201217044 六、發明說明： 【發明所屬之技術領域】 本發明係關於玎除去半導體製造等所使用之氮氣、氛 氣等惰性氣體所含之烴類、氫、一氧化碳、二氧化碳、氧 及水之純化方法與其裝置。 【先前技術】 半導體製造步驟中必需要氮氣、氬氣等高純度惰性氣 體。此等惰性氣體一般係以深冷式空氣分離裝置製造。深 冷式空氣分離裝置所製造之惰性氣體中，含有ppm至ppb 等級之曱烷、氫、一氧化碳、二氧化碳、氧、水等不純物。 近年來，隨著半導體之高度集積化，要求半導體製造 步驟所使用之惰性氣體中的不純物濃度為ppb以下。因 此’有必要再純化惰性氣體之原料氣體’但難以有效率的 去除原料氣體中所含有之烴類。 此外’隨著近年來半導體工薇之大規模化，惰性氣體 使用f亦大幅增加。伴隨而來的是進行大型惰性氣體純化 設備之導入，但隨著半導體激熱的價格競爭，強烈要求惰 性氣體純化設備之成本降低。 專利文獻1已揭示將原料氣體中微量不純物除去之純 化方法。於專利文獻1提出藉由觸媒將烴類、一氧化碳、 氧及氫轉換為二氧化碳氣體及水後，以觸媒層除去氧，且 以第-吸著層除去二氧化碳’並以第二吸著層除去水份之 方法。但此方法中，因觸媒與原料氣體反應會產生大量水 份，由此影響而有觸媒層中氧氣除去效率降低之問題。 323444 4 201217044 專利文獻2提出純化原料氣體之其他方法，係使用錯 吸氣劑（zirconium getter)除去不純物之方法。 ° 但因結吸氣劑高價且不可再生，故此方法並不適合大 量原料氣體之純化。 專利文獻3中揭π藉由還原金屬除去原料氣體中的氧 與一氧化碳’接著以沸石（ze〇lite)等吸著劑除去二氧化碳 與水之方法。此方法因可用氫氣再生吸著不純物後之還^ 金屬，故還原金屬可再利用。 但原料氣體中二氧化碳分壓為ppb等級時，沸石之二 氧化碳吸著量會變得非常少。因此，純化大量惰性氣體時 需要大量沸石’此係裝置大型化與成本提升的要因。 專利文獻4中揭示藉由氧化鋅除去原料氣體中之二氧 化碳後’藉由鎳觸媒或銅觸媒去除氧與一氧化碳，再藉由 合成沸石除去水。 此純化方法中，在藉由鎳觸媒除去一氧化碳與氧時， 因觸媒作用而產生微量之二氧化碳。因此，為了再吸著因 觸媒作用而產生之二氧化碳’需充填大量合成沸石。結果 使吸著塔變大，且使惰性氣體純化設備之成本提高。 專利文獻5與專利文獻6中揭示藉由氧化鋁去除原料 氣體中的二氧化碳之方法。因兩方法中之氧化鋁皆含有鹼 金屬、驗土類金屬，故可增加氧化紹之二氧化碳吸著量。 但兩方法除去對象皆為空氣中之二氧化碳，即400ppm左右 之高濃度二氧化碳，對於低濃度二氧化碳之吸著處理並無 檢證。此外，400ppm左右高濃度二氧化碳之吸著處理中， 5 323444 201217044 與氧化鋁相較，沸石吸著較多二氧化碳。故以往之純化裝 置中，二氧化碳吸著劑以使用沸石為主。 上述之先前發明方法中，任一者為了純化大量原料氣 體，皆需要對應之大吸著塔。此外因吸著劑係高價，故製 造成本亦變高。因此冀求有效率的純化大量惰性氣體之方 法。 [先前技術文獻] [專利文獻] [專利文獻1] [專利文獻2] [專利文獻3] [專利文獻4] [專利文獻5] [專利文獻6] 曰本特許第2640513號公報 曰本特許第2741622號公報 曰本特許第2602670號公報 曰本特許第3462604號公報 曰本特開平11-518號公報 日本特開2001-104737號公報 【發明内容】 (發明欲解決之課題） 本發明之課題為在由氮氣或稀有氣體（noble gas)所 成原料氣體之純化中，於除去烴類、氫、一氧化碳、二氧 化碳、氧及水時，可將純化裝置緻密化（compact)、可降低 高價觸媒之充填量、且可降低純化成本。 (解決課題之方法） 為解決相關問題： 第1發明係一種氣體之純化方法，係除去由氮氣或稀 有氣體所構成之原料氣體中之烴類、氫、一氧化碳、二氧 6 323444 201217044 化碳、氧及水之氣體純化方法，此方法具有以下步驟：使 前述原料氣體與觸媒接觸，而使前述烴類、氳及一氧化碳 與氧化性氣體反應，藉此生成二氧化碳與水之步驟；使與 前述觸媒接觸後之前述原料氣體與水份吸著劑接觸，藉以 除去水之步驟；使除去前述水後之前述原料氣體與鎳觸媒 接觸，藉以除去反應殘渣之氧之步驟；以及使除去前述氧 後之前述原料氣體與含有鈉0. 1至10wt%之氧化鋁接觸， 藉以除去二氧化碳之步驟。 第2發明係如第1發明所述之氣體之純化方法，其中， 相對於使在前述觸媒進行反應之烴類、氫及一氧化碳的 量，前述原料氣體中未含有在化學計量法（stoichiometry) 上得以氧化之量以上之氧化性氣體時，則於前述原料氣體 供給氧化性氣體，直到成為化學計量法上得以氧化烴類、 氫及一氧化碳以上的量為止後，使原料氣體與前述觸媒接 觸。 第3發明係如第1或第2發明所述之氣體之純化方 法，其中，前述原料氣體中的二氧化碳分壓為19Pa以下者。 第4發明係如第1至第3發明中任一項所述之氣體之 純化方法，其中，以前述鎳觸媒之體積換算充填量為 Va(L)、以前述氧化鋁之體積換算充填量為Vb(L)時，此等 之充填量比（Va/Vb)係滿足Va/Vb<l之關係者。 第5發明係如第1至第4發明中任一項所述之氣體之 純化方法，其中，前述觸媒係在活性氧化|g、石夕藻土、活 性炭之任一者或兩者以上所構成之擔體，擔載0. 01至5wt 7 323444 201217044 %之Pt、Pd、Ru、Ag、Cu、Μη之任一者或兩者以上而成者。 第6發明係如第1至第5發明中任一項所述之氣體之 純化方法，其中，前述氧化性氣體為氧者。 第7發明係如第1至第6發明中任一項所述之氣體之 純化方法，其中，前述烴類為曱烷者。 第8發明係一種氣體純化裝置，係除去由氮氣或稀有 氣體所構成之原料氣體中之烴類、氫、一氧化碳、二氧化 碳、氧及水之氣體純化裝置，該裝置具有充填觸媒之觸媒 塔；以及設置於前述觸媒塔之下流側，由前述原料氣體流 入側向流出側依序充填水份吸著劑、鎳觸媒以及含有鈉之 氧化銘而成之吸著塔。 (發明之效果） 本發明之氣體純化方法係使氮氣或稀有氣體所成原料 氣體與觸媒接觸，藉此預先使原料氣體中之烴類、氩、及 一氧化碳與氧化性氣體反應而轉換為二氧化碳與水。