201211002 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用以藉由減少其雜質而將含有乙烷及/ 或丙烯、以及異丁烷及/或正丁烷作為雜質之低純度丙烷 高純度化之純化方法及純化裝置。 【先前技術】 液化石油氣（LPG，Liquefied Petroleum Gas)或火力發電 用燃料等中所使用之丙烷通常藉由分餾作為原料之石油而 進行工業純化。因此，通常所普及之丙烷係含有來自原料 之乙烷及/或丙烯、以及異丁烷及/或正丁烷作為雜質，且 其純度為98.5 vol%左右之低純度者。 另一方面，近年來，越來越需要雜質濃度較低之高純度 丙烷。例如，作為高耐壓碳化矽（Sic)半導體之原料，丙烷 舄长不斷&局，為了貫現此種碳化石夕之高耐壓性，較佳 為將丙垸之雜質濃度設為未達10 volppm。 因此，考慮藉由對通常所普及之純度為98 5 v〇1%左右之 低純度丙烷進行蒸餾而純化高純度丙烷。但是，於對低純 度丙烧進行蒸—純化高純度丙烧之情形時，設備之規模 變大且需要大量之能源’尤其於含有丙烯作為雜質之情形 時’因丙燒與丙烯之沸點差較小，故藉由蒸館之純化變得 困再者’ A 了使作為烯烴之丙稀自作為鏈燒烴之丙烧 中分離’已知有使含有硝酸銀之水溶液選擇性地吸收丙稀 之方法（參照專利文糾，但該方法無法使㈣鏈烧煙之丙 烧* '乙燒'異丁烷、正丁烷相互公鉍.^ 156726.doc 201211002 法，亦無法純化為高純度丙烷。 [先行技術文獻] [專利文獻] [專利文獻1]國際專利公開2009/11(M92號 【發明内容】 [發明所欲解決之問題] 先前之純化技術存在如下之問題：無法不利用蒸餾技術 而使低純度丙烷中所包含之作為雜質之乙烷及/或丙稀、 以及異丁烷及/或正丁烷變成極微量，為了獲得高純度丙 烧’設備大規模化且能源成本增加。本發明之目的在於提 供一種可解決此種先前技術之課題的丙烷之純化方法及純 化裝置。 [解決問題之技術手段] 本案發明者等人著眼於構成低純度丙院之丙烧、乙院、 丙烯、異丁烷、正丁烷各自之特性，想到藉由使用分子篩 及活性碳作為吸附劑之純化技術自低純度丙烷純化高純度 丙燒之本發明。 即，若將分子篩之細孔之有效孔徑設定為使異丁烷、正 丁烷之分子進入至細孔内之值，則丙烷分子亦進入至細孔 内，故無法僅藉由分子篩使雜質自丙烷中分離。另一方 面’乙院、丙烯與異丁烷、正丁烷相比，難以吸附於活性 碳上。因此，於僅藉由無分子篩功能之活性碳吸附雜質之 情形時，異丁烷、正丁烷優先吸附於吸附劑上而阻礙乙 燒、丙烯之吸附’故亦無法僅藉由活性碳使雜質自丙烷中 I56726.doc 201211002 分離。尤其’乙燒與異丁院、正丁烧相比分子量較小且對 於活性碳之吸附力較弱，故僅藉由活性碳使雜質自丙烧中 分離較困難》 本發明之方法係一種用以將含有乙烷及/或丙烯、以及 . 異丁烷及/或正丁烷作為雜質之低純度丙烷高純度化之純 化方法’其特徵在於：向吸附器内填充較丙烧優先吸附乙 烷及/或丙烯之分子篩、及較丙烷優先吸附異丁烷及/或正 丁烷之活性碳，繼而，藉由向上述吸附器内導入氣體狀之 上述低純度丙烷，而利用上述分子筛及上述活性碳吸附上 述雜質，繼而，將通過了上述吸附器之氣體作為高純度丙 烧加以回收。 藉此’利用分子篩將與異丁烷、正丁烷相比難以吸附於 活性碳之乙烷及/或丙烯自丙烷中分離。又，異丁烷及/或 正丁烧因分子量及凡得瓦力（van der Waals force)大於丙 烧’故對於活性碳之吸附力較強，因此可利用活性碳使異 丁烷及/或正丁烷自丙烷中分離。藉此，可將通過了吸附 器之氣體作為高純度丙烧加以回收。 本發明之裝置係一種用以將含有乙烧及/或丙稀、以及 異丁烧及/或正丁烷作為雜質之低純度丙烷高純度化之純 化裝置’其特徵在於：具備填充有較丙烷優先吸附乙烷及/ 或丙烯之分子篩、及較丙烷優先吸附異丁烷及/或正丁烷 之活性碳的吸附器，上述吸附器具有連接於上述低純度丙 烧之供給源之氣體導入口、及連接於高純度丙烧之回收容 器之氣體回收口，利用上述分子篩及上述活性碳吸附自上 156726.doc 201211002 述氣體導入口導入至上述吸附器内之氣體狀之上述低純度 丙烧中所包含的上述雜質，藉此將通過了上述吸附器之氣 體作為高純度丙烷經由上述氣體回收口而回收至上述回收 容器内。 根據本發明之裝置’可實施本發明之方法。 上述分子篩較佳為設為4A型。藉此，可使用通用之分子 筛。 於本發明方法中，較佳為自上述吸附器之氣體導入口導 入上述低純度丙烷，並且自上述吸附器之氣體回收口回收 上述高純度丙烷，藉此於超過大氣壓之壓力下吸附上述雜 質，並且回收上述高純度丙烷，於回收上述高純度丙烷之 後，以使上述吸附器之内壓成為大氣壓之方式，經由上述 氣體導入口使上述吸附器之内部與大氣壓區域連通，藉此 將殘存於上述吸附器内之氣體排出至大氣壓區域然後， 於上述吸附器内使内部溫度上升，並且使再生用氣體自上 述氣體回收口朝向上述氣體導入口流通。藉此，可藉由於 超過大氣虔之屋力下吸附雜質而提高吸附效率。又，於藉 由使吸附器之内部與大氣㈣域連通而排出殘存於吸附器曰 内之氣體後’使吸附器之内部溫度上升並使再生用氣體於 吸附器内流通，藉此可使分子篩及活性碳再生。 於此情形時’為了實施本發明之方法，較佳為本發明之 裝置包括··第!連接切換機構，其將上述氣體導入口擇一 地連接於上述低純度丙烧之供給源及大氣㈣射之任一 者；第2連接切換機構，其將上述氣體回收口擇一地連接 156726.doc 201211002 於上述回收容器及再生用氣體之供給源中之任一者；背壓 調整器，其調整上述吸附器之内部壓力；以及溫度調整 器’其調整上述吸附器之内部溫度。 於本發明之方法中，較佳為所獲得之高純度丙烷之純度 為99.9 vol%以上，更佳為99.99 v〇l%以上。例如，於將所 回收之上述高純度丙烷用作碳化矽半導體之原料方面，更 佳為所回收之上述高純度丙烷之純度為99 999 v〇1%以上。 [發明之效果] 根據本發明，可提供一種用以自低純度丙烷獲得高純度 丙院之簡便、能源利用效率優異、且於工業上有利之方法 及裝置，可將所獲得之高純度丙烷用作碳化矽半導體之原 料。 【實施方式】 圖1所示之丙烷之純化裝置丨係用以將含有乙烷及/或丙 烯、以及異丁烷及/或正丁烷作為雜質之低純度丙烷高純 度化者，其包括具有第1吸附塔2a及第2吸附塔2b之吸附器 2°於第1吸附塔2a内填充有較丙烷優先吸附乙烷及丙烯之 分子筛α。於第2吸附塔2b内填充有較丙烷優先吸附異丁烷 及正丁烷之活性碳β。該低純度丙烷只要含有乙烷及/或丙 烯、以及異丁烷及/或正丁烷作為雜質即可，其純度並無 特別限定，但較佳為設為95〜99 vol%，通常可使用藉由分 顧石油而進行工業純化之純度為98.5 vol%以下之低純度丙 炫* °所獲得之高純度丙烷之純度只要高於作為純化對象之 低純度丙烷’則並無特別限定，但較佳為99 9 ν〇ι。/。以上， 156726.doc 201211002 更佳為99.99 vol%以上，於用作碳化矽半導體之原料方 面，更佳為設為99.999 vol°/。以上。 將填充於第1吸附塔2a内之分子篩α之細孔的有效孔徑設 定為使乙烷分子及丙烯分子進入至細孔内，並且使丙燒分 子不進入至細孔内之值，藉此可使乙烷及丙烯較丙烷優先 吸附於分子篩α上。本實施形態之分子篩〇1被設為4八型，藉 此分子篩α之細孔之有效孔徑被設為〇 4 nm (4Α)。作為分 子篩α，例如可使用分子篩活性碳或分子篩沸石，特佳為 使用乙烷及丙烯之吸附速度較快之分子篩活性碳。再者， 分子篩《之細孔之有效孔徑若成為〇3 nm，則無法使乙烷 分子進入至細孔内，若成為〇 5 nm，則異丁烷分子及正丁 烷分子亦可進入至細孔内。因此，於使用4A型以外之分子 篩α之情形時，只要以可取得根據尺寸挑選分子之分子篩 功能之方式，將細孔之有效孔徑設定為〇 3 nm〜〇 5 nm之 間，即，使乙烧分子及丙烯分子進入至細孔内，並且使丙 烷分子不進入至細孔内之均勻化之值即可。分子篩α之形 態並無特別限定，例如可設為粒狀或顆粒狀。又，於低純 度丙烷中含有乙烷及丙烯中之一者作為雜質之情形時，分 子篩α之細孔之有效孔徑只要設定為使該一者的分子進入 至細孔，並且使丙烷分子不進入至細孔内之均勻化之值即 可，可藉由設定為〇.4 nm而使用4Α型之分子篩α。 填充於第2吸附塔2b中之活性碳仏要具有較丙烧優先吸 附異丁烧及正T烧之特性即可’較佳為細孔徑未被均句 化、不取得分子筛功能，且細孔之平均有效孔徑為0.5 nm 156726.doc 201211002 以上。不取得分子㈣能之通常之活性碳的細孔之平均有 效孔徑為0.5 nm以上’可使異丁烷及正丁烷之分子進入至 、田孔内X，為了防止雜質混入至高純度丙烧中，較佳為 使用未添加有酸、驗等化學品者作為活性別，例如可使 用椰叙活性碳或煤質活性碳。活性碳0之形態並無特別限 定，例如可設為粒狀或顆粒狀。再者，活性碳陆並非對 乙烧'丙缔、丙烧、異丁院、及正丁统取得分子筛功能 者，則亦可使其細孔徑均勻化。該情形下之活性碳p之細 孔的有效孔徑較佳為以異丁烧及正丁烧之各分子可進入至 細孔内之方式，設為 0.5 nm以上。 第1吸附塔2a及第2吸附塔2b係串聯地進行配管連接。設 置於第1吸附塔2a上之氣體導入口 2c係經由開關閥3、流量 調整器4、壓力調整器5、開關閥6而與低純度丙烧之供給 源7進行配管連接。設置於第2吸附塔孔上之氣體回收口^ 係經由調整吸附器2之内部壓力之背壓調整器9、開關閥n 而連接於高純度丙烷之回收容器12。於各吸附塔2a、“上 設置有作為用以調整吸附器2之内部溫度之溫度調整器的 電加熱器16a、16b。設置有測定各吸附器2之内部溫度之 溫度計17a、17b。設置有測定氣體回收口 2d與背壓調整器 9間之壓力之壓力計2 0。背壓調整器9與開關閥11之間係經 由開關閥21而與大氣壓區域連通。設置有對回收容器I〗内 之高純度丙烷進行加熱或冷卻之恆溫水循環裝置24。 氣體導入口 2c係經由開關閥13而與大氣壓區域連通。藉 此，開關閥3、開關閥1 3構成將氣體導入口 2c擇一地連接 156726.doc 201211002 於低純度丙烷之供給源7、回收容器12、及大氣壓區域中 之任一者的第1連接切換機構。 氣體回收口 2d係經由開關閥18而連接於再生用氣體供給 源19。藉此，開關閥丨丨、開關閥18構成將氣體回收口 2(1擇 一地連接於回收容器12及再生用氣體之供給源19中之任一 者的第2連接切換機構。 根據上述純化裝置1，可實施如下之純化方法：將由供 給源7所供給之氣體狀之低純度丙烧自氣體導入口 &導入 至吸附器2内’於第1吸附塔2a中藉由分子篩a而吸附乙院 及/或丙烯’於第2吸附塔2b中藉由活性碳β而吸附異丁烷 及/或正丁烷，然後將通過了吸附器2之氣體作為高純度丙 烧自氣體回收口 2d回收至回收容器12内，藉此將低純度丙 炫高純度化。 為了有效利用作為吸附劑之分子篩α及活性碳(3之吸附容 量’較佳為將吸附器2中之吸附壓力設為丙烷於常溫下不 會液化之超過大氣壓之壓力，例如以錶壓計設為〇 5〜〇 6 Mpa左右。因此，於本實施形態中，最初進行如下之初始 吸附步驟：藉由低純度丙烷之導入而使吸附器2内之麼力 變成特定值，且將於後述之再生步驟中使用之再生用氣體 自吸附器2内排出。即，於初始吸附步驟中，打開開關閥 3、6、21，並關閉開關閥11、13、18，藉由流量調整器4 而調整低純度丙烷之流量，藉由壓力調整器5而調整壓 力，藉由電加熱器16a、16b而使吸附器2内變成室溫，藉 由背壓調整器9而將吸附器2内之壓力設定為吸附壓力。使 I56726.doc 10· 201211002 藉由壓力調整器5所調整之低純度丙烷之壓力高於藉由背 壓調整器9所設定之吸附器2内之壓力。