-1,1,1,2,3,3,3_propane heptafluoride, 1-chloro-1,1,2,2,3,3,3-propane heptafluoride , 1-chloro-1,2,2,2-tetrafluoroethane, 1-chloro-1,1,2,2-tetrafluoroethane, 1,2-dichloro-1,1,2, 2-Fluorocarbon selected from at least one of ethane tetrafluoride, propylene hexafluoride, and 1 Η-propanefluoride. The octafluorocyclobutane of the present invention is characterized in that the content of impurities formed by the carbon fluoride is less than 0.0001% by mass, and the purity is 99.9999% by mass or more. The fluorinated carbon can be 2-chloro-1,1,1,2,3,3,3-Seven Daihua C, 1-chloro-1,1,2,2'3'3,3 — this paper Standards are applicable to China National Standard (CNS) A4 specifications (210 × 297 mm) Clothing 1T ^ (Please read the precautions on the back before filling this page) -12- Printed by Jiqilang Intellectual Property Bureau Employee Consumption Cooperative 5 2. Description of the invention (such as propane hexafluoride, 1-chloro-1,2,2,2-tetrafluoroethane, 1-chloro-1,1,2,2-tetrafluoroethane, 1,2- At least one selected from the group consisting of dichloro-1,1,2,2-tetrafluoroethane, propylene hexafluoride, and 1H-propanefluoride. The gas of the present invention is characterized by containing the above-mentioned eight The fluorinated cyclobutane. The etching gas of the present invention is characterized by being formed of the above-mentioned gas. The cleaning gas of the present invention is characterized by being formed of the above-mentioned gas. Detailed description of the invention [Method for purifying octafluorocyclobutane] The refining method of octafluorocyclobutane invented is that, under heating, the crude octafluorocyclobutane containing impurities is contacted with the impurity decomposition agent, and then the adsorbent, and the crude A method for substantially removing impurities in fluorinated cyclobutane. The purification method will be described in detail below. Also, in the present specification, crude octafluorocyclobutane refers to octafluorocyclobutane containing impurities which has not been purified in the present invention. Alkane. Substantial removal means completely or almost no impurities. Impurities decomposing agent In the present invention, impure decomposition agents formed by using iron oxide and alkaline earth metal compounds are preferred. The iron oxide such as ferrous oxide, trioxide Among them, ferric oxide is preferred. Among them, r—FeOOOH (r-iron hydroxide) and r—Fe2O3 (r—iron oxide) are preferred. Jiaben paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) --------- Approved clothing ------, 玎 ------ line, (Please read the back first Please note this page before filling in this page) -13- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 1243809 A7 B7 V. Description of the invention (1) 1, more preferably r — Fe〇〇H. The iron oxide can be used alone or It is assumed that 7 * — F e〇〇H or t — F e2〇3 is more suitable than 7 — F e2〇3. It is related to the activity of iron oxide. R-FeOOH or r-F e 2 0 3 has higher reactivity, and the activity for chlorine compounds is, in order, r —F e〇〇H> 7 — F e2〇3> 7 * — F〇〇H >> F e2〇3> > r-F e 2 03. Furthermore, it is speculated that the difference in the activity of the chlorine compound is due to the fact that the iron atom in r — F e〇OH or r_F e2 03 is The bonding energy of oxygen atoms is smaller than r-F e〇〇Η and the like. The alkaline earth metal compound used in the present invention is preferably an hydroxide, oxide or carbonate of an alkaline earth metal. The alkaline earth metal is, for example, magnesium, calcium, scandium or barium. Among the alkaline earth metal compounds, calcium hydroxide or oxide is more preferable, and calcium hydroxide is more preferable. The alkaline earth metal compound may be used alone or in combination. Among the impure decomposition agents used in the present invention, the total mass of the impure decomposition agent is preferably 5 to 50% by mass of iron oxide, 60 to 95% by mass of alkaline earth metal compounds, and more preferably iron oxide 2 0 to 30% by mass, and alkaline earth metal compounds 70 to 80% by mass. When the content of iron oxide and alkaline earth metal compounds in the impurity decomposition agent is within the above range, it is estimated that the decomposition of impurities and the decomposition products generated by the decomposition of impurities can be effectively removed as described below, and the characteristics of iron oxide and alkaline earth metal compounds can be used to the limit Refining efficiently. The size of the iron oxide and alkaline earth metal compounds that constitute the impurity decomposer are in accordance with the Chinese National Standard (CNS) A4 specification (210 × 297 mm). I line for clothes ordering (please read the precautions on the back before filling this page)- 14- Printed and issued by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1243809 A7 ___B7_ V. Description of the invention (the shape is not limited, but it is preferably in the form of particles. When the shape of iron oxide and alkaline earth metals is in the form of particles, That is, the average particle diameter before the impurity decomposition agent is not formed is preferably 100 / zm or less, more preferably 10 / zm or less, particularly preferably 1 / zm or less, and the lower limit 値 thereof is preferably 0.001 to 1. 〇〇 // m, more preferably 〇1 to lo ^ zm, particularly preferably 〇1 to 1 β m 〇 When the average particle diameter of the iron oxide and alkaline earth metal compound particles is 10 0 / zm or less The higher purity cyclobutane octane can be obtained and efficiently refined. It is speculated that when the impurity decomposition agent contacts the impurity, iron oxide and alkaline earth metal compounds are in a fine powder form, so the specific surface area can be increased and the Combining iron oxide and alkaline earth metals Disperse each other, so it can increase the contact area and opportunity of crude octafluorocyclobutane containing impurities with iron oxide and alkaline earth metals. Without affecting the decomposition ability of impurities in crude octafluorocyclobutane, iron oxide and alkaline earth The concentration and type of impurities in the metal compound are not particularly limited. The shape of the impurities is not limited, and may be any shape suitable for purification, but it is preferably a granular granule. The specific shape of the granule is, for example, particle diameter , Spherical, etc. In addition, the average particle diameter of the granules is preferably 0.5 to 10 mm, more preferably 1 to 5 mm. When the average particle diameter is in the above range, the fluorine contained in the crude cyclobutane octafluoride can be increased. Impurities such as carbonized carbon and the impurity decomposition agent will be able to contact and efficiently decompose and remove the impurity. When the average particle diameter of the impurity decomposition agent is greater than 10 mm, the surface area of gas adsorption and diffusion will be relatively reduced, and the paper size will be reduced Applicable to China National Standard (CNS) M specifications (210X297 mm 1 --------- ^ ------, order ------ 0 (Please read the precautions on the back before filling in this Page -15- Employees of Intellectual Property Bureau, Ministry of Economic Affairs Consumption cooperation TI Indus 1243809 A7 B7 V. Description of the invention (h Slow diffusion speed, and when the average particle size is less than 0.5 mm, it will relatively increase the surface area of adsorption and diffusion, and accelerate the diffusion speed, but will increase the force α The amount of gas is processed to increase the differential pressure. There is no limitation on the method for producing the impure decomposition agent from iron oxide and alkaline earth metal compounds, and it is possible to add iron oxide and alkaline earth metal compound powders and mix them. When manufacturing granules according to the above addition ratio, add water After that, it can be fully granulated. When the particle size of iron oxide or alkaline earth metal compound is relatively coarse, water and a binder can be added for granulation. Without affecting the performance of the impure decomposition agent obtained, the type and amount of the binder are not limited, and may be an inorganic binder, such as clay 'gypsum, or an organic binder, such as methyl cellulose, polyethylene Alcohol, starch and other known things. The granules of the granular impurity decomposition agent can be prepared by mixing iron oxide and alkaline earth metal compounds, adding an appropriate amount of water and kneading, and then granulating the kneaded material.

調製粒劑所需之混煉機可爲，同時進行混合及造粒， 或分開進行混合及造粒之物。該混煉機如，同時混合及造 粒用之漢氏混合機，縱型混合機等，或以漢氏混合機或V 型混合機等混合後，再以皿型造粒機，鼓式造粒機等造粒 〇 爲了提高所得粒劑之硬度較佳爲，於空氣或氮等不活 性氣流中，以1 〇 〇至1 5 0 °C乾燥3至5小時，使水分 蒸發。又，乾燥後可利用風環乾燥機，以1 1 〇 °C乾燥2 至3小時，使不純物分解劑所含水分量減至1質量％以下 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） 訂 線 (請先閲讀背面之注意事項再填寫本頁) -16- 經濟部智慧財產局員工消費合作社印¾ 1243809 A7 B7 五、發明説明（如 推斷使用該不純物分解劑時，粗八氟化環丁烷中氟化 碳等不純物會與不純物分解劑中鹼土類金屬化合物反應而 分解。例如，不純物之C F C - 2 1 7 6 a會與不純物分 解劑中鹼土類金屬之氫氧化物，氧化物或碳酸鹽反應，而 生成鹼土類金屬之氟化物或氯化物，一氧化碳及水。其後 以鐵爲觸媒，使所生成之一氧化碳及水反應，而生成氫或 甲烷。又，推測該連續反應後，C F C — 2 1 7 b a中氯 會受所生成之水取代，而生成2 Η -七氟化丙烷（以下稱 爲「H F C — 2 2 7 e a」）。接著可利用後述吸附劑去 除 HFC — 227ea。 另外，加熱下八氟化環丁烷本身接觸不純物分解劑時 ，會有數百質量P pm產生分解，而生成環六氟化環丁烯 (以下稱爲「F C - C 1 3 1 6」），但可利用後述吸附 劑去除。 吸附劑 本發明之精製方法中，加熱下將粗八氟化環丁烷接觸 不純物分解劑後，再接觸吸附劑。 該吸附劑較佳爲，活性碳，分子篩分離碳及賦活碳中 所選出至少1種。又，該活性碳，分子篩分離碳及賦活碳 較佳爲，經酸處理，熱處理，少蒸氣處理等前處理之物。 其中又以經前處理之賦活碳爲佳，更佳爲利用後述含 下列4個步驟之方法製得的賦活碳。 該吸附劑可單獨使用或複數倂用。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） t.IT^ (請先閲讀背面之注意事項再填寫本頁) -17- 1243809 A7 B7 五、發明説明（1)5 (賦活碳之製造方法） 下面將詳細說明特佳之賦活碳製造方法。又，賦活碳 製造方法包含下列4個步驟。 (1 )步驟1 ··以酸及水洗淨賦活碳之原料碳的步驟 (2 )步驟2 :不活性氣體中，以5 〇至2 5 0 °C將The kneader required to prepare the granules can be a mixture and a granulate simultaneously, or a mixture and a granulate separately. The mixer is, for example, a Han's mixer, a vertical mixer for simultaneous mixing and granulation, or a Han's mixer or a V-type mixer, followed by a dish-type granulator and a drum-type mixer. Granulation by a granulator or the like. In order to increase the hardness of the granules obtained, it is preferable to dry it at 100 to 150 ° C in air or nitrogen for 3 to 5 hours to evaporate water. In addition, after drying, the air ring dryer can be used to dry at 110 ° C for 2 to 3 hours, so that the moisture content of the impurity decomposition agent can be reduced to less than 1% by mass. The Chinese paper standard (CNS) A4 specification applies to this paper standard ( 210X29 * 7mm) Ordering line (please read the precautions on the back before filling this page) -16- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1243809 A7 B7 V. Description of the invention (such as inferring the use of the impure decomposition agent , Impurities such as carbon fluoride in crude octafluorocyclobutane will react with the alkaline earth metal compounds in the impure decomposition agent to decompose. For example, the CFC-2 1 7 6 a of the impurities will react with the hydrogen of the alkaline earth metals in the impure decomposition agent. Oxides, oxides, or carbonates react to form fluorides or chlorides of alkaline earth metals, carbon monoxide, and water. Iron is then used as a catalyst to react the generated carbon monoxide and water to produce hydrogen or methane. It is speculated that after this continuous reaction, the chlorine in CFC — 2 1 7 ba will be replaced by the generated water to form 2 Η-propanefluoride (hereinafter referred to as “HFC — 2 2 7 ea”). The adsorbent removes HFC — 227ea. In addition, when the octafluorocyclobutane itself comes into contact with the impurity decomposing agent under heating, hundreds of mass P pm will be decomposed, and cyclohexafluorocyclobutene (hereinafter referred to as “FC -C 1 3 1 6 ″), but it can be removed by the adsorbent described later. Adsorbent In the purification method of the present invention, the crude cyclobutane octafluoride is contacted with an impurity decomposing agent under heating, and then the adsorbent is contacted. The adsorbent Preferably, at least one selected from activated carbon, molecular sieve separation carbon, and activated carbon. The activated carbon, molecular sieve separation carbon, and activated carbon are preferably pretreated materials such as acid treatment, heat treatment, and less steam treatment. Among them, pre-treated activated carbon is preferable, and activated carbon prepared by a method including the following 4 steps described later is more preferable. The adsorbent can be used alone or in combination. This paper size is applicable to Chinese national standards ( CNS) A4 specification (210X297mm) t.IT ^ (Please read the notes on the back before filling out this page) -17- 1243809 A7 B7 V. Description of the invention (1) 5 (Manufacturing method of activated carbon) Details will be given below Description Activated carbon manufacturing method. In addition, the activated carbon manufacturing method includes the following four steps. (1) Step 1 · Step (2) of washing the activated carbon raw carbon with acid and water. Step 2: In an inert gas, 5 〇 to 2 5 0 ° C

原料碳加熱進行原料碳之脫氧處理及/或脫水處理的步驟 (3 )步驟3 :不活性氣流中，以5 0 〇至7 0 0 °C 將原料碳加熱進行原料碳之再碳化處理的步驟 (4 )步驟4 :含不活性氣體’二氧化碳及水蒸氣之 混合氣流中，以7 0 0至9 0 0 °C將原料碳加熱進行原料 碳之賦活化處理的步驟。 又，經步驟1洗淨之原料碳雖可作爲吸附劑用，但以 利用包含步驟2至4之方法，由經步驟1之原料碳製得的 賦活碳爲佳。 (賦活碳之原料碳） 所使用之賦活碳的原料碳可爲，椰子殼碳，石碳，木 碳及焦瀝青中所選出至少1種。其中，考量細孔發達所需 之碳細密性及作爲吸附劑所需硬度等，又，以椰子殼碳爲 佳。 該原料碳爲加熱碳化（碳化處理）之物，又，碳化溫 度並無特別限制，較佳爲以細孔幾乎未發達之4 0 0至 600 t，更佳爲400至500 °C進行碳化處理之物。 所得原料碳又以利用，以酸及水進行洗淨處理之步驟 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------裝-- (請先閲讀背面之注意事項再填寫本頁) 、!! 線 經濟部智慈財產局員工消资合作社印製 -18- 1243809 經濟部智慧財產局員工消費合作社印奴 A7 B7五、發明説明（也 (步驟1)，進行脫氧及/或脫水之步驟（步驟2)，進 行再碳化處理之步驟（步驟3 )，賦活化處理之步驟（步 驟4)之一連串步驟處理爲佳。 (步驟1 ) 首先以酸及水對賦活碳之原料碳進行洗淨處理。 步驟1之酸洗淨用的酸如，鹽酸，硫酸，硝酸，磷酸 等無機酸，或乙酸，三氟乙酸等有機酸。其中又以無機酸 爲佳，更佳爲鹽酸及/或硫酸，又，考量所生成之金屬鹽 下，特佳爲鹽酸。 酸濃度較佳爲1至1 0 0 0莫耳/m3，更佳爲2 0 0 至500莫耳/m3。 酸濃度小於1莫耳/m 3時，會減少金屬去除效果，又 ，大於1 0 0 0莫耳/m 3時，洗淨效果爲飽和狀態。對原 料碳之酸洗淨用酸溶液的體積比（酸溶液之體積/原料碳 之體積）較佳爲1/1至5/1，更佳爲1/1/至2/ 1。體積比小於1 / 1時，會減少酸洗淨效果，又，體積 比大於5 / 1時，酸洗淨效果爲飽和狀態。 利用酸之洗淨時間會因洗淨溫度而異，並無特別限制 。例如，洗淨溫度較高（如3 0至1 0 0 °C )時放置數小 時（如1至1 2小時），常溫（如1 0至3 0 °C )時放置 一夜（如1 2至2 4小時）下，可充分洗淨原料碳所含金 屬。 酸洗淨後所進行之水洗淨處理爲，將原料碳中殘留之 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) -裝· 訂 線 -19- 經濟部智慧財產局員工消費合作社印製 1243809 A7 _B7_ 五、發明説明（如 原料碳所溶解的金屬鹽洗淨。因此，所使用之水較佳爲， 自來水等金屬鹽較少之水或純水。又，利用水之洗淨方法 並無特別限制，無論連續或分批式均可充分洗淨。 水洗淨後，洗淨液之P Η較佳爲p Η 3至5。 將水洗淨後原料碳乾燥之操作可於後述步驟2之前單 獨進行，或於進行脫酸及/或脫水之步驟2中進行。 經上述酸及水洗淨原料碳時，可去除原料碳中之金屬 成分，特別是鹼金屬。原料碳中殘留金屬成分，特別是鹼 金屬時，會成爲後述步驟4之觸媒，而使賦活氣體（水蒸 氣，二氧化碳）與原料碳中碳原子反應，結果將難控制細 孔徑。 (步驟2 ) 步驟2爲，不活性氣流中，將原料碳加熱進行原料碳 之脫氧處理及/或脫水處理的步驟。 所使用之不活性氣體可爲各種不活性氣體，其中又以 氮氣爲佳。 不活性氣體之流量及處理時間並無特別限制，可由能 平順將原料碳所放出之氧氣及水分排至系外之氣體流量及 處理時作適當選擇。 不活性氣流下將原料碳加熱之溫度可爲，比步驟3之 加熱溫度更低之一定溫度，且爲不再碳化之溫度。步驟2 之加熱溫度較佳爲5 0至2 5 0 t，更佳爲10 0至 2 5 CTC。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I--------^------、玎------^ (請先閲讀背面之注意事項再填寫本頁) -20- 絰濟邹智慧財產局員工消費合作社印製 1243809 A7 ___B7 五、發明説明（也 步驟2之加熱溫度爲上述範圍時，可快速升溫至步驟 3之再碳化溫度。 將原料碳加熱進行脫氧及/或脫水處理時，可減少進 行再碳化處理之步驟3的氧源影響力。 (步驟3 ) 步驟3爲，加熱下對原料碳進行再碳化處理之步驟。 由步驟2移行至步驟3之升溫速度以快爲佳，更佳由 3 0 〇至5 0 0 °C/h r作適當選擇。 升溫速度小於3 0 0 °C / h 1：時，將無法去除乾餾揮 發物之焦油成分，而有粗孔不發達之傾向。又以不活性氣 流下升溫爲佳。 再碳化處理之溫度較佳爲5 0 0至7 0 0 °C，更佳爲 600 至 700 °C。 再碳化溫度低於5 0 0°C時，會有無法充分去除揮發 成分，使細孔分布幅度變寬，高溫時碳基質收縮及細孔收 縮等問題。又，再碳化溫度高於7 0 0 °C時，同樣會造成 碳基質收縮及微細孔收縮。 再碳化處理時間可爲1至2小時。 再碳化處理較佳於不活性氣流中進行，所使用之不活 性氣體可爲各種不活性氣體，又以氮氣爲佳。 對處理原料碳每1 &lt;之不活性氣體流量較佳爲2至 10《/mi η ，更佳爲3至5之/mi η。 上述般將原料碳再碳化，使經步驟1去除金屬之原料 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） I 裝 訂 線 (請先閲讀背面之注意事項再填寫本頁) -21 - 經濟部智慧財產局員工消費合作社印製 1243809 B7 五、發明説明（1)9 碳加熱乾餾時，可使焦油成分分解’發現並發達碳化粗孔 及使焦油成分碳化，而使步驟4有效發現並發達細孔。 (步驟4 ) 步驟4爲，加熱下將經步驟3再碳化之原料碳接觸混 合氣體，使原料碳賦活化之步驟。 又，本說明書中，賦活化係指使原料碳之細孔發達， 而將原料碳活性化。 推測該賦活化過程爲，先將原料碳內部結晶體內之閉 鎖的細孔開放（第一階段），再將接鄰之細孔間壁完全消 除，而形成孔徑較大之細孔。 無損賦活化下，步驟4所使用之混合氣體並無限定， 但以不活性氣體，二氧化碳及水蒸氣所形成之混合氣體爲 佳。該不活性氣體並無限定，但以氮爲佳。 步驟4所使用之氣體爲上述混合氣體時，因混合與碳 反應比水蒸氣慢之二氧化碳，不活性氣體之氮及水蒸氣， 故可緩和進行賦活化反應。 又，以空氣（氧氣）爲混合氣體之成分時，會因氧與 原料碳之反應爲發熱量大的反應，而難調節爐內溫度，造 成部分過熱，故難均勻進行賦活。因水蒸氣與碳之反應較 激烈，故單獨使用水蒸氣進行賦活處理時，將難控制細孔 徑。 由不活性氣體，二氧化碳及水蒸氣形成之混合氣體對 全部混合氣體之體積比較佳爲，不活性氣體5 0至8 9體 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I.--------I------1T------^ (請先閲讀背面之注意事項再填寫本頁) -22- 絰濟部智慧財產局8工消費合作社印¾ 1243809 A7 B7 五、發明説明（ 積％，二氧化碳1 〇至3 0體積％，水蒸氣1至2 0體積 %，更佳爲不活性氣體7 0至8 0體積％，二氧化碳1 5 至2 5體積％，水蒸氣2至1 0體積％。 該混合氣體之比率爲上述範圍時，可使原料碳中的碳 與水蒸氣穩定反應及有效進行賦活化處理。 對處理原料碳每1 &lt;之混合氣體流量較佳爲〇 . 5至 3，/mi η，更佳爲 1 至 2 &lt;/mi η。 步驟2至3之各步驟係於加熱下進行，因此以連續進 行爲佳，特佳爲高溫下連續進行步驟3及步驟4之處理步 驟。 由步驟3到步驟4之升溫速度較佳爲1 0 0至2 0 0 〇C / h I·。 升溫速度爲上述範圍時，可有效率進行步驟3移行至 步驟4。 步驟3移行至步驟4之升溫速度小於1 0 0 °C / h I* 時，將無法開放碳結晶體內閉鎖之細孔，而無法增加表面 積，又，升溫速度大於2 0 0 t/h r時，會有增加比表 面積及細孔徑之傾向。 賦活化處理之溫度較佳爲7 0 0至9 0 0 °C，更佳爲 800 至 900 °C。 賦活處理溫度低於7 0 0 °C時，將無法充分開放及擴 大細孔，又，溫度高於9 0 0 °C時，將難控制細孔開放及 擴大等。 賦活化處理之時間太長時，會有進行賦活時增加活性 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------私衣------，1T------線 (請先閲讀背面之注意事項再填寫本頁) •23- 唆齊郎皆綣时4笱員X.消費合作社印製 1243809 A7 B7 五、發明説明（办 碳細孔徑之傾向，又，處理時間會因吸附去除對象之不純 物大小而異，並無特別限定。 例如，將吸附八氟化環丁烷中所含不純物時，處理時 間較佳爲1至2 0小時，更佳爲5至1 8小時。 步驟4於完成原料碳之賦活化處理後，較佳於不活性 氣流下將原料碳冷卻至常溫。賦活化處理實質不產生細孔 變化下，此時之降溫速度以快爲佳，例如，降溫速度較佳 爲 200 至 300 °C / hr。 降溫速度低於2 0 0 °C / h r時，會因降溫所需時間 而有控制細孔徑之吸附劑造成細孔變化之傾向。 爲了將吸附劑所持有之熱量平順去除至系外，冷卻時 所使用之不活性氣體流量以大爲佳，但以處理碳每1 &lt;爲 1 . 5 至 3〈/mi η 爲佳。 所得之賦活碳因係以酸及水洗淨處理原料碳，故特別 是鹼金屬含量較少。賦活碳所含鹼金屬之總含量較佳爲 lOOOppm以下，更佳爲50至lOOOppm。特 別是鉀含量較佳爲5 0 0 P pm以下，更佳爲2 0 0 ppm以下，特佳爲10至200ppm。 吸附劑中鹼金屬含量之測定方法可爲，將吸附劑焚燒 後溶解於酸中，再以 ICP (Inductively Coupled Plasma Emission Spectro-chemical analysis:誘導結合形等離子分析 法）測定。 所得賦活碳之碘吸附量較佳爲7 0 0至1 0 〇 〇mg / g。又，可依據J I S K 1 4 7 4測定碘吸附量。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I 訂 線 (請先閲讀背面之注意事項再填寫本頁) -24- 經濟部智慧財產局8工消费合作社印¾ 1243809 A7 B7 五、發明説明（金 祖八氟化環丁烷之精製方法 本發明之氟化環丁烷精製方法係由，加熱下將含不純 物之粗八氟化環丁烷接觸不純物分解劑之步驟（精製步驟 1 )及，再接觸吸附劑之步驟（精製步驟2 )所構成。適 用於本發明精製方法之粗八氟化環丁烷可爲已知方法所製 得之物，或市售物。 (精製步驟1 ) 利用不純物分解劑之粗八氟化環丁烷中氟化碳等不純 物的分解反應操作中，所使用之接觸方法並無特別限制， 可爲將不純物分解劑塡入分解反應器後，將粗八氟化環丁 烷供給分解反應器，使粗八氟化環丁烷接觸不純物分解劑 ，又以利用固定床之流通法進行連續操作等爲佳。 反應壓力可爲加壓或不加壓下，以一般易處理之壓力 進行處理，但以表壓0至2MP a爲佳，更佳爲〇至1 Μ P a 〇 分解反應器之大小（容積）及空間速度於粗八氟化環 丁烷與不純物分解劑間具有某程度接觸時間下，並無特別 限制，但以分解反應器中粗八氟化環丁烷滯留時間1至 30 s e c爲佳，更佳爲4至30 s e c。 分解反應器中分解反應溫度較佳爲2 5 0至3 8 0°C ，更佳爲2 8 0至3 6 0 t。分解反應溫度爲前述範圍時 ，將不會造成不純物分解劑分解，而維持其活性。分解反 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I 訂 線 (請先閲讀背面之注意事項再填寫本頁) -25- 唆齊郎智慧时產局員工消費合作社印製 1243809 A7 B7____ 五、發明説明（僉 應溫度低於2 5 0 °c時’將無法提升不純物分解劑之活性 ，而難進行分解，又，分解反應溫度超過3 8 0°C時’會 因熱而使不純物分解劑本身分解’因此無法進行粗八氟化 環丁烷中不純物分解。 (精製步驟2 ) 將精製步驟1所生成或殘留之氟化碳等不純物接觸吸 附劑而實質去除後，可得高純度之八氟化環丁烷。 吸附操作方法可爲，將吸附劑塡入吸附塔中’再供給 分解反應後之粗八氟化環丁烷。該吸附操作方法並無限定 ，可爲已知之方法，又以利用固定床之流通法進行連續操 作爲佳。 將精製步驟1所得粗八氟化環丁烷接觸吸附劑時，可 爲氣相或液相。又，氣相接觸法之線速度較佳爲1至1 0 m/m i η，更佳爲1至5 m/m i η，液相接觸法之線 速度較佳爲0 · 2至5m/hr，更佳爲0 . 5至2m/ hr 〇 處理壓力可爲一般易處理之壓力，無需特別加壓等操 作，一般表壓又以0至2MP a爲佳。 吸附操作之溫度無需加溫或冷卻，可爲一般室溫。 又，吸附劑之吸附能爲飽和狀時，可再生利用。吸附 劑之再生方法可爲，使用氮氣等各種不注性氣體，並將高 溫之該不活性氣體通過吸附劑，而使吸附劑所吸附之氟化 碳等不純物，八氟化環丁烷脫附而得。 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X297公釐） — 裝 I 訂 線 (請先閲讀背面之注意事項再填寫本頁) -26- 1243809 A7 B7Step (3) of heating raw carbon to perform deoxidation and / or dehydration treatment of raw carbon. Step 3: Step of heating raw carbon in an inactive gas stream at 500 to 700 ° C for recarbonization of raw carbon. (4) Step 4: a step of heating the raw carbon to activate the raw carbon at a temperature of 700 to 900 ° C in a mixed gas stream containing an inert gas such as carbon dioxide and water vapor. In addition, although the raw material carbon washed in step 1 can be used as an adsorbent, it is preferable to use activated carbon prepared from the raw material carbon in step 1 by a method including steps 2 to 4. (Raw carbon raw material carbon) The raw carbon used to activate carbon may be at least one selected from coconut shell carbon, stone carbon, wood carbon, and coke pitch. Among them, considering the fineness of carbon required for the development of fine pores and the hardness required as an adsorbent, coconut shell carbon is preferred. The raw carbon is a substance that is carbonized by heating (carbonization treatment), and the carbonization temperature is not particularly limited. It is preferably carbonized with 400 to 600 t, and more preferably 400 to 500 ° C with fine pores that are hardly developed. Thing. The obtained raw carbon is reused and washed with acid and water. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- install-(Please read first Note on the back, please fill out this page again), !! Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -18-1243809 Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Consumers Cooperative A7 B7 ), The step of deoxidation and / or dehydration (step 2), the step of recarbonization (step 3), and a series of steps provided with the step of activation treatment (step 4) are preferred. (Step 1) First, the acid and Water is used to wash the activated carbon raw material carbon. The acid used for the acid cleaning in step 1 includes inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or organic acids such as acetic acid and trifluoroacetic acid. Among them, inorganic acids are used as Hydrochloric acid and / or sulfuric acid are more preferred, and hydrochloric acid is particularly preferred in consideration of the generated metal salt. The acid concentration is preferably 1 to 100 mol / m3, and more preferably 200 to 500. Moore / m3. When the acid concentration is less than 1 Moore / m3, the metal removal effect will be reduced, In addition, when it is more than 100 mol / m 3, the cleaning effect is saturated. The volume ratio of the acid solution for acid cleaning of the raw carbon (the volume of the acid solution / the volume of the raw carbon) is preferably 1 / 1 to 5/1, more preferably 1/1 / to 2/1. When the volume ratio is less than 1/1, the pickling effect is reduced, and when the volume ratio is greater than 5/1, the pickling effect is saturated. The washing time with acid will vary depending on the washing temperature and is not particularly limited. For example, when the washing temperature is high (such as 30 to 100 ° C), it can be left for several hours (such as 1 to 12 hours) At room temperature (such as 10 to 30 ° C), it can be fully washed at room temperature (such as 12 to 24 hours) to fully clean the metal contained in the raw carbon. The water washing treatment after pickling is to The size of this paper remaining in the raw carbon is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page)-Binding · -19-Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative 1243809 A7 _B7_ V. Description of the invention (such as washing the metal salt dissolved in the raw carbon. Therefore, the water used is preferably tap water Water or pure water with less metal salts. There is no particular restriction on the method of washing with water, and it can be fully washed regardless of continuous or batch type. After washing with water, P Η of the washing liquid is preferably p Η 3 to 5. The operation of drying the raw material carbon after washing with water can be performed separately before step 2 described later, or in step 2 of deacidifying and / or dehydrating. When the raw material carbon is washed with the above acid and water, Removal of metal components in raw carbon, especially alkali metals. Residual metal components in raw carbon, especially alkali metals, will act as catalysts in step 4 described below, so that activated gas (water vapor, carbon dioxide) and raw carbon The carbon atoms react, and as a result, it is difficult to control the pore diameter. (Step 2) Step 2 is a step of heating the raw carbon to perform deoxidation treatment and / or dehydration treatment of the raw carbon in an inert gas stream. The inert gas used may be various inert gases, and nitrogen is preferred. There is no particular limitation on the flow rate and processing time of the inert gas, and the gas flow rate and treatment that can smoothly discharge the oxygen and moisture released from the raw carbon to the system can be selected appropriately. The temperature at which the raw carbon is heated under the inert gas stream may be a temperature lower than the heating temperature in step 3, and a temperature at which carbonization is no longer performed. The heating temperature in step 2 is preferably 50 to 25 0 t, and more preferably 100 to 2 5 CTC. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) I -------- ^ ------, 玎 ------ ^ (Please read the notes on the back first (Fill in this page again) -20- Printed by Jiuzou Intellectual Property Bureau Employee Cooperative Cooperative 1243809 A7 ___B7 V. Description of the invention (also when the heating temperature in step 2 is in the above range, it can be quickly heated up to the recarbonization temperature in step 3. When the raw carbon is heated for deoxidation and / or dehydration, the influence of the oxygen source in step 3 of the recarbonization treatment can be reduced. (Step 3) Step 3 is a step of recarbonizing the raw carbon under heating. From step 2 It is better to move to step 3 with a faster heating rate, more preferably from 300 to 500 ° C / hr. If the heating rate is less than 300 ° C / h 1: dry distillation volatiles will not be removed The tar composition tends to be underdeveloped with coarse pores. It is also preferable to increase the temperature under an inert gas flow. The temperature for the recarbonization treatment is preferably 500 to 700 ° C, and more preferably 600 to 700 ° C. When the recarbonization temperature is lower than 500 ° C, the volatile components may not be sufficiently removed, and the pore distribution amplitude may be changed. , Carbon matrix shrinkage and pore shrinkage at high temperatures. Also, when the recarbonization temperature is higher than 700 ° C, the carbon matrix shrinkage and pore shrinkage will also be caused. The recarbonization treatment time can be 1 to 2 hours. The carbonization treatment is preferably performed in an inert gas stream. The inert gas used may be various inert gases, and nitrogen is preferred. The flow rate of the inert gas per 1 &lt; of the treated raw material carbon is preferably 2 to 10 " / mi η, more preferably 3 to 5 / mi η. Recarbonize the raw material carbon as described above, so that the raw material from which the metal is removed in step 1 The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) I Binding (Please read the precautions on the back before filling this page) -21-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 1243809 B7 V. Description of the invention (1) 9 When carbon is retorted, it can decompose the tar component. Develop carbonized coarse pores and carbonize the tar component, so that step 4 is effectively found and developed pores. (Step 4) Step 4 is to contact the raw carbon recarbonized in step 3 with a mixed gas under heating to activate the raw carbon. step In this specification, activation means the development of pores of the raw carbon and activation of the raw carbon. It is speculated that the activation process is to first open the closed pores in the internal crystals of the raw carbon (first stage). Then, the adjacent pore walls are completely eliminated to form pores with a larger pore size. Under non-destructive activation, the mixed gas used in step 4 is not limited, but it is formed by inactive gas, carbon dioxide and water vapor. A mixed gas is preferred. The inert gas is not limited, but nitrogen is preferred. When the gas used in step 4 is the above-mentioned mixed gas, since the carbon dioxide, which reacts slower than water vapor with carbon and the nitrogen and water vapor of the inert gas, are mixed, the activation reaction can be relaxed. In addition, when air (oxygen) is used as a component of the mixed gas, the reaction between oxygen and the raw carbon becomes a large calorific reaction, and it is difficult to adjust the temperature in the furnace, resulting in partial overheating, so it is difficult to uniformly activate. Because the reaction between water vapor and carbon is fierce, it is difficult to control the pore diameter when water vapor is used alone for the activation treatment. The volume of the mixed gas formed by the inert gas, carbon dioxide and water vapor is better for the total mixed gas. The inactive gas is 50 to 8 9 volumes. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) I .-------- I ------ 1T ------ ^ (Please read the precautions on the back before filling out this page) -22- 8 Industrial Consumers Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs Print ¾ 1243809 A7 B7 V. Description of the invention (volume%, carbon dioxide 10 to 30% by volume, water vapor 1 to 20% by volume, more preferably 70 to 80% by volume of inert gas, carbon dioxide 15 to 2 5 vol%, water vapor 2 to 10 vol%. When the ratio of the mixed gas is in the above range, the carbon in the raw carbon can be stably reacted with water vapor and the activation treatment can be effectively performed. The flow rate of the mixed gas is preferably 0.5 to 3, / mi η, more preferably 1 to 2 &lt; / mi η. Each step of steps 2 to 3 is performed under heating, so it is better to perform continuously, especially Preferably, the processing steps of steps 3 and 4 are continuously performed at a high temperature. The heating rate from step 3 to step 4 is preferably 100. 2 0 〇C / h I ·. When the heating rate is in the above range, you can efficiently move from step 3 to step 4. When the temperature rising rate from step 3 to step 4 is less than 100 ° C / h I *, The closed pores in the carbon crystal body cannot be opened, and the surface area cannot be increased. Moreover, when the heating rate is greater than 200 t / hr, the specific surface area and the pore diameter tend to be increased. The activation treatment temperature is preferably 7 0 0 To 900 ° C, more preferably 800 to 900 ° C. When the activation temperature is lower than 700 ° C, the pores cannot be fully opened and enlarged, and when the temperature is higher than 900 ° C, It is difficult to control the opening and expansion of pores, etc. When the activation treatment is too long, the activation will increase when the activation is performed. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ------- --Private clothing ------, 1T ------ line (please read the notes on the back before filling this page) 1243809 A7 B7 V. Description of the invention (the tendency of carbon pores, and the processing time will vary depending on the size of the impurities to be removed by adsorption. Do not limit. For example, when the impurities contained in cyclobutane octafluoride are adsorbed, the treatment time is preferably 1 to 20 hours, more preferably 5 to 18 hours. Step 4 After completing the activation treatment of the raw carbon It is better to cool the raw material carbon to normal temperature under an inert gas stream. The activation treatment is substantially free of pore changes. At this time, the cooling rate is preferably fast. For example, the cooling rate is preferably 200 to 300 ° C / hr. . When the cooling rate is lower than 200 ° C / h r, there is a tendency for the pores of the adsorbent to control the pore diameter to change due to the time required for cooling. In order to smoothly remove the heat held by the adsorbent to the outside of the system, the flow rate of the inert gas used during cooling is preferably large, but the treated carbon is preferably 1.5 to 3 </ mi η per 1 &lt;. The activated carbon obtained is treated with acid and water to clean the raw material carbon, so the alkali metal content is particularly small. The total content of the alkali metal contained in the activated carbon is preferably 1,000 ppm or less, and more preferably 50 to 1,000 ppm. In particular, the potassium content is preferably 500 P pm or less, more preferably 200 ppm or less, and particularly preferably 10 to 200 ppm. The measuring method of the alkali metal content in the adsorbent may be that the adsorbent is dissolved in an acid after being incinerated, and then measured by ICP (Inductively Coupled Plasma Emission Spectro-chemical Analysis: Induced Coupled Plasma Analysis). The iodine adsorption amount of the obtained activated carbon is preferably from 700 to 100 mg / g. The iodine adsorption amount can be measured based on J I S K 1 4 7 4. This paper size applies to China National Standard (CNS) A4 (210X297 mm) I Thread (please read the precautions on the back before filling this page) -24- Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economy ¾ 1243809 A7 B7 V. Description of the invention (refining method of Jinzu octafluorocyclobutane The fluorinated cyclobutane refining method of the present invention is a step of refining crude octafluorocyclobutane containing impurities with an impurity decomposing agent under heating (refining Step 1) and the step of recontacting the adsorbent (refining step 2). The crude cyclobutane octafluoride suitable for the refining method of the present invention may be a product prepared by a known method or a commercially available product. Refining step 1) The method of contacting impure substances such as carbon fluoride in crude octafluorocyclobutane using an impure substance decomposing agent is not particularly limited. The impregnating agent may be used after the impure substance decomposing agent is charged into the decomposition reactor. It is better to supply the crude octafluorocyclobutane to a decomposition reactor, to contact the crude octafluorocyclobutane with an impure decomposition agent, and to perform continuous operation by a fixed-bed flow method. The reaction pressure may be pressurized or not. The reduction is carried out at a pressure that is generally easy to handle, but the gauge pressure is preferably 0 to 2MP a, more preferably 0 to 1 MPa. The size (volume) and space velocity of the decomposition reactor are in the crude octafluoride ring. There is no particular limitation for a certain degree of contact time between butane and the impure decomposition agent, but the residence time of the crude octafluorocyclobutane in the decomposition reactor is preferably 1 to 30 sec, and more preferably 4 to 30 sec. The decomposition reaction temperature in the reactor is preferably 250 to 380 ° C, and more preferably 280 to 360. The decomposition reaction temperature is in the aforementioned range, which will not cause the decomposition of impurities to be decomposed, and will be maintained. Its activity. The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). I Thread (please read the precautions on the back before filling this page) Printed by the cooperative 1243809 A7 B7____ 5. Description of the invention (When the response temperature is lower than 2 50 ° c, 'the activity of the impure decomposition agent will not be improved, and it will be difficult to decompose, and when the decomposition reaction temperature exceeds 3 8 0 ° C' Decomposition of the impurity decomposition agent itself due to heat 'Therefore, it is not possible to decompose the impurities in the crude octafluorocyclobutane. (Refining step 2) After the impurities such as carbon fluoride produced or remaining in the purification step 1 are contacted with the adsorbent and substantially removed, a high-purity octafluoride is obtained Cyclobutane. The method of adsorption operation may be to pour the adsorbent into the adsorption tower and then supply the crude cyclobutane octafluoride after the decomposition reaction. The method of adsorption operation is not limited, and it can be a known method and use The continuous operation of the fixed bed flow method is preferred for continuous operation. When the crude cyclobutane obtained in the purification step 1 is contacted with the adsorbent, it may be a gas phase or a liquid phase. In addition, the linear velocity of the gas phase contact method is preferably 1 to 10 m / mi η, more preferably 1 to 5 m / mi η, and the linear velocity of the liquid phase contact method is preferably 0.2 to 5 m / hr, and more preferably 0.5 to 2 m / hr. The pressure is generally easy to handle, no special pressurization and other operations are needed, and the normal gauge pressure is preferably 0 to 2MP a. The temperature of the adsorption operation does not need to be heated or cooled, and can be ordinary room temperature. When the adsorption energy of the adsorbent is saturated, it can be recycled. The regeneration method of the adsorbent may be the use of various injectable gases such as nitrogen, and passing the high-temperature inactive gas through the adsorbent to desorb impurities such as carbon fluoride adsorbed by the adsorbent, and cyclobutane octafluoride. To get. This paper size applies Chinese National Standard (CNS) M specification (210X297mm) — binding I (please read the precautions on the back before filling this page) -26- 1243809 A7 B7

五、發明説明（A 吸附劑再生時，不活性氣體之溫度較佳爲1 〇 〇至 400°C，更佳爲 10 0 至 200°C。 —--------裝-- (請先閲讀背面之注意事項再填寫本頁) 〔八氟化環丁烷之製造方法〕 本發明之八氟化環丁烷製造方法爲，製造粗八氟化環 丁烷後，適當組合使用上述精製方法。具體而言即，製造 粗八氟化環丁烷後，可組合使用精製步驟，及精製步驟2 〇 該粗八氟化環丁烷之合成方法並無限定，可採用已知 之方法。例如可爲，上述般製造四氟化乙烯（F C -1 1 1 4)或六氟化丙烯（FC-1 2 1 6)時所得副產 物。又，FC - 1 1 14 或 FC-1216 可如 EP45 1 7 9 3號公報所記載般，將氯二氟化甲烷（HC F C — 2 2 )熱分解而得。 線 製造粗八氟化環丁烷後，利用精製步驟1及精製步驟 2可得實質去除不純物之八氟化環丁烷。 暧齊郎眘慧时產局員工消費合作社印製 〔高純度八氟化環丁烷〕 利用本發明精製方法時，可實質去除粗八氟化環丁烷 中氯氟化碳類或氫氟化碳類等氟化碳所形成之不純物，例 如2 —氯—1，1，1，2，3，3，3 -七氟化丙烷（ CFC-2176ba)，1 -氯-1，1，2，2，3 ，3’3 - 七氟化丙烷（CFC — 217ca) ，1—氯 —1，2，2，2 —四氟化乙烷（或2 —氯—1 ，1 ，1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -27- 經濟部智慧財產局員工消費合作社印髮 1243809 A7 ____B7 五、發明説明（灰 ，2 —四氟化乙烷，HCFC— 124) ，1—氯一 1， 1 ，2，2 —四氟化乙烷（HCFC— 124a) ，ι ， 2 —二氯—1，1，2，2 —四氟化乙烷（CFC — 114)，六氟化丙烯（FC — 1216)及1H —七氟 化丙烷（HFC - 2 2 7 c a )等氟化碳所形成之不純物 ，特別是CFC - 2 17b a，而得高純度八氟化環丁院 〇 粗八氟化環丁烷所含之不純物含量一般爲1 〇至 10，000質量ppm，但，利用本發明精製方法時， 可將粗八氟化環丁烷中所含該不純物去除至低於1質量 ppml 〇，〇〇〇/質量％)，而使精製後所得八氟化 環丁烷純度爲99.9999質量％以上。 該八氟化環丁烷之純度定義爲，由1 0 0質量％減去 八氟化環丁烷以外之氟化碳成分的値。又，純度 9 9 · 9 9 9 9質量％以上之八氟化環丁烷製品的分析法 可爲，（1)氣相色譜（GC)之TCD法，FID法（ 以上均含預切法），ECD法或（2)利用氣相色譜質量 分析計（G C DM S )等分析機器。 〔用途〕 因本發明精製方法或製造方法所得之八氟化環丁烷可 實質去除不純物，故適用爲半導體裝置製造過程中，蝕刻 步驟之蝕刻氣體。 具體而言即適用爲，LS I或TFT等半導體裝置之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） — 裝 訂 線 (請先閲讀背面之注意事項再填寫本頁) -28- 1243809 A7 ___ B7_ 五、發明説明（全 製造過程中，利用C V D法，濺射法或鍍著法等形成薄膜 或厚膜後，形成回路圖型用之蝕刻氣體。 又，適用爲半導體裝置製造過程中，淸潔步驟用之淸 潔氣體。 即，形成薄膜或厚膜之裝置中，去除裝置內壁，夾具 等所堆積不要之堆積物用的淸潔氣體。因該不要的堆積物 係產生微片之原因，故製造良質膜時需隨時去除不要的堆 積物，因此該淸潔氣體適用本發明之八氟化環丁烷。 本發明之氣體爲，含有高純度八氟化環丁烷之氣體。 該氣體可單獨含有八氟化環丁烷，或另含有適當之其他氣 體。該其他氣體如，He，Me，Ar ，〇2等。又，其他 氣體之添加量並無限定，例如以本發明之高純度八氟化環 丁烷作爲鈾刻氣體或淸潔氣體時，會因蝕刻對象之化合物 種類，厚度等而異，且可依淸潔對象之附著量，厚度等作 決定。 發明效果 利用本發明之八氟化環丁烷精製方法或製造方法可實 質去除目前難去除之氟化碳等不純物，而易得高純度八氟 化環丁烷。又，因本發明精製方法所得之八氟化環丁烷實 質不含不純物，故適用爲半導體裝置製造過程中等所使用 之蝕刻氣體或淸潔氣體。 實施例 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) -裝· 訂 绶濟郎智慧財產局R工消费合作社印災 -29 - 1243809 經濟部智慧財產局員工消費合作钍印製 Α7 Β7 五、發明説明（余 下面將以實施例說明本發明’但非限於此例。 實施例1至3 〔調製不純物分解管〕 將不純物分解劑中氧化鐵及鹼土類金屬化合物的添加 率調製爲，r — Fe〇OH (石原產業（股）製）/Ca (〇Η) 2 (吉沢石灰工業（股）製）= 30/70質量％ (實施例1) ，r — Fe2〇3(戶田工業（股）製）/ Ca (〇H) 2=20/80 質量％ (實施例 2) ，r 一 ?6〇〇11/〇3&lt;：〇3(奧多摩工業（股）製）=20/ 8 0質量％ (實施例3 )後加水造粒’再以1 0 5 °C乾燥 處理2小時，篩選後得粒徑〇 · 8 5至2 · 8 m m粒狀物 。將不純物分解劑1.9&amp;以層高8(：111(容積15^) 方式塡入內徑1 6mm之不銹鋼管（反應管）後，氮氣流 中以3 0 0 °C處理3小時以上，作爲不純物分解管用。 〔調製吸附劑及吸附塔〕 以下列方法製造吸附劑。 以3 0 〇m ο 1 / m3濃度之鹽酸洗淨原料碳的椰子殻 碳（菲律賓產）75 &lt;後，以水洗淨3次。又，300 mo Ι/m3濃度之鹽酸使用量同洗淨對象原料碳之體積量 ，且將鹽酸加入原料碳後靜置1 5小時再拔液。水洗時之 水量爲原料碳的5倍體積量，當洗淨後洗淨液之p Η爲4 時，確認結束洗淨。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） I 私衣1Τ^ (請先閲讀背面之注意事項再填寫本頁) -30 - 1243809 A7 B7 經濟部智慧財產局員工消費合作社印製 五'發明説明（螽 表3 _ 酸洗豐前碳中金屬分析結果 _炭中金屬分析 ____ (質量ρ pm) 成分 酸洗淨前 酸洗淨後 N a 812 119 K 4950 132 C a 462 112 F e 837 103 A 1 876 100 將所得原料碳放入燒成爐（電外熱式金屬旋轉審爐： 回轉數設定爲8 r pm，爐內徑9 5 0mm，直胴部 620mm，50kw，150A (max)，90。。下 進行2小時氮乾燥。又，所使用之氮爲純度9 9 %以上之 物，且流量爲5 0 m i η。其後依表4所示條件，對 燒成爐中乾燥的原料碳進行脫氧/脫水處理（步驟2 )， 再碳化處理（步驟3 )及賦活化處理（步驟4 )。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） I 裝 訂 線 (請先閱讀背面之注意事項再填寫本頁) -31 - 1243809 B7 五、發明説明（太 表4 段階 步驟 溫度(。〇 時間(hr) N2( t /min) C〇2( &lt; /min) H2〇( t /min) 1 脫氧/脫水處理 150 2 50 0 0 2 昇溫 150^650 1 300 0 0 3 再碳化處理 650 2 300 0 0 4 昇溫 650^850 1 72 20 8 5 賦活化處理 850 16 72 20 8 6 降溫 850-600 1 72 20 8 7 降溫 600- 1 100 0 0 (請先閲讀背面之注意事項再填寫本頁) 絮·V. Description of the invention (A When the adsorbent is regenerated, the temperature of the inert gas is preferably 100 to 400 ° C, and more preferably 100 to 200 ° C. ---------- pack-- ( (Please read the precautions on the back before filling this page) [Method for producing octafluorocyclobutane] The method for producing octafluorocyclobutane according to the present invention is to produce crude octafluorocyclobutane, and then use the appropriate combination of the above Refining method. Specifically, after producing crude octafluorocyclobutane, a purification step may be used in combination, and purification step 20. The synthesis method of the crude octafluorocyclobutane is not limited, and a known method may be adopted. For example, it may be a by-product obtained when the above-mentioned ethylene tetrafluoride (FC-1 1 1 4) or propylene hexafluoride (FC-1 2 1 6) is produced. In addition, FC-1 1 1 14 or FC-1216 may be EP45 1 7 9 3 is obtained by thermally decomposing chlorodifluoromethane (HC FC-2 2). After producing crude cyclobutane octafluoride by wire, it can be obtained by purification step 1 and purification step 2. Substantial removal of impure octafluorocyclobutane. Printed by Jiqilang Shenhui Shishi Bureau Employee Consumer Cooperative [High Purity Cyclobutane] When the purification method of the present invention is used, impurities such as chlorofluorocarbons or hydrofluorocarbons in crude octafluorocyclobutane can be substantially removed, such as 2-chloro-1,1,1,2 , 3,3,3-propane heptafluoride (CFC-2176ba), 1-chloro-1,1,2,2,3,3'3 -propane heptafluoride (CFC-217ca), 1-chloro-1 ， 2,2,2—Ethylene tetrafluoride (or 2—Chloro-1, 1, 1.1) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -27- Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperatives issued 1243809 A7 ____B7 V. Description of the invention (ash, 2-tetrafluoroethane, HCFC-124), 1-chloro-1, 1, 2, 2, 2-tetrafluoroethane (HCFC-124a), ι , 2-dichloro-1,1,2,2,2-tetrafluoroethane (CFC — 114), propylene hexafluoride (FC-1216) and 1H — propane hexafluoride (HFC-2 2 7 ca), etc. Impurities formed by fluorinated carbon, especially CFC-2 17b a, to obtain high-purity cyclic fluorinated cyclobutane. 