因此 與不使用觸媒之以往之純化方法相異，可將原料氣體中的 烴類轉換為二氧化碳及水而除去。 使與觸媒接觸後之原料氣體與水份吸著劑接觸，藉此 可除去原料氣體中的水。因此，可防止設置於水份吸著劑 下流側之鎳觸媒因水而降低機能。此外，因使氫及一氧化 碳與氧化性氣體反應，故僅需藉由鎳觸媒除去反應殘渣之 氧。因此，鎳觸媒之充填量只要為僅可除去反應殘潰之氡 的量即可，與以往方法相較可減少充填量。 以往沸石對二氧化碳的吸著量少，雖然Ni觸媒也會 8 323444 201217044[Technical Field] The present invention relates to a method for purifying hydrocarbons, hydrogen, carbon monoxide, carbon dioxide, oxygen, and water contained in an inert gas such as nitrogen or an atmosphere used for semiconductor manufacturing or the like. And its device. [Prior Art] A high-purity inert gas such as nitrogen or argon is required in the semiconductor manufacturing step. These inert gases are typically produced by cryogenic air separation plants. The inert gas produced by the cryogenic air separation unit contains impurities such as decane, hydrogen, carbon monoxide, carbon dioxide, oxygen, and water in a ppm to ppb grade. In recent years, with the high concentration of semiconductors, the concentration of impurities in the inert gas used in the semiconductor manufacturing step is required to be ppb or less. Therefore, it is necessary to purify the raw material gas of the inert gas, but it is difficult to efficiently remove the hydrocarbons contained in the raw material gas. In addition, with the large-scale production of semiconductor workers in recent years, the use of inert gas f has also increased significantly. Accompanying is the introduction of large inert gas purification equipment, but with the price competition of semiconductor heat, the cost of inert gas purification equipment is strongly demanded. Patent Document 1 discloses a purification method for removing trace impurities in a material gas. Patent Document 1 proposes to convert hydrocarbons, carbon monoxide, oxygen, and hydrogen into carbon dioxide gas and water by a catalyst, to remove oxygen by a catalyst layer, and to remove carbon dioxide by a first sorption layer, and to use a second absorbing layer. The method of removing water. However, in this method, a large amount of water is generated by the reaction of the catalyst with the material gas, thereby affecting the problem that the oxygen removal efficiency in the catalyst layer is lowered. 323444 4 201217044 Patent Document 2 proposes another method of purifying a raw material gas, which is a method of removing impurities by using a zirconium getter. ° However, this method is not suitable for the purification of a large amount of raw material gases because the getter is expensive and non-renewable. Patent Document 3 discloses a method of removing oxygen and carbon monoxide in a material