藉此，向吸附器2 内導入低純度丙烧’並經由開關閥21而排出吸附器2内之 再生用氣體。較理想的是藉由該初始吸附步驟，.於吸附器 2内再生用氣體濃度為1〇 voippm以下、且剩餘由低純度丙 烧填滿。該吸附器2内之再生用氣體於接下來之純化步驟 中到達回收容器12内’但藉由純化之進行而變得稀薄且濃 度降低，因此不需要分離再生用氣體之步驟。 若初始吸附步驟結束’則關閉開關閥21，並打開開關閥 11，藉由壓力調整器5而將由供給源7所供給之低純度丙烧 之壓力調整為預先設定之值，藉由流量調整器4而調整流 量。使藉由壓力調整器5所調整之低純度丙烷之壓力高於 藉由背壓調整器9所設定之吸附器2内之壓力。因此，進行 如下之純化步驟：將低純度丙烧自氣體導入口 2c導入至吸 附器2内，於吸附器2内，在超過大氣壓之壓力下利用分子 篩α及活性碳β吸附低純度丙烧中所包含之雜質，然後將通 過了吸附器2之氣體作為高純度丙烷回收至回收容器12 内。利用恆溫水循環裝置24對回收容器12内之高純度丙烧 進行冷卻，藉此使回收容器12内之壓力低於由壓力計20所 指示之吸附器2内之壓力。 純化步驟係於吸附器2内之吸附劑喪失所期望之吸附功 能而開始失效之前結束。該開始失效之前的時間只要藉由 實驗而預先求出即可。若純化步驟結束，則關閉開關閥 3、6、11。其後，藉由打開開關閥13，吸附器2之内部經 156726.doc 201211002 由氣體導入口 2c而與大氣壓區域連通。藉此’將殘存於吸 附器2内之氣體排出至大氣壓區域，直至吸附器2内之壓力 成為大氣壓’並進行大氣壓清洗步驟。 大氣壓清洗步驟結束之後，一面利用電加熱器l6a、i6b 使吸附器2之内部溫度上升，一面利用溫度計i7a、i7b進 打確認。又，藉由打開開關閥18，將來自供給源19之再生 用氣體自氣體回收口 2d導入至吸附器2内，然後自氣體導 入口 2c排出至大氣壓區域。藉此，進行在與純化步驟中之 低純度丙院之流動方向相反的方向上，使再生用氣體於吸 附器2内流通之再生步驟。#生步冑中之吸附器2内之溫度 較佳為200°C〜30(TC，更佳為設為25〇t左右。若該溫度未 達200°C，則再生用時間變長，若超過3〇〇(>c，則存在能源 成本上升，並且分子篩活性碳β發生粉化之可能性。若 將自氣體導入口 2c排出之再生用氣體中所包含之各種雜質 的濃度變成50 ppm以下，則可使吸附容量恢復至分子篩α 及活性碳β之初始吸附容量之9〇%以上。如此，吸附容量 恢復之前之再生時間會根據再生用氣體之流量、雜質之吸 附量、吸附器2内之溫度而變動，因此較佳為以實驗方式 求出。再者，作為再生用氣體，較佳為使用對於再生步驟 中所接觸之丙烷、分子篩α、活性碳β、純化裝置〗等不具 有活性之氣體，例如氦氣或氬氣等惰性氣體。若再生步驟 、’·°束，則關閉開關閥13、1 8。其後，使吸附器2内之溫度 下降至至溫為止，而返回至上述初始吸附步驟。 根據上述實施形態，利用分子篩α將低純度丙烷中所含 156726.doc 201211002 有之雜質之中，與異丁烷、正丁烷相比難以吸附於活性碳 之乙烷及/或丙烯自丙烷中分離，又，利用活性碳β將異丁 烷及/或正丁烷自丙烷中分離，藉此可將通過了吸附器2之 氣體作為高純度丙烧加以回收。由於該分子篩α設為4Α 型，故可使用通用之分子篩。又，藉由於超過大氣壓之壓 力下吸附雜質，可提高吸附效率，於分子篩α及活性碳β之 吸附能力下降之情形時，藉由使吸附器2之内部與大氣壓 區域連通，而將殘存於吸附器2内之氣體排出，其後，使 吸附器2之内部溫度上升並使再生用氣體於吸附器2内流 通’藉此可使分子篩α及活性碳β再生。 [實施例1] 使用上述實施形態之純化裝置1，於以下之條件下自低 純度丙烧純化tfj純度丙烧。 第1吸附塔2a係設為直徑為28.4 mm、高度為1000 mm之 圓管狀，且自其下端至980 mm之位置為止填充有分子篩 α。使用直徑為2.3 mm之4A型粒狀分子篩活性碳（japan201211002 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a low purity for containing ethane and/or propylene, and isobutane and/or n-butane as impurities by reducing impurities thereof. A purification method and a purification device for purifying a propane. [Prior Art] Propane used in liquefied petroleum gas (LPG, Liquefied Petroleum Gas) or a fuel for thermal power generation is usually industrially purified by fractionating petroleum as a raw material. Therefore, the propane which is generally used generally contains ethane and/or propylene derived from a raw material, and isobutane and/or n-butane as impurities, and has a purity of about 98.5 vol%. On the other hand, in recent years, high-purity propane having a low impurity concentration has been increasingly required. For example, as a raw material of a high-resistance tantalum carbide (Sic) semiconductor, the propane ruthenium is continuously & in order to achieve high carbon pressure resistance of the carbonized stone, it is preferable to set the impurity concentration of the bismuth bismuth to less than 10 volppm. Therefore, it is considered to purify high-purity propane by distillation of a generally-purified low-purity propane having a purity of about 98 5 v 〇 1%. However, in the case of steaming-purifying high-purity propylene burning of low-purity propylene, the scale of the equipment becomes large and a large amount of energy is required, especially when propylene is contained as an impurity, because of the difference in boiling point between propylene and propylene. Small, so it is difficult to purify by the purification of the steaming hall. 'A. The separation of propylene as an alkene from the firing of a chain of hydrocarbons. A method for selectively absorbing propylene by an aqueous solution containing silver nitrate is known. (Refer to the patent text, but this method can not make the (four) chain burning of the burning of the burning * 'B-burning' isobutane, n-butane mutual public. ^ 156726.doc 201211002 method, can not be purified into high-purity propane. [Provisional Technical Documents] [Patent Document] [Patent Document 1] International Patent Publication No. 2009/11 (M92) [Disclosure of the Invention] [Problems to be Solved by the Invention] The prior purification technique has the following problems: it cannot be made without using distillation technology. The ethane and/or propylene as an impurity contained in the low-purity propane and the isobutane and/or n-butane become extremely small, and the apparatus is large-scale and the energy cost is increased in order to obtain high-purity propylene. Purpose Provided to provide a purification method and a purification apparatus for propane which can solve the problems of the prior art. [Technical means for solving the problem] The inventors of the present invention have focused on the formation of a low-purity propylene, a hospital, a propylene, an butyl The characteristics of each of alkane and n-butane are considered to be the purification of high-purity propane from low-purity propane by a purification technique using molecular sieves and activated carbon as an adsorbent. That is, if the effective pore diameter of the pores of the molecular sieve is set to When the molecules of isobutane and n-butane enter the pores, the propane molecules also enter the pores, so that the impurities cannot be separated from the propane by only the molecular sieve. On the other hand, 'B-yard, propylene and different Butane and n-butane are difficult to adsorb on activated carbon. Therefore, when only the activated carbon is adsorbed by the activated carbon without molecular sieve function, isobutane and n-butane are preferentially adsorbed on the adsorbent and hinder B. The adsorption of propylene and propylene is not able to separate impurities from propane by I56726.doc 201211002 only by activated carbon. In particular, 'Ethylene-Baked is smaller than Isomity and n-butadiene. The adsorption of carbon is weak, so it is difficult to separate the impurities from the propylene by only the activated carbon. The method of the present invention is a method for containing ethane and/or propylene, and isobutane and/or positive A purification method for purifying low-purity propane as a impurity, characterized in that: the adsorber is filled with a molecular sieve which preferentially adsorbs ethane and/or propylene, and preferentially adsorbs isobutane and/or is more than propane. Activated carbon of butane, and then introducing the gaseous low-purity propane into the adsorber, and adsorbing the impurities by the molecular sieve and the activated carbon, and then passing the gas passing through the adsorber as high-purity C This is burned and recovered. Thereby, the molecular sieve is used to separate ethane and/or propylene which are difficult to adsorb to activated carbon from isobutane and n-butane from propane. Moreover, the molecular weight of isobutane and/or n-butadiene and the van der Waals force are higher than those of activated carbon, so the adsorption of activated carbon is stronger, so that activated carbon can be used to make isobutane and/or N-butane is separated from propane. Thereby, the gas that has passed through the adsorber can be recovered as high-purity acrylic. The apparatus of the present invention is a purification apparatus for purifying low-purity propane containing ethylene and/or propylene, and isobutylidene and/or n-butane as impurities, which is characterized in that it is filled with propane. a molecular sieve which preferentially adsorbs ethane and/or propylene, and an adsorber which preferentially adsorbs activated carbon of isobutane and/or n-butane than propane, wherein the adsorber has a gas introduction port connected to a supply source of the low-purity propylene And the gas recovery port connected to the high-purity propylene-fired recovery container, wherein the molecular sieve and the activated carbon are adsorbed into the gas-like low-purity propylene burned into the adsorber from the gas introduction port of 156726.doc 201211002 The impurities contained therein are used to collect the gas that has passed through the adsorber as high-purity propane into the recovery container through the gas recovery port. The method according to the invention can be practiced in accordance with the invention. The above molecular sieve is preferably set to the 4A type. Thereby, a general molecular sieve can be used. In the method of the present invention, preferably, the low-purity propane is introduced from a gas introduction port of the adsorber, and the high-purity propane is recovered from a gas recovery port of the adsorber, thereby adsorbing the impurities at a pressure exceeding atmospheric pressure. And recovering the high-purity propane, and after recovering the high-purity propane, the inside of the adsorber is communicated with the atmospheric pressure region via the gas introduction port so that the internal pressure of the adsorber becomes atmospheric pressure, thereby remaining in the above The gas in the adsorber is discharged to the atmospheric pressure region, and then the internal temperature is raised in the adsorber, and the regeneration gas is caused to flow from the gas recovery port toward the gas introduction port. Thereby, the adsorption efficiency can be improved by adsorbing impurities under the force of the atmosphere. Further, after the inside of the adsorber is communicated with the atmosphere (4), the gas remaining in the adsorber crucible is discharged, and the internal temperature of the adsorber is increased, and the regeneration gas is circulated in the adsorber, whereby the molecular sieve can be made. And activated carbon regeneration. In this case, in order to carry out the method of the present invention, it is preferable that the apparatus of the present invention includes a first connection switching mechanism that selectively connects the gas introduction port to the supply source of the low-purity propylene and the atmosphere (4) And a second connection switching mechanism that selectively connects the gas recovery port to any one of 156726.doc 201211002 in the supply container of the recovery container and the regeneration gas; and the back pressure regulator adjusts The internal pressure of the above adsorber; and the temperature regulator 'which adjusts the internal temperature of the above adsorber. In the method of the present invention, it is preferred that the purity of the obtained high-purity propane is 99.9 vol% or more, more preferably 99.99 v〇l% or more. For example, in the case where the above-mentioned high-purity propane recovered is used as a raw material of a niobium carbide semiconductor, it is more preferable that the purity of the above-mentioned high-purity propane recovered is 99 999 v〇1% or more. [Effect of the Invention] According to the present invention, it is possible to provide a method and apparatus for obtaining high-purity propylene from a low-purity propane, which is excellent in energy utilization efficiency and industrially advantageous, and can be used for the high-purity propane obtained. Used as a raw material for tantalum carbide semiconductors. [Embodiment] The propane purification apparatus shown in Fig. 1 is for purifying a low-purity propane containing ethane and/or propylene, and isobutane and/or n-butane as impurities, and includes The adsorber 2 of the first adsorption tower 2a and the second adsorption tower 2b is filled with a molecular sieve α which preferentially adsorbs ethane and propylene than propane in the first adsorption tower 2a. The second adsorption column 2b is filled with activated carbon β which preferentially adsorbs isobutane and n-butane than propane. The low-purity propane is not particularly limited as long as it contains ethane and/or propylene, and isobutane and/or n-butane as impurities, but is preferably 95 to 99 vol%, and is usually used. The purity of the high-purity propane obtained by industrially purifying the purity of 98.5 vol% or less by the petroleum is not particularly limited as long as the purity of the high-purity propane obtained by the purification is higher than that of the low-purity propane to be purified. Good for 99 9 ν〇ι. /. Above, 156726.doc 201211002 is more preferably 99.99 vol% or more, and is preferably used as a raw material for a tantalum carbide semiconductor, and is preferably set to 99.999 vol°/. the above. The effective pore diameter of the pores of the molecular sieve α filled in the first adsorption tower 2a is set such that the ethane molecules and the propylene molecules enter the pores, and the molecules of the molecules are not allowed to enter the pores, thereby Ethane and propylene are preferentially adsorbed on the molecular sieve α than propane. The molecular sieve 〇1 of the present embodiment is set to a type of eight, whereby the effective pore diameter of the pores of the molecular sieve α is set to 〇 4 nm (4 Α). As the molecular sieve α, for example, molecular sieve activated carbon or molecular sieve zeolite can be used, and particularly preferred is molecular sieve activated carbon which uses ethane and propylene at a relatively fast adsorption speed. Furthermore, if the effective pore size of the pores of the molecular sieve is 〇3 nm, the ethane molecules cannot enter the pores. If it becomes 〇5 nm, the isobutane molecules and n-butane molecules can also enter the fine Inside the hole. Therefore, in the case of using the molecular sieve α other than the 4A type, the effective pore diameter of the pores is set to be between 〇3 nm and 〇5 nm in such a manner that the molecular sieve function of selecting molecules according to the size can be obtained, that is, the The burned molecules and the propylene molecules enter the pores, and the propane molecules do not enter the value of homogenization into the pores. The form of the molecular sieve α is not particularly limited, and may be, for example, granular or granular. Further, when low-purity propane contains one of ethane and propylene as an impurity, the effective pore diameter of the pores of the molecular sieve α is set such that the molecules of the one enter the pores, and the propane molecules are not allowed to enter. The value of homogenization into the pores can be used, and the molecular sieve α of the 4 Α type can be used by setting it to 〇.4 nm. The activated carbon ruthenium filled in the second adsorption tower 2b has the characteristics of preferentially adsorbing the isobutyl sinter and the positive T sinter prior to the propylene burning. It is preferable that the pore diameter is not uniform, the molecular sieve function is not obtained, and the pores are obtained. The average effective pore size is 0.5 nm 156726.doc 201211002 or more. The average effective pore diameter of the pores which do not obtain the usual (4) energy of the activated carbon is 0.5 nm or more 'to allow the molecules of isobutane and n-butane to enter the X hole in the field, in order to prevent the impurities from being mixed into the high-purity Preferably, those who do not add an acid, a test or the like are used as the activity, and for example, coconut activated carbon or coal activated carbon can be used. The form of the activated carbon 0 is not particularly limited, and for example, it may be in the form of granules or granules. Furthermore, activated carbon is not the same as the molecular sieve function of B-Boiler's B-, C-, D-Ding, and Ding Ding, and it can also make the pore diameter uniform. The effective pore diameter of the pores of the activated carbon p in this case is preferably 0.5 nm or more in such a manner that each of the molecules of the isobutadiene and the n-butadiene can enter the pores. The first adsorption tower 2a and the second adsorption tower 2b are connected in series by piping. The gas introduction port 2c provided in the first adsorption tower 2a is connected to the supply source 7 of the low-purity propylene gas via the on-off valve 3, the flow rate regulator 4, the pressure regulator 5, and the on-off valve 6. The gas recovery port provided in the second adsorption column hole is connected to the high-purity propane recovery container 12 via a back pressure regulator 9 and an on-off valve n that adjust the internal pressure of the adsorber 2. The electric heaters 16a and 16b which are temperature regulators for adjusting the internal temperature of the adsorber 2 are provided in each adsorption tower 2a. The thermometers 17a and 17b which measure the internal temperature of each adsorber 2 are provided. The pressure gauge 20 for measuring the pressure between the gas recovery port 2d and the back pressure regulator 9. The back pressure regulator 9 and the switching valve 11 communicate with the atmospheric pressure region via the on-off valve 21. The collection container is provided with a container The high-purity propane is heated or cooled by the constant-temperature water circulation device 24. The gas introduction port 2c communicates with the atmospheric pressure region via the on-off valve 13. Thereby, the on-off valve 3 and the on-off valve 13 constitute a gas inlet port 2c. 156726.doc 201211002 The first connection switching mechanism of the low-purity propane supply source 7, the recovery container 12, and the atmospheric pressure region. The gas recovery port 2d is connected to the regeneration gas supply source 19 via the on-off valve 18. Thereby, the on-off valve 丨丨 and the on-off valve 18 constitute a second connection switching mechanism that connects the gas recovery port 2 (one of the supply ports 19 to the recovery container 12 and the regeneration gas). According to the above-described purification apparatus 1, a purification method in which a gaseous low-purity propylene gas supplied from a supply source 7 is introduced from a gas introduction port & into a adsorber 2 in a first adsorption tower 2a by a molecular sieve can be carried out a, while adsorbing the hospital and/or propylene' adsorbs isobutane and/or n-butane by the activated carbon β in the second adsorption tower 2b, and then the gas that has passed through the adsorber 2 is burned as a high-purity The recovery port 2d is recovered into the recovery container 12, thereby purifying the low-purity propylene. In order to effectively utilize the molecular sieve α and the activated carbon as the adsorbent (the adsorption capacity of 3 is preferably the adsorption pressure in the adsorber 2) The pressure exceeding the atmospheric pressure at which propane does not liquefy at normal temperature is, for example, about 〇5 to M6 Mpa in terms of gauge pressure. Therefore, in the present embodiment, the initial adsorption step is as follows: by low purity The introduction of propane causes the force in the adsorber 2 to become a specific value, and the regeneration gas used in the regeneration step described later is discharged from the adsorber 2. That is, in the initial adsorption step, the on-off valves 3, 6 are opened. ,twenty one, The switching valves 11, 13, 18 are closed, the flow rate of the low-purity propane is adjusted by the flow regulator 4, the pressure is adjusted by the pressure regulator 5, and the inside of the adsorber 2 is changed to the room temperature by the electric heaters 16a, 16b. The pressure in the adsorber 2 is set to the adsorption pressure by the back pressure regulator 9. The pressure of the low-purity propane adjusted by the pressure regulator 5 is higher than that of the back pressure regulator by I56726.doc 10· 201211002 The pressure in the adsorber 2 is set to 9. The low-purity propylene is introduced into the adsorber 2, and the regeneration gas in the adsorber 2 is discharged through the on-off valve 21. Preferably, the initial adsorption is performed. In step, the concentration of the gas for regeneration in the adsorber 2 is 1 〇 voi ppm or less, and the remaining is filled with low-purity propylene. The regeneration gas in the adsorber 2 reaches the recovery vessel 12 in the subsequent purification step, but is thinned and reduced in concentration by purification, so that the step of separating the regeneration gas is not required. If the initial adsorption step ends, the on-off valve 21 is closed, and the on-off valve 11 is opened, and the pressure of the low-purity C-spin supplied from the supply source 7 is adjusted to a preset value by the pressure regulator 5, by the flow regulator 4 and adjust the flow. The pressure of the low-purity propane adjusted by the pressure regulator 5 is higher than the pressure in the adsorber 2 set by the back pressure regulator 9. Therefore, a purification step is carried out in which low-purity propylene is introduced into the adsorber 2 from the gas introduction port 2, and in the adsorber 2, the molecular sieve α and the activated carbon β are used to adsorb low-purity propane in a pressure exceeding atmospheric pressure. The impurities contained therein are then recovered into the recovery vessel 12 as a high-purity propane gas passing through the adsorber 2. The high-purity propane burn in the recovery container 12 is cooled by the constant-temperature water circulation device 24, whereby the pressure in the recovery container 12 is lower than the pressure in the adsorber 2 indicated by the pressure gauge 20. The purification step ends before the adsorbent in the adsorber 2 loses the desired adsorption function and begins to fail. The time before the start of the failure may be determined in advance by experiments. If the purification step is completed, the on-off valves 3, 6, 11 are closed. Thereafter, by opening the on-off valve 13, the inside of the adsorber 2 is communicated with the atmospheric pressure region via the gas introduction port 2c via 156726.doc 201211002. Thereby, the gas remaining in the adsorber 2 is discharged to the atmospheric pressure region until the pressure in the adsorber 2 becomes atmospheric pressure' and the atmospheric pressure washing step is performed. After the completion of the atmospheric pressure washing step, the internal temperatures of the adsorber 2 are raised by the electric heaters l6a and i6b, and they are confirmed by the thermometers i7a and i7b. Further, by opening the on-off valve 18, the regeneration gas from the supply source 19 is introduced into the adsorber 2 from the gas recovery port 2d, and then discharged from the gas introduction port 2c to the atmospheric pressure region. Thereby, a regeneration step of circulating the regeneration gas in the adsorber 2 in a direction opposite to the flow direction of the low-purity broth in the purification step is performed. The temperature in the adsorber 2 in the step is preferably 200 ° C to 30 (TC, more preferably about 25 〇 t. If the temperature is less than 200 ° C, the regeneration time becomes longer, if When it is more than 3 〇〇 (>c, there is a possibility that the energy cost increases and the molecular sieve activated carbon β is pulverized. The concentration of various impurities contained in the regeneration gas discharged from the gas introduction port 2c becomes 50 ppm. In the following, the adsorption capacity can be restored to 9% or more of the initial adsorption capacity of the molecular sieve α and the activated carbon β. Thus, the regeneration time before the recovery of the adsorption capacity is based on the flow rate of the regeneration gas, the adsorption amount of the impurities, and the adsorber 2 It is preferable to experimentally determine the temperature in the inside. Further, as the gas for regeneration, it is preferable to use propane, molecular sieve α, activated carbon β, purification apparatus, etc. which are contacted in the regeneration step. An active gas such as an inert gas such as helium or argon. If the regeneration step, '·° beam, the switching valves 13 and 18 are closed. Thereafter, the temperature in the adsorber 2 is lowered to the temperature, and then returned. To the above initial adsorption According to the above embodiment, among the impurities of 156726.doc 201211002 contained in the low-purity propane, it is difficult to adsorb to the activated carbon of ethane and/or propylene from isobutane or n-butane by using the molecular sieve α. Separation of propane, and separation of isobutane and/or n-butane from propane by activated carbon β, whereby the gas passing through the adsorber 2 can be recovered as high-purity propane. Since the molecular sieve α is set 4Α type, it is possible to use a general-purpose molecular sieve. Moreover, by adsorbing impurities under a pressure exceeding atmospheric pressure, the adsorption efficiency can be improved, and when the adsorption capacity of the molecular sieve α and the activated carbon β is lowered, the inside of the adsorber 2 is made The gas remaining in the adsorber 2 is discharged in communication with the atmospheric pressure region, and thereafter, the internal temperature of the adsorber 2 is raised and the regeneration gas is circulated in the adsorber 2, whereby the molecular sieve α and the activated carbon β can be made. [Example 1] Using the purification apparatus 1 of the above-described embodiment, the tfj purity was burned from a low-purity propylene burning under the following conditions: The first adsorption column 2a was set to have a diameter of 28.4 mm and a height of 1 It has a round tubular shape of 000 mm and is filled with molecular sieve α from its lower end to 980 mm. The 4A type granular molecular sieve activated carbon (japan) with a diameter of 2.3 mm is used.
Enviro Chemicals製造，CMS-4A-B)作為分子篩 α。第 2吸 附塔2b係設為直徑為28 4 mm、高度為1〇〇〇 mm之圓管 狀，且自其下端至98〇 mm之位置為止填充有活性碳p。使 用粒度為10〜20篩目之椰殼破碎碳（Kuraray Chemical製 造，Kuraray Coal GG)作為活性碳p。 作為初始吸附步驟’將含有未達〇1 v〇lppm之乙烷、未 達0.1 v〇lPPm之丙烯、未達〇」v〇lppm2異丁烷、未達i volppm之正丁烷的高純度丙烷導入至吸附器2内對在蓄 156726.doc -13- 201211002 壓步驟前被設為大氣壓之吸附器2内所填充之作為再生用 氣體的氦氣進行置換，將藉由氣相層析儀·熱導度檢測器 (GC-TCD，Gas Chromatography-Thermal Conductivity Detector)所測定之氦氣濃度變成丨v〇l%以下，並利用背壓 調整器9將兩吸附塔2a、2b内之吸附壓力以錶壓計設定為 0.50 MPa。 其次’作為純化步驟，將含有6868 volppm之乙烧、 3961 volppm之丙稀、2820 volppm之異 丁烧、2210 volppm 之正丁烧的氣體狀之低純度丙烷導入至吸附器2内，純化 高純度丙烧。此時’將壓力調整器5之設定壓以錶壓計設 為0_53 MPa ’將流量調整器4之設定流量於標準狀態下設 為5 70 mL/miη，將兩吸附塔2a、2b内之溫度設為室溫，將 純化時間設為250分鐘。 圖2表示純化步驟中自氣體回收口 2d所回收之純化丙烷 之純度（vol%)的經時變化、及該純化丙烷中所含有之各種 雜質之濃度（v〇lPpm)的經時變化。該純化丙烷之純度與各 種雜質之濃度係藉由氣相層析儀-火焰離子化檢測器⑴匚― FID，Gas Chromatography-Flame I〇nizati〇n Detector)進行 測定。於將各種雜質之濃度之測定值達到1 v〇lppm的時間 點設為針對各種雜質之吸附劑之失效時間點的情形時，關 於自純化開始至失效為止之時間，乙烷為1〇7分鐘，異丁 烷為91分鐘，正丁烷為225分鐘，丙烯於純化時間内未失 效。 根據實施例1，若將純化時間設為91分鐘，則可純化含 156726.doc 14 201211002 有 0.1 volppm之乙烷、未達(u v〇lppn^丙烯、〇 2 v〇ippm 之異丁烧、未達0·1 volppm之正丁烷的純度為99 999 v〇1% 以上之高純度丙烷。該情形時之高純度丙烷之獲得量為 102 g，產率為 51.3%。 [實施例2] 於初始吸附步驟中，藉由背壓調整器9而將吸附壓力設 定為0.60 MPa，於純化步驟中，將壓力調整器5之設定壓 以錶壓計設為0.62 MPa，除此以外，以與實施例1相同之 條件自低純度丙院純化高純度丙炫。 圖3表示純化步驟中自氣體回收口 2d所回收之純化丙烧 之純度（vol%)的經時變化、及該純化丙烷中所含有之各種 雜質之濃度（volppm)的經時變化。該純化丙烷之純度與各 種雜質之濃度係藉由氣相層析儀-火焰離子化檢測器（Gc_ FID)進行測定。於將各種雜質之濃度之測定值達到丄 volppm的時間點設為針對各種雜質之吸附劑之失效時間點 的情形時，關於自純化開始至失效為止之時間，乙烧為 119分鐘，異丁烷為129分鐘，正丁烷為228分鐘丙烯於 純化時間内未失效。 根據實施例2，若將純化時間設為121分鐘，則可純化含 有0.4 V〇lppm之乙烷、未達〇」v〇lppm之丙烯、未達〇」 volppm之異丁烧、未達01 volppm之正丁烷的純度為 99.999 v〇l%以上之高純度丙烷。該情形時之高純度丙烷之 獲得量為135 g，產率為52.6%。 本發明並不限定於上述實施形態或實施例。例如，本發 156726.doc •15- 201211002 明t所應用之低純度丙炫於上述實施例中設為含有乙燒、 丙烯、異丁院、及正丁院作為雜質者，但因低純度丙烧中 之雜質之濃度存在不均，故只要含有乙貌與丙稀中之至少 —者、及正丁烷與異丁烷中之至少—者作為雜質即可。 又，本發明中所應用之低純度丙烷亦可含有乙烷、丙烯、 異丁烷、及正丁烷以外之雜質。於上述實施形態中，於利 用分子篩α吸附乙烷及/或丙烯之後，利用活性碳p吸附異 丁烷及/或正丁烷，但亦可藉由更換第1吸附塔以及第2吸 附塔2b之配置使吸附順序相反。利用分子篩吸附乙烷及/ 或丙烯與利用活性碳吸附異丁烷及/或正丁烷之順序並無 限定。於上述實施形態中，將分子篩α與活性碳0填充至個 別之吸附塔2a、2b中，但亦可利用填充有分子篩及活性碳 之單一之吸附塔構成吸附器。於此情形時，於單一之吸附 塔内分子篩與活性碳可不進行混合而堆積成層狀，亦可進 行混合。 【圖式簡單說明】 圖1係本發明之實施形態之丙烷之純化裝置的構成說明 圖。 圖2係表示本發明之第丨實施例中之丙烷純度之經時變化 及雜質濃度之經時變化的圖。 圖3係表示本發明之第2實施例中之丙烧純度之經時變化 及雜質濃度之經時變化的圖。 【主要元件符號說明】 1 純化裝置 156726.doc -16· 201211002 2 . 吸附器 2a 第1吸附塔 2b 第2吸附塔 2c 氣體導入口 2d 氣體回收口 3 ' 13 開關閥（第1連接切換機構） 4 流量調整器 5 壓力調整器 6 開關閥（第1連接切換機構） 7 丙烧之供給源 9 背壓調整器 11、18 開關閥（第2連接切換機構） 12 回收容器 16a 、 16b 電加熱器（溫度調整器） 19 再生用氣體之供給源 20 壓力計 21 開關閥（第2連接切換機構） 24 循環裝置 a 分子篩 β 活性碳 156726.doc - 17-Manufactured by Enviro Chemicals, CMS-4A-B) as molecular sieve alpha. The second adsorption tower 2b is a circular tube having a diameter of 28 mm and a height of 1 mm, and is filled with activated carbon p from the lower end to a position of 98 mm. As the activated carbon p, coconut shell crushed carbon (manufactured by Kuraray Chemical, Kuraray Coal GG) having a mesh size of 10 to 20 mesh was used. As the initial adsorption step, it will contain ethane of less than 1 v〇lppm, propylene of less than 0.1 v〇l PPm, unpurinated v〇lppm2 isobutane, and high-purity propane of less than i volppm of n-butane. The helium gas as a regeneration gas filled in the adsorber 2 which is set to atmospheric pressure before the pressure step 156726.doc -13 - 201211002 is introduced into the adsorber 2, and is replaced by a gas chromatograph. The concentration of helium measured by a gas-conductivity detector (GC-TCD, Gas Chromatography-Thermal Conductivity Detector) becomes 丨v〇l% or less, and the adsorption pressure in the two adsorption towers 2a, 2b is controlled by the back pressure regulator 9 The gauge is set to 0.50 MPa. Next, as a purification step, a gas-like low-purity propane containing 6868 volppm of ethidium, 3961 volppm of propylene, 2820 volppm of isobutyl bromide, and 2210 volppm of n-butyl sinter is introduced into the adsorber 2 to purify high purity. C-burning. At this time, 'set the pressure regulator 5 to 0_53 MPa by the gauge pressure meter'. Set the flow rate of the flow regulator 4 to 5 70 mL/miη under standard conditions, and set the temperature in the two adsorption towers 2a and 2b. Set to room temperature and set the purification time to 250 minutes. Fig. 2 is a graph showing the temporal change of the purity (vol%) of the purified propane recovered from the gas recovery port 2d in the purification step, and the time-dependent change in the concentration (v〇l Ppm) of various impurities contained in the purified propane. The purity of the purified propane and the concentration of each impurity were determined by a gas chromatograph-flame ionization detector (1) F-FID, Gas Chromatography-Flame I〇nizati〇n Detector). When the time point at which the measured value of the concentration of each impurity reaches 1 v〇lppm is set as the failure time point of the adsorbent for various impurities, the ethane is 1 〇 7 minutes from the start of purification to the time of failure. The isobutane was 91 minutes and the n-butane was 225 minutes. The propylene did not expire during the purification time. According to Example 1, if the purification time is set to 91 minutes, it is possible to purify 156726.doc 14 201211002 with 0.1 volppm of ethane, less than (uv〇lppn^propene, 〇2 v〇ippm of isobutylate, not The purity of n-butane of 0.11 volppm is 99 999 v〇1% or more of high-purity propane. In this case, the yield of high-purity propane is 102 g, and the yield is 51.3%. [Example 2] In the initial adsorption step, the adsorption pressure is set to 0.60 MPa by the back pressure regulator 9, and in the purification step, the set pressure of the pressure regulator 5 is set to 0.62 MPa by the gauge pressure, and other methods are implemented. Purification of high-purity propylene from low-purity propylene by the same conditions as in Example 1. Figure 3 is a graph showing the change in the purity (vol%) of the purified propylene burned from the gas recovery port 2d in the purification step, and the purified propane. The change of the concentration (volppm) of various impurities contained in the time. The purity of the purified propane and the concentration of various impurities are determined by a gas chromatograph-flame ionization detector (Gc_FID). When the measured value of the concentration reaches 丄 volppm, it is set for each In the case of the failure time point of the adsorbent of the impurity, the time from the start of purification to the time of failure was 119 minutes for ethylene, 129 minutes for isobutane, and 228 minutes for n-butane, and propylene did not fail during the purification time. According to Example 2, if the purification time is set to 121 minutes, it is possible to purify ethane containing 0.4 V 〇lppm, propylene which is less than 〇v〇lppm, and bisppm which is less than 〇 volppm, which is less than 01 volppm. The purity of n-butane is 99.999 v〇l% or more. In this case, the yield of high-purity propane is 135 g, and the yield is 52.6%. The present invention is not limited to the above embodiment or example. For example, the low-purity styrene used in the above-mentioned examples is exemplified by the above-mentioned embodiment, which contains ethylene bromide, propylene, isobutylene, and Zhengdingyuan as impurities, but because of low purity. The concentration of the impurities in the propylene is uneven, so that at least one of the acetonitrile and the propylene, and at least one of the n-butane and the isobutane may be contained as an impurity. Further, the present invention is applied. Low purity propane can also contain ethane, propylene, An impurity other than isobutane and n-butane. In the above embodiment, after adsorbing ethane and/or propylene by molecular sieve α, isobutane and/or n-butane are adsorbed by activated carbon p, but it is also possible to borrow The order of adsorption is reversed by the arrangement of the first adsorption tower and the second adsorption tower 2b. The order of adsorption of ethane and/or propylene by the molecular sieve and the adsorption of isobutane and/or n-butane by the activated carbon are not limited. In the embodiment, the molecular sieve α and the activated carbon 0 are filled in the individual adsorption towers 2a and 2b, but the adsorber may be constituted by a single adsorption tower filled with molecular sieves and activated carbon. In this case, the molecular sieve and the activated carbon in a single adsorption column may be stacked in a layered form without mixing, and may be mixed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the configuration of a propane purification apparatus according to an embodiment of the present invention. Fig. 2 is a graph showing changes with time in the purity of propane and changes in the concentration of impurities in the third embodiment of the present invention. Fig. 3 is a graph showing changes with time in the purity of the burnt-through and the change in the concentration of the impurity in the second embodiment of the present invention. [Description of main component symbols] 1 Purification device 156726.doc -16· 201211002 2 . Adsorber 2a First adsorption tower 2b Second adsorption tower 2c Gas introduction port 2d Gas recovery port 3 ' 13 On-off valve (first connection switching mechanism) 4 Flow regulator 5 Pressure regulator 6 On-off valve (1st connection switching mechanism) 7 Supply source of Propylene 9 Back pressure regulator 11, 18 On-off valve (2nd connection switching mechanism) 12 Recycling container 16a, 16b Electric heater (Temperature adjuster) 19 Supply source of regeneration gas 20 Pressure gauge 21 On-off valve (2nd connection switching mechanism) 24 Circulating device a Molecular sieve β Activated carbon 156726.doc - 17-