0 Impurities contained in crude cyclic fluorinated cyclobutane are generally 10 to 10,000 mass ppm. However, using the present invention In the production method, the impurity contained in the crude cyclobutane octafluoride can be removed to less than 1 mass ppm (100,000 /% by mass), and the purity of the cyclobutane octafluoride obtained after purification can be 99.9999 mass The purity of the octafluorocyclobutane is defined as 100% by mass minus fluorene of a fluorinated carbon component other than the octafluorocyclobutane. The analysis method for octafluorocyclobutane products having a purity of 9 9 · 9 9 9 9% by mass or more can be: (1) TCD method of gas chromatography (GC), FID method (the above include precut method) , ECD method or (2) using a gas chromatography mass spectrometer (GC DM S) and other analysis equipment. [Use] Because the octafluorocyclobutane obtained by the refining method or manufacturing method of the present invention can substantially remove impurities, it is suitable as an etching gas in the etching step in the manufacturing process of semiconductor devices. Specifically, the paper size of semiconductor devices such as LS I or TFT is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) — gutter (please read the precautions on the back before filling this page) -28 -1243809 A7 ___ B7_ V. Description of the invention (In the entire manufacturing process, the CVD method, sputtering method, or plating method is used to form a thin film or a thick film, and then an etching gas is used to form a circuit pattern. It is also suitable for semiconductor device manufacturing In the process, the cleaning gas is used in the cleaning step. That is, in the device for forming a thin film or a thick film, the cleaning gas for removing unnecessary deposits accumulated on the inner wall of the device, the jig, etc. is generated due to the unnecessary deposits. Due to microchips, unnecessary deposits need to be removed at any time when manufacturing a good quality film, so the clean gas is suitable for the octafluorocyclobutane of the present invention. The gas of the present invention is a high-purity cyclobutane Gas. This gas may contain cyclobutane octafluoride alone, or it may contain other appropriate gas. The other gas such as He, Me, Ar, 〇2, etc. Moreover, the addition amount of other gas is not limited. If the high-purity cyclobutane of the present invention is used as a uranium etching gas or a cleaning gas, it will vary depending on the type and thickness of the compound to be etched, and it can be determined according to the amount and thickness of the cleaning object. ADVANTAGE OF THE INVENTION By using the octafluorocyclobutane refining method or manufacturing method of the present invention, impurities such as carbon fluoride that are currently difficult to remove can be substantially removed, and high-purity cyclobutane octane is easily obtained. Furthermore, the purification method of the present invention The obtained cyclobutane octafluoride is substantially free of impurities, so it is suitable as an etching gas or a cleaning gas used in the manufacturing process of semiconductor devices. Example This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page)-Assembling and ordering Jilang Intellectual Property Bureau R Industry Consumer Cooperatives Printing Disaster-29-1243809 Employee Cooperative Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs Printing Α7 Β7 (The rest of the invention will be described in the following examples by way of example, but is not limited to this example. Examples 1 to 3 [Preparation of Impurity Decomposition Tube] Iron oxide and alkaline earth gold in the impure decomposition agent The addition rate of the metal compound is adjusted as follows: r — Fe〇OH (made by Ishihara Industry Co., Ltd.) / Ca (〇Η) 2 (made by Jisao Lime Industry Co., Ltd.) = 30/70% by mass (Example 1), r — Fe2〇3 (manufactured by Toda Industry Co., Ltd.) / Ca (〇H) 2 = 20/80% by mass (Example 2), r −6000011 / 〇3 &lt;: 03 (Otama Industry (Made by the company) = 20/8% by mass (Example 3) after adding water to granulate, and then drying treatment at 105 ° C for 2 hours, the particle size of 0.85 to 2 · 8 mm after screening The impure decomposition agent 1.9 & was poured into a stainless steel tube (reaction tube) with an inner diameter of 16 mm at a layer height of 8 (: 111 (volume 15 ^)), and then treated at 300 ° C for more than 3 hours in a nitrogen stream. It can be used as decomposition of impurities. [Preparation of adsorbent and adsorption tower] An adsorbent was produced by the following method. Coconut shell carbon (made in the Philippines) 75 &lt; was washed with hydrochloric acid having a concentration of 300 m 1 / m3 and then washed 3 times with water. In addition, the amount of hydrochloric acid used at a concentration of 300 mol / m3 is the same as the volume of the raw material carbon to be washed, and after adding hydrochloric acid to the raw material carbon, it is left to stand for 15 hours and then the liquid is drawn. The amount of water during washing is 5 times the volume of the raw carbon. When p 当 of the washing solution after washing is 4, confirm that the washing is completed. This paper size applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) I Clothing 1T ^ (Please read the precautions on the back before filling out this page) -30-1243809 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation of five 'invention description (螽 Table 3 _ Analysis of metal in carbon before pickling _ Analysis of metal in carbon ____ (mass ρ pm) Ingredients before pickling After pickling N a 812 119 K 4950 132 C a 462 112 F e 837 103 A 1 876 100 Put the obtained raw carbon into a firing furnace (electric external thermal metal rotary furnace: the number of revolutions is set to 8 r pm, the furnace inner diameter is 950 mm, the straight section 620 mm, 50 kw, 150A (max), 90 ° C for 2 hours of nitrogen drying. The nitrogen used is a substance with a purity of 99% or more, and the flow rate is 50 mi η. Thereafter, the firing was performed according to the conditions shown in Table 4. The raw carbon dried in the furnace is subjected to deoxidation / dehydration treatment (step 2), re-carbonization treatment (step 3) and activation treatment (step 4). This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) I Gutter (Please read the notes on the back before filling out this page) -31-1 243809 B7 V. Description of the invention (Table 4 Step temperature (°) Time (hr) N2 (t / min) C〇2 (&lt; / min) H2〇 (t / min) 1 Deoxidation / dehydration treatment 150 2 50 0 0 2 Temperature increase 150 ^ 650 1 300 0 0 3 Recarbonization treatment 650 2 300 0 0 4 Temperature increase 650 ^ 850 1 72 20 8 5 Activated treatment 850 16 72 20 8 6 Temperature decrease 850-600 1 72 20 8 7 Temperature decrease 600 -1 100 0 0 (Please read the notes on the back before filling this page)

J 將上述方法所得之吸附劑8 3 g塡入外徑1 / 2英寸 之不銹鋼管（吸附塔，內徑1 lmmx塔長1 5 0 cm， 容積1 3 0 m£)後，氮氣流中以1 6 0 °C處理7小時計8 小時，自接連於塡充不純物分解劑之不純物分解管後方。 〔調製粗八氟化環丁烷（FC — C318)〕 經濟部智慧財1局員工消費合作社印製 所使用之粗八氟化環丁烷爲，製造FC-1114時 之副產物。即，將HCFC - 2 2熱分解以製造F C -1114時，會因FC—1114二聚化而有八氟化環丁 烷副產物，將副產物蒸餾後，得粗八氟化環丁烷。接著以 氣相色譜將所得粗八氟化環丁烷中不純物量定量。又，氣 相色譜分析之分析條件如下所示。 •機器本體GC-18A((股）島津製作所製） 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -32- 1243809 A7 B7 經濟部智慧財產局員工消费合作社印製 五、發明説明（ά) •載氣 He •檢驗器 氫焰離子化檢驗器（F I D ) •試料量 0 . 2 τη£ •定量 絕對檢量線 結果粗八氟化環丁烷中氟化碳不純物之成分組成中， CFC — 217ba 爲 350 質量 ppm，CFC — 217ca 爲 20 質量 ppm，HCFC — 124， HCFC—124a及CFC—114各自爲10質量 p p m 〇 〔精製粗八氟化環丁烷〕 0 . 2 Μ P a壓力下，將所得粗八氟化環丁烷以不純 物分解管中空間速度爲7 5 0 H r — 1，吸附塔中線速度爲 1 m/m i η方式，以氣相流通其中。又，不純物分解管 之分解反應溫度爲3 5 0 °C。收集通過不純物分解管後及 通過吸附塔後之八氟化環丁烷，再以上述條件之氣相色譜 定量。 結果粗八氟化環丁烷開始起流通5小時，1 0小時， 1 5小時後，反應管出口及吸附塔出口的八氟化環丁烷中 氟化碳不純物類之分析結果如表5所示。 由表得知，CFC — 217ba，CFC — 217 ca，HCFC-124，HCFC— 124a 及 CFC - 1 1 4會受不純物分解劑分解，因此不純物分解管出口 幾乎未驗出，且生成HFC - 227ea，FC — 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） I 裝 訂 線 (請先閲讀背面之注意事項再填寫本頁) -33- 1243809J Pour 8 3 g of the adsorbent obtained by the above method into a stainless steel tube with an outer diameter of 1/2 inch (adsorption tower, inner diameter 1 lmmx tower length 150 cm, volume 130 m £). Treated at 160 ° C for 7 hours and 8 hours, it is connected behind the impurity decomposition tube filled with impurity decomposition agent. [Modified crude octafluorocyclobutane (FC — C318)] Printed by the Consumer Cooperative of the 1st Bureau of Intellectual Property of the Ministry of Economic Affairs The crude octafluorocyclobutane used is a by-product of the production of FC-1114. That is, when HCFC-2 2 is thermally decomposed to produce F C-1114, by-dimerization of FC-1114, a by-product of cyclobutane octafluoride is obtained. The by-product is distilled to obtain crude cyclobutane octafluoride. Then, the amount of impurities in the obtained crude cyclobutane octafluoride was quantified by gas chromatography. The analysis conditions for gas chromatography analysis are shown below. • Machine body GC-18A (made by Shimadzu Corporation) This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) -32- 1243809 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of invention (ά) • Carrier gas He • Tester hydrogen flame ionization tester (FID) • Sample amount 0.2 0.2 τη £ • Quantitative absolute calibration line results Quantitative carbon fluoride impurities in crude octafluorocyclobutane In the composition, CFC-217ba is 350 mass ppm, CFC-217ca is 20 mass ppm, HCFC-124, HCFC-124a and CFC-114 are each 10 mass ppm. 〇 [refined crude octafluorocyclobutane] 0. 2 Μ Under the pressure of Pa, the obtained crude octafluorocyclobutane was circulated in the gas phase in a manner that the space velocity in the impure decomposition tube was 7 50 H r -1 and the linear velocity in the adsorption tower was 1 m / mi η. The decomposition reaction temperature of the impurity decomposition tube was 350 ° C. The cyclobutane octafluoride after passing through the impurity decomposition tube and after passing through the adsorption column was collected and quantified by gas chromatography under the above conditions. Results Crude octafluorocyclobutane began to flow for 5 hours, 10 hours, and 15 hours later. The analysis results of the impure carbon fluoride in the octafluorocyclobutane at the exit of the reaction tube and the exit of the adsorption tower are shown in Table 5. Show. It is known from the table that CFC — 217ba, CFC — 217 ca, HCFC-124, HCFC — 124a, and CFC-1 1 4 will be decomposed by the impurity decomposition agent, so the outlet of the impurity decomposition tube is hardly detected, and HFC-227ea is generated. FC — This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) I gutter (please read the precautions on the back before filling this page) -33- 1243809

7 7 A B 瞍齊郎智慧时產局員工涓黄合作社印製 五、發明説明（洳7 7 A B 瞍 Qilang Printed by Employees of Smart Time Bureau Cooperative Cooperative V. Invention Description (发明

C 1 3 1 6等。又，該生成物會受吸附劑吸附，而由F CC 1 3 1 6 and so on. In addition, the product is adsorbed by the adsorbent, and is converted by F C

—C318 中去除 CFC — 217ba，CFC — 217 ca，HCFC— 124，HCFC - 124a 及 CFC —1 1 4，因此能精製八氟化環丁烷。 另外，吸附塔出口未驗出HFC - 227ea，FC —C 1 3 1 6。 表5 分解管出口及吸附塔出口之各不純物濃度變化（實施 例1 ) _ 經過 各巧 S 純物濃度變化（質量ppm) 時間 CFC- CFC- HCFC- HCFC- CFC-114 HFC- FC- (時間） 217ba 217ca 124 124a 227ea C1316 供給試 350 20 10 10 10 0 0 料 分解管 5 0 0 0 0 0 57 121 出口 10 0 0 0 0 0 58 99 15 0 0 0 0 0 43 29 吸附塔 5 0 0 0 0 0 0 0 出口 10 0 0 0 0 0 0 0 15 0 0 0 0 0 0 0 又，粗八氟化環丁烷開始流通起2小時，5小時後吸 附塔出口的八氟化環丁烷中CFC - 2 1 7b a之濃度變 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇&gt;&lt;297公釐） I 裝 訂 線 (請先閲讀背面之注意事項再填寫本頁) -34- 蛵濟邹智慧財產局員工消費合作社印製 1243809 A7 B7 五、發明説明（全 化及至吸附轉效的c F C - 2 1 7 b a去除量如表8所示 〇 又，以吸附塔出口驗出1 p p m氟化碳不純物之時間 爲吸附轉效時間，且以此時爲止之C F C - 2 1 7 b a流 通量爲CFC_217ba去除量。 所使用之三氧化二鐵爲r 一 Fe2〇3時（實施例2) 及，所使用之鹼土類金屬化合物爲C a C 〇3時（實施例3 )，對CFC — 217ba去除量均具高效能，故可精製 八氟化環丁烷。 比較例1 除了無利用不純物分解劑分解粗八氟化環丁烷中氟化 碳不純物之步驟外，其他同實施例1之條件進行。 同樣以氣相色譜將通過活性碳前後之不純物濃度定量 〇 又，八氟化環丁烷開始流通起5小時，1 0小時及 1 5小時後吸附塔出口之八氟化環丁烷中氟化碳不純物的 分析結果如表6所示。 CFC — 217ba 及 CFC — 217ca 幾乎與八 氟化環丁烷開始流通的同時吸附轉效，因此僅利用吸附劑 時，將無法吸附去除CFC — 2 1 7b a &amp;CFC- 2 1 7 c a ° 利用本發明精製方法時（實施例1 )之H C F C — 124，HCFC— 124a 及 CFC — 1 14 之去除量 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 4衣 訂 線 (請先閲讀背面之注意事項再填寫本頁) -35- 1243809—C318 removes CFC — 217ba, CFC — 217 ca, HCFC — 124, HCFC — 124a, and CFC — 1 1 4; therefore, cyclobutane octafluoride can be refined. In addition, HFC-227ea and FC-C 1 3 1 6 were not detected at the outlet of the adsorption tower. Table 5 Changes in the concentration of impurities in the outlet of the decomposition tube and the outlet of the adsorption tower (Example 1) _ The change in the concentration of the impurities (mass ppm) after each QS time CFC- CFC- HCFC- HCFC- CFC-114 HFC- FC- (time ) 217ba 217ca 124 124a 227ea C1316 supply test 350 20 10 10 10 0 0 material decomposition tube 5 0 0 0 0 57 121 outlet 10 0 0 0 0 0 58 99 15 0 0 0 0 0 43 29 adsorption tower 5 0 0 0 0 0 0 0 Outlet 10 0 0 0 0 0 0 0 15 15 0 0 0 0 0 0 0 The crude octafluorocyclobutane began to flow for 2 hours, and after 5 hours, the octafluorocyclobutane at the outlet of the adsorption tower was adsorbed. CFC-2 1 7b a Concentration Variation Paper Size Applies Chinese National Standard (CNS) A4 Specification (21〇 &gt; &lt; 297mm) I Binding Line (Please read the precautions on the back before filling this page) -34 -Printed by the Consumers' Cooperative of the Jiuzou Intellectual Property Bureau 1243809 A7 B7 V. Description of the invention (full FC and the conversion to adsorption of FC FC-2 1 7 ba are shown in Table 8) The time of 1 ppm fluorocarbon impurity is the adsorption conversion time, and the circulation time is CFC-2 1 7 ba It is the removal amount of CFC_217ba. When the ferric oxide used is r-Fe2O3 (Example 2) and when the alkaline earth metal compound used is CaC03 (Example 3), for CFC — 217ba The removal amount is highly efficient, so cyclobutane octafluoride can be purified. Comparative Example 1 The conditions of Example 1 are the same except that there is no step of decomposing the carbon fluoride impurities in the crude cyclobutane octafluoride with an impure decomposition agent. Similarly, the concentration of impurities before and after passing through activated carbon was quantified by gas chromatography. Also, octafluorocyclobutane began to circulate for 5 hours, 10 hours, and 15 hours after the octafluorocyclobutane at the outlet of the adsorption tower. The analysis results of the impure carbon fluoride are shown in Table 6. CFC — 217ba and CFC — 217ca began to circulate with cyclobutane octafluoride at the same time that they began to circulate. Therefore, when only the adsorbent is used, CFC — 2 cannot be removed by adsorption. 1 7b a &amp; CFC- 2 1 7 ca ° Removal amount of HCFC — 124, HCFC — 124a and CFC — 1 14 when using the refining method of the present invention (Example 1) This paper standard applies Chinese National Standard (CNS) A4 Specifications (210X297 mm) 4 Order Line (Read the back of the precautions to fill out this page) -35-1243809

7 7 A B 五、發明説明（全 及’僅利用吸附精製時（比較例1 )之去除量如表7所示 〇 又’以吸附塔出口之八氟化環丁烷中各不純物濃度爲 1質量P p m之時間爲吸附轉效點，且以此時爲止之各不 純物流通量爲去除量。由實施例1及比較例1之結果得知 ，僅利用吸附雖可去除HCFC - 1 24，HCFC — 1 2 4 a及C F C - 1 1 4，但如實施例1般吸附前加入 分解步驟時，可使HCFC— 124，HCFC — 1 24 a及CFC - 1 1 4本身分解而完全去除，因此， 比目前吸附精製法更有效提高去除量。 表6 吸附塔出口之各不純物濃度變化（比較例1 ) 經過時間 各不純物濃度化（質量p p m ) (Hr) CFC- CFC- HCFC-124 HCFC- CFC-114 217ba 217ca 124a 供給試料 350 20 10 10 10 5 350 20 0 0 0 10 350 20 0 0 0 15 350 20 0 0 9 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I 裝 訂 線 (請先閲讀背面之注意事項再填寫本頁) -36- 1243809 A7 ____B7五、發明説明（如 表7 HCfc- 124，HCFC- 124a 及 CFC-ϋ4之去除量 ------* · 一 .…— 氟化碳不純物去除量（g) HCFC-124 HCFC-124a CFC-114 例1 7.0 7.0 2.3 生里例1 3.5 3.5 1.3 暧齊郎皆慧时產苟員工消費合作社印製 比較例2至4 除了使用之不純物分解劑爲r _ F e〇〇Η = 1 〇 〇 質量％ (比較例2) ，7_1?62〇3=1〇〇質量％(比 較例3) ，〇3(〇1^)2=1〇〇質量％(比較例4)外 ，其他同實施例1至3之條件進行試驗。又，以吸附塔出 口驗出八氟化環丁烷中氟化碳不純物濃度爲1質量P pm 之時間爲吸附轉效點。 結果八氟化環丁烷開始流通起2小時，5小時後，吸 附塔出口之八氟化環丁烷中CFC - 2 1 7b a之濃度變 化及吸附轉效爲止之CFC - 2 1 7b a去除量如表8所 示。 僅利用三氧化二鐵（比較例2，3 )時，將無法保持 不純物分解劑之形狀而崩解，因此C F C - 2 1 7 b a之 吸附轉效點較早。又，僅利用鹼土類金屬化合物（比較例 4)時，幾乎無法進行CFC- 2 1 7b a之分解反應， 故CFC - 2 1 7b a去除量極少。因此，除非使用以適 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) •裝. 訂 線 -37- 1243809 A7 B7 五、發明説明（釦 參考例1及2 除了不純物分解管中分解溫度外，其他同實施例1之 條件進行試驗。7 7 AB V. Description of the invention (the total and 'removal amounts when using only adsorption purification (Comparative Example 1) are shown in Table 7' and the concentration of each impurity in cyclobutane octafluoride at the exit of the adsorption tower is 1 mass The time of P pm is the adsorption conversion point, and the flux of each impure stream up to this time is the amount of removal. From the results of Example 1 and Comparative Example 1, it is known that HCFC-1 24, HCFC can be removed only by adsorption. 1 2 4 a and CFC-1 1 4, but when the decomposition step is added before adsorption as in Example 1, HCFC-124, HCFC-1 24 a and CFC-1 1 4 can be decomposed and completely removed by themselves. At present, the adsorption purification method is more effective in improving the removal amount. Table 6 Changes in the concentration of each impurity at the exit of the adsorption tower (Comparative Example 1) The concentration of each impurity (mass ppm) over time (Hr) CFC- CFC- HCFC-124 HCFC- CFC-114 217ba 217ca 124a Supply sample 350 20 10 10 10 5 350 20 0 0 0 10 350 20 0 0 0 15 350 20 0 0 9 This paper size applies to China National Standard (CNS) A4 size (210X297 mm) I Binder (please (Please read the notes on the back before filling out this page) -36- 124380 9 A7 ____B7 V. Description of the invention (such as Table 7 Removal of HCfc-124, HCFC-124a and CFC-ϋ4 ------ * · I .... — Removal of fluorocarbon impurities (g) HCFC-124 HCFC -124a CFC-114 Case 1 7.0 7.0 2.3 Case 1 3.5 3.5 1.3 Printed by Comparative Example 2 to 4 by Qiqi Langjie Huishi Production Employee Cooperative Cooperative Except for impure decomposition agent r _ F e〇〇Η = 1 〇 〇mass% (Comparative Example 2), 7_1 to 62〇3 = 100% by mass (Comparative Example 3), 〇3 (〇1 ^) 2 = 100% by mass (Comparative Example 4), other implementations are the same The tests were performed under the conditions of Examples 1 to 3. In addition, the time at which the concentration of the impurity of carbon fluoride in the cyclobutane octafluoride was 1 mass P pm was detected as the adsorption conversion point. As a result, the cyclobutane octafluoride was started. Table 2 shows the change in the concentration of CFC-2 1 7b a in the octafluorocyclobutane at the outlet of the adsorption tower and the amount of CFC-2 1 7b a removal until the conversion efficiency after 2 hours from the circulation. When using ferric oxide (Comparative Examples 2, 3), the shape of the impurity decomposer cannot be disintegrated, so the adsorption conversion point of CFC-2 1 7 ba is earlier. In addition, when only alkaline earth metal compounds (Comparative Example 4) were used, the decomposition reaction of CFC-2 1 7b a was almost impossible, so the amount of CFC-2 2 7b a removal was extremely small. Therefore, unless using the Chinese paper standard (CNS) A4 size (210X297 mm) at the proper paper size (please read the precautions on the back before filling this page) • Binding. Thread-37- 1243809 A7 B7 V. Invention Explanation (Refer to Reference Examples 1 and 2 except that the decomposition temperature in the impurity decomposition tube is the same as that of Example 1 for testing.

不純物分解管之分解溫度條件爲2 4 0 °C (參考例1 )，4 0 0 〇C (參考例2 )。 結果八氟化環丁烷開始流通起2小時，5小時及1 〇 小時後，反應管出口之CFC - 2 1 7b a濃度變化如表 9所示。 由試驗結果得知，溫度爲過低之2 4 0 °C時，將無法 提升不純物分解劑之活性而無法進行分解，又，溫度爲^ 高之4 0 0 °C時，會因熱而造成不純物分解劑本身分解’ 因此吸附塔出口之CFC - 2 1 7b a會太早吸附轉效’ 而使C F C — 2 7 1 b a去除量爲幾乎未去除之lmg以 下。 (請先閱讀背面之注意事項再填寫本頁) .裝. 訂 線 唑齊郎时4¾員工消费合ft社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -39- 1243809 A7 B7 五、發明説明（h 表9 唆濟郎智慧財產局8工消资合作社印製 因分解溫度而造成之吸附塔出口的C F C - 2 1 7 b a濃 度變化 經過時間 (時間） CFC-217ba濃度變化（質量ppm) 實施例1 (350〇C ) 參考例1 (240〇C ) 參考例2 (400°C ) 供給試料 350 350 350 2 0 190 225 5 0 325 350 10 0 350 350 I 訂 線 (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（210X297公釐） -40-The decomposition temperature conditions of the impurity decomposition tube are 240 ° C (Reference Example 1) and 400 ° C (Reference Example 2). Results The concentration change of CFC-2 17b at the outlet of the reaction tube was shown in Table 9 2 hours, 5 hours, and 10 hours after the cyclobutane octafluoride began to circulate. It is known from the test results that when the temperature is too low at 240 ° C, the activity of the impurity decomposer cannot be improved and decomposition cannot be performed. When the temperature is ^ high at 400 ° C, it will be caused by heat. The impurity decomposing agent decomposes itself, so the CFC-2 1 7b a at the exit of the adsorption tower will be adsorbed and converted too early, so that the removal amount of CFC-2 7 1 ba is less than 1 mg which is hardly removed. (Please read the precautions on the back before filling out this page). Binding. Zirconium 4¾ Employee Consumption Co., Ltd. Printed on this paper The size of the paper applies to Chinese National Standard (CNS) A4 (210X297 mm) -39- 1243809 A7 B7 V. Description of the invention (h Table 9: CFC-2 1 7 ba concentration change elapsed time (time) printed at the exit of the adsorption tower due to decomposition temperature produced by the Jijilang Intellectual Property Bureau 8 industrial consumer cooperatives CFC-217ba Concentration change (ppm by mass) Example 1 (350 ° C) Reference Example 1 (240 ° C) Reference Example 2 (400 ° C) Sample 350 350 350 2 0 190 225 5 0 325 350 10 0 350 350 I Order (Please read the precautions on the back before filling out this page) The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -40-

Claims (1)

1243809 έ88 ^ ^ ό C8 · D8 六、申請專利範圍 第9 1 1 00390號專利申請案 中文申請專利範圍修正本 民國94年8月s日修正 1 · 一種八氟化環丁烷之精製方法，其特徵爲，加熱 下將含不純物之粗八氟化環丁烷接觸不純物分解劑後，再 接觸吸附劑，而由該粗八氟化環丁烷中實質去除不純物。 2 ·如申請專利範圍第1項之八氟化環丁烷之精製方 法，其中，該不純物分解劑係由氧化鐵及鹼土類金屬化合 物所形成。 3 ·如申請專利範圍第2項之八氟化環丁烷之精製方 法，其中，該氧化鐵爲三氧化二鐵。 4 ·如申請專利範圍第3項之八氟化環丁烷之精製方 法，其中，該三氧化二鐵爲r 一氫氧化氧化鐵及/或r -三氧化二鐵。 5 ·如申請專利範圍第2項之八氟化環丁烷之精製方 法’其中，該鹼土類金屬化合物爲至少一種選自鎂，鈣， 緦及鋇中任何一種鹼土類金屬之氧化物，氫氧化物及碳酸 鹽0 6 ·如申請專利範圍第1項之八氟化環丁烷之精製方 法’其中，該不純物分解劑中，對該不純物分解劑而言， 含有5至40質量％之氧化鐵，60至95質量％，鹼土 類金屬化合物。 7 ·如申請專利範圍第6項之八氟化環丁烷之精製方 法’其中，該不純物分解劑係由平均粒徑1 0 0 // m以下 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先聞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 1243809 Αδ Β8 C8 D8 六、申請專利範圍 之氧化鐵粉末及’平均粒徑1 0 0 e m以下鹼土類金屬化 合物粉末所形成之粒劑。 (請先閲讀背面之注意事項再填寫本頁) 8 .如申請專利範圍第1項之八氟化環丁烷之精製方 法，其中，該不純物分解劑爲平均粒徑0 · 5至1 0 m m 之粒劑。 9 .如申請專利範圍第1項之八氟化環丁烷之精製方 法，其中，將該粗八氟化環丁烷接觸該不純物分解劑之溫 度爲250至380 °C。 i 〇 .如申請專利範圍第‘1項之八氟化環丁烷之精製 方法，其中，該吸附劑爲至少一種選自活性碳，分子舖分 離碳及賦活碳中。 11 .如申請專利範圍第1 0項之八氟化環丁烷之精 製方法，其中，該賦活碳係由，以酸及水洗淨原料碳之步 驟（步驟1 )及，不活性氣流中，以5 0至2 5 0 t加熱 原料碳而對該原料碳進行脫氧處理及/或脫水處理之步驟 (步驟2 )及’不活性氣流中，以5 0 0至7 0 0 加熱 緩濟部智慧財產局員工消費合作社印製 原料碳而對該原料碳進行再碳化處理之於步驟（步驟3 ) 及’含惰性氣體’二氧化碳及水蒸氣之混合氣體中，以 7 0 0至9 0 0 X：加熱原料碳而對原料碳進行賦活化處理 之步驟（步驟4 )所形成之方法而得。 1 2 ·如甲請專利範圍第1 1項之八氟化環丁烷之精 製方法’其中’該原料碳爲，以4 0 0至6 0 0 °C將至少 自W子·殻碳，石碳，木碳及焦瀝青中加熱進行碳化 處理而得者。 私錄尺度適用中關家揉準（CNS) Α4· ( 2igx297公董） 2- 12438〇9 B8 C8 D81243809 έ88 ^ ^ C8 · D8 VI. Application for Patent Scope No. 9 1 1 00390 Chinese Patent Application Amendment Amendment 1 August s of the Republic of China Amendment 1 · A method for refining octafluorocyclobutane, which It is characterized in that the crude octafluorocyclobutane containing impurities is contacted with the decomposer of the impurities under heating and then the adsorbent, and the impurities are substantially removed from the crude octafluorocyclobutane. 2. The method for purifying cyclobutane octafluoride as described in item 1 of the scope of patent application, wherein the impurity decomposition agent is formed of iron oxide and alkaline earth metal compounds. 3. The method for refining cyclobutane octafluoride according to item 2 of the patent application, wherein the iron oxide is ferric oxide. 4. The method for refining cyclobutane octafluoride according to item 3 of the application, wherein the ferric oxide is r-iron hydroxide and / or r-iron trioxide. 5. The method for purifying cyclobutane octafluoride octafluoride according to item 2 of the scope of the patent application, wherein the alkaline earth metal compound is at least one oxide of alkaline earth metal selected from magnesium, calcium, scandium and barium, and hydrogen. Oxides and carbonates 0 6 · According to the method for purifying cyclobutane octafluoride octafluoride according to item 1 of the scope of the patent application, wherein the impure decomposition agent contains 5 to 40% by mass of the impure decomposition agent. Iron, 60 to 95% by mass, alkaline earth metal compound. 7 · If the method for refining cyclobutane octafluoride in item 6 of the scope of the application for patent, wherein the impure decomposition agent is composed of an average particle size of 1 0 0 // m or less, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives to print 1243809 Αδ Β8 C8 D8 6. Patented iron oxide powder and 'average particle size 1 Granules formed from powders of alkaline earth metal compounds below 0 0 em. (Please read the precautions on the reverse side before filling out this page) 8. If the method for purifying octafluorocyclobutane in item 1 of the scope of patent application, the impure decomposition agent has an average particle size of 0.5 to 10 mm Granules. 9. The method for refining cyclobutane octafluoride according to item 1 of the patent application scope, wherein the temperature at which the crude cyclooctafluorooctabutane is contacted with the impurity decomposition agent is 250 to 380 ° C. i. The method for refining cyclobutane octafluoride according to item 1 of the scope of the patent application, wherein the adsorbent is at least one selected from the group consisting of activated carbon, molecular detached carbon, and activated carbon. 11. The method for refining cyclobutane octafluoride according to item 10 of the patent application scope, wherein the activated carbon is composed of a step (step 1) of washing raw carbon with acid and water, and in an inert gas stream, Steps of heating raw material carbon at 50 to 250 t for deoxidizing and / or dehydrating the raw material carbon (step 2) and 'inactive gas flow', heating 500 to 700 Employees of the property bureau consume raw carbon to print and re-carbonize the raw carbon in steps (step 3) and a mixed gas of carbon dioxide and water vapor containing "inert gas" in the range of 70 to 9 0 X: It is obtained by the method formed by the step (step 4) of heating the raw carbon and subjecting the raw carbon to an activation treatment. 1 2 · As described in Article 11 of the patent, the method for refining octafluorinated cyclobutane 'wherein' the raw material carbon is at least 40 W to 6 0 ° C. Carbon, lignin and coke pitch are obtained by heating and carbonizing. The private recording standard is applicable to Zhongguan Jiazheng Standard (CNS) Α4 · (2igx297 public director) 2- 12438〇9 B8 C8 D8 :'中請專利範圍 1 3 .如申請褢利範圍第1 1或1 2項之八氟化環丁 燒之精製方法，其中，酸爲無機酸，且該酸濃度爲1至 1 0 0 Q莫耳/ m 3範圍者。 1 4 ·如申請專利範圍第1 3項之八氟化環丁烷之精 製方法，其中，該酸爲鹽酸及/或硫酸。 1 5 ·如申請專利範圍第1 1項之八氟化環丁烷之精 製方法，其中，結束該步驟2後移行至該步驟3時係於惰 性氣流下，以3 0 〇至5 〇 〇 / h r之速度將經步驟2 的原料碳升溫至5 0 〇至7 〇 〇 °C溫度範圍。 1 6 ·如申請專利範圍第1 1項之八氟化環丁烷之精 製方法，其中，結束該步驟3後移行至該步驟4時係於惰 性氣流下，以1 0 0至2 0 0 t / h r之速度將經步驟3 的原料碳升溫至7 〇 〇至9 0 0 °c範圍。 1 7 .如申請專利範圍第1 1項之八氟化環丁烷之精 製方法，其中，該混合氣體中，對全部混合氣體之體積的 不活性氣體含量爲5 0至8 9體積％，二氧化碳含量爲 1 0至3 0體積％，水蒸氣含量爲1至2 0體積％。 1 8 ·如申請專利範圍第1 1項之八氟化環丁烷之精 製方法，其中，結束該步驟4後係於惰性氣流下，以 2〇0至3 0 0 °C / h r之速度將經步驟4之賦活碳降溫 至常溫。 1 9 .如申請專利範圍第1 1項之八氟化環丁烷之精 製方法，其中，賦活碳之碘吸附量爲7 〇 〇至1 〇 〇〇 m g / g 〇 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先聞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 -3- 1243809 B8 C8 __ D8 — ------------ ' ....... T、申請專利範圍 (請先閱讀背面之注意事項再填寫本頁) 2 0 ·如申請專利範圍第1 1項之八氟化環丁烷之精 製方法’其中，該賦活碳所含鹼金屬之總含量爲1 0〇〇 P P m以下。 2 1 ·如申請專利範圍第2 〇項之八氟化環丁烷之精 製方法’其中，該鹼金屬爲鉀，且賦活碳所含之總含量爲 5 〇 〇 P P m 以下。 2 2 ·如申請專利範圍第1項之八氟化環丁烷之精製 方法’其中，該粗八氟化環丁烷之該不純物含量爲1 0至 1〇，0〇 ◦質量ppm。 2 3 .如申請專利範圍第2 2項之八氟化環丁烷之精 製方法，其中，不純物爲至少一種選自2 —氯一 1 ，1 ， 1 ’ 2，3，3 ，3 - 七氟化丙院，1—氯—1 ，1 ，2 ，2，3，3，3 - 七氟化丙烷，1—氯—1，2，2, 2 -四氟化乙烷，1—氯—1 ，1 ，2 ，2 —四氟化乙烷 ，1 ，2〜二氯一 1 ，1 ，2，2 —四氟化乙烷，六氟化 丙烯及1 Η -七氟化丙烷中之氟化碳。 經濟部智慧財產局員工消費合作社印製 2 4 ·如申請專利範圍第2 3項之八氟化環丁烷之精 製方法，其中，，實質去除不純物之八氟化環丁烷中殘留 的不純物濃度低於1質量p p m。 25 · —種八氟化環丁烷之製造方法，其特徵爲，製 造含不純物之粗八氟化環丁烷後，加熱下將該粗八氟化環 丁烷接觸不純物分解劑，再接觸吸附劑，而得實質去除不 純物之八氟化環丁烷。 2 6 .如申請專利範圍第2 5項之八氟化環丁烷之製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -4 - 1243809 A8 B8 C8 D8 六、申請專利範圍 造方法’其中，含該不純物之粗八氟化環丁烷的製造步驟 爲’將氯二氟化甲烷熱分解。 (請先聞讀背面之注意事項再填寫本頁) 2 7 .如申請專利範圍第2 5或2 6項之八氟化環丁 烷之製造方法，其中，不純物爲至少1種選自2 -氯- 1 ，1 ，1 ，2，3，3 ’ 3 —七氟化丙烷，1—氯—1 ， 1 ’ 2 ，2，3 ，3 ，3 —七氟化丙院，1—氯—1 ，2 ’ 2 ，2 —四氟化乙院，1—氯—1 ，1 ，2 ，2 —四氟 化乙院，1 ，2 —二氯一 1 ，1 ，2 ，2 —四氧化乙院， 六氟化丙烯及1 Η -七氟化丙烷中之氟化碳。 2 8 · —種八氟化環丁烷，其特徵爲，氟化碳所形成 之不純物含量低於0 · 〇〇〇 1質量％，且純度爲 99 . 9999質量％以上。 2 9 ·如申請專利範圍第2 8項之八氟化環丁烷，其 中，氟化碳爲至少1種選自2 —氯—1 ，1 ，1 ，2，3 ，3 ，3 —七氟化丙烷，1 一氯—1 ，1 ，2，2，3， 3 ，3 —七氟化丙烷，1 —氯—1 ，2 ，2，2 —四氟化 乙烷，1—氯一 1 ，1 ，2，2 —四氟化乙烷，1 ，2 — 經濟部智慧財產局員工消費合作社印製 二氯一 1 ，1 ，2，2 -四氟化乙烷，六氟化丙烯及1Η -七氟化丙烷中之氟化碳。 30·—種氣體，其特徵爲，含有含量低於 〇.〇〇01質量％之至少1種選自2 —氯一1 ，1 ，1 ，2，3，3，3 —七氟化丙烷，1—氯—1，1，2， 2 ’ 3 ’ 3 ’ 3 —七氣化丙院，1—氯—1 ’ 2 ’ 2 ’2 一四氟化乙烷，1—氯—1 ，1 ，2 ，2 —四氟化乙烷， 本紙張尺度適用中國國家標準（CNS ) Α4规格（210Χ297公嫠） -5- 1243809 A8 B8 C8 D8 六、申請專利範圍 1 ，2 —二氯—1 ，1 ，2 ，2 -四氟化乙烷，六氟化丙 燒及1 Η -七赢化丙院中之氧化碳所形成之不純物，且純 度爲99 · 9999質量％以上之八氟化環丁院。 3 1 ·如申請專利範圍第3 0項之氣體，其係用於蝕 刻氣體。 3 2 ·如申請專利範圍第3 0項之氣體，其係用於淸 潔用氣體。 (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 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -6-: 'Please request the patent range 1 3. If you apply for the purification method of octafluorocyclobutane roasting item No. 11 or 12 in the scope of application, wherein the acid is an inorganic acid, and the acid concentration is 1 to 1 0 0 Q Mohr / m 3 range. 14. The method for purifying cyclobutane octafluorofluoride according to item 13 of the scope of patent application, wherein the acid is hydrochloric acid and / or sulfuric acid. 1 5. According to the method for purifying cyclobutane octafluorofluoride in item 11 of the scope of patent application, wherein after the step 2 is completed, the process is shifted to the step 3 under an inert gas flow at 300 to 500 / The rate of hr will raise the raw carbon through step 2 to a temperature range of 500 to 700 ° C. 16 · According to the method for purifying cyclobutane octafluorofluoride in item 11 of the scope of patent application, wherein after the completion of step 3, the process is moved to step 4 under an inert gas flow at 100 to 2 0 t The rate of / hr raises the raw carbon through Step 3 to the range of 7000 to 900 ° C. 17. The method for refining cyclobutane octafluoride according to item 11 of the scope of patent application, wherein the mixed gas has an inactive gas content of 50 to 89% by volume with respect to the volume of the entire mixed gas, and carbon dioxide. The content is 10 to 30% by volume, and the water vapor content is 1 to 20% by volume. 18 · If the method for purifying cyclobutane octafluorofluoride in item 11 of the scope of application for patent, wherein after the end of step 4, it is placed under an inert gas stream at a speed of 2000 to 300 ° C / hr. After the activated carbon of step 4 is cooled to normal temperature. 19. The method for refining cyclobutane octafluoride according to item 11 of the scope of patent application, wherein the adsorption amount of iodine to activate carbon is 7000 to 1000 mg / g. This paper standard is applicable to Chinese national standards. (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling out this page), 1T Printed by the Consumer Consumption Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs -3- 1243809 B8 C8 __ D8 — ----- ------- '....... T. Scope of patent application (please read the notes on the back before filling this page) The method for purifying alkanes' wherein the total content of alkali metals contained in the activated carbon is 1000 ppm or less. 2 1. According to the method for purifying cyclobutane octafluoride octafluoride in item 20 of the patent application, wherein the alkali metal is potassium, and the total content of activated carbon is 500 P P m or less. 2 2 · The method for purifying octafluorocyclobutane according to item 1 of the scope of the patent application, wherein the crude octafluorocyclobutane has an impurity content of 10 to 10,000 ppm by mass. 2 3. The method for purifying octafluorocyclobutane according to item 22 of the patent application scope, wherein the impurity is at least one kind selected from 2-chloro-1,1,1,1'2,3,3,3-heptafluoro Chemical House, 1-Chloro-1,1,2,2,3,3,3-Propane Heptafluoride, 1-Chloro-1,2,2,2,2-Tetrafluoroethane, 1-Chloro-1 1,2,2—2-tetrafluoroethane, 1,2 ~ dichloro-1,1,2,2-2-tetrafluoroethane, hexafluorinated propylene and 1 fluorene-propeptafluorinated fluorination carbon. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 4 · If the method for refining octafluorocyclobutane in the scope of patent application No. 23 is used, the concentration of the impurities remaining in the octafluorocyclobutane that substantially removes the impurities Less than 1 mass ppm. 25. A method for producing octafluorocyclobutane, characterized in that after producing crude octafluorocyclobutane containing impurities, the crude octafluorocyclobutane is contacted with an impure decomposition agent under heating and then contacted with an adsorbent. Cyclopentane octafluoride which substantially removes impurities. 2 6. If the scope of the patent application is No. 25, the standard of the paper used for the production of cyclobutane octafluoride shall be Chinese National Standard (CNS) A4 (210X297 mm)-4-1243809 A8 B8 C8 D8. The method 'wherein, the manufacturing step of the crude octafluorocyclobutane containing the impurity is' the thermal decomposition of chlorodifluoromethane. (Please read the precautions on the reverse side before filling out this page) 2 7. For the method of manufacturing octafluorocyclobutane with the scope of patent application No. 25 or 26, at least one of the impurities is selected from 2- Chloro-l, 1,1,2,3,3'3-propane heptafluoride, 1-chloro-1, 1'2, 2,3,3,3-propane heptafluoride house, 1-chloro-1 ， 2 '2 ， 2—Tetrafluoride ethyl academy, 1—Chlorine-1，1,2，2-—tetrafluoroethyl academy, 1,2—dichloro-1，1,2,2，2-tetramethylene tetroxide , Carbon fluoride in propylene hexafluoride and 1 Η-heptafluoride. 28. A cyclobutane octafluoride characterized in that the content of impurities formed by carbon fluoride is less than 0.001 mass% and the purity is 99.9999 mass% or more. 2 9 · According to the 28th item of the scope of patent application for cyclobutane octafluoride, wherein the carbon fluoride is at least one selected from the group consisting of 2-chloro-1,1,1,2,3,3,3-heptafluoro Propane, 1-chloro-1,1,2,2,2,3,3,3-propanefluoride, 1-chloro-1,2,2,2,2-tetrafluoroethane, 1-chloro-1, 1,2,2 — ethane tetrafluoride, 1,2 — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, dichloro-1,1,2,2-ethane tetrafluoride, propylene hexafluoride and 1Η- Carbon fluoride in propane hexafluoride. 30 · —a gas, characterized in that it contains at least one selected from the group consisting of 2-chloro-1,1,1,2,3,3,3-propane heptafluoride with a content of less than 0.0001% by mass, 1-Chloro-1,1,2,2'3'3'3-Seven Gasification C, 1-Chloro-1'2'2'2 Tetrafluoroethane, 1-Chloro-1,1, 2, 2 — Ethylene tetrafluoride, this paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -5- 1243809 A8 B8 C8 D8 6. Application scope of patents 1, 2 —dichloro-1, 1 2,2-Impurities formed by carbon tetraoxide in ethane tetrafluoride, hexafluoride propylene, and 1 Η-Qiyinghua Cingyuan, and purity of 99.9999% by mass or more. . 3 1 · As for the gas in the scope of patent application No. 30, it is used for etching gas. 3 2 · If the gas in the scope of patent application No. 30, it is used for cleaning. (Please read the notes 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) Α4 specification (210 × 297 mm) -6-