gas by a reducing metal and then removing carbon dioxide and water with a sorbent such as zeolite (ze〇lite). This method can be reused because the hydrogen can be regenerated by absorbing the impurities after the impurities are regenerated. However, when the partial pressure of carbon dioxide in the raw material gas is ppb, the amount of carbon dioxide adsorbed by the zeolite becomes very small. Therefore, a large amount of zeolite is required for purifying a large amount of inert gas, which is a factor for increasing the size and cost of the apparatus. Patent Document 4 discloses that after removing carbon dioxide in the material gas by zinc oxide, oxygen and carbon monoxide are removed by a nickel catalyst or a copper catalyst, and water is removed by synthesizing the zeolite. In this purification method, when carbon monoxide and oxygen are removed by a nickel catalyst, a trace amount of carbon dioxide is generated by the action of a catalyst. Therefore, in order to resorb the carbon dioxide generated by the action of the catalyst, a large amount of synthetic zeolite is required to be filled. As a result, the sorption column is made larger, and the cost of the inert gas purification equipment is increased. Patent Document 5 and Patent Document 6 disclose a method of removing carbon dioxide in a raw material gas by alumina. Since the alumina in both methods contains alkali metal and soil-measuring metal, the amount of carbon dioxide adsorbed by the oxidation can be increased. However, both methods remove the carbon dioxide in the air, that is, a high concentration of carbon dioxide of about 400 ppm, which is not verified for the sorption treatment of low-concentration carbon dioxide. In addition, in the adsorption treatment of high concentration carbon dioxide of about 400 ppm, 5 323 444 201217044 compared with alumina, the zeolite absorbs more carbon dioxide. Therefore, in the conventional purification apparatus, the carbon dioxide sorbent is mainly composed of zeolite. In any of the above prior invention methods, in order to purify a large amount of raw material gas, a corresponding large sorption column is required. In addition, due to the high price of the sorbent, the manufacturing cost is also high. Therefore, a method of efficiently purifying a large amount of inert gas is sought. [Prior Art Document] [Patent Document 1] [Patent Document 1] [Patent Document 2] [Patent Document 3] [Patent Document 4] [Patent Document 5] [Patent Document 6] 曰本权第2640513号Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the purification of a raw material gas formed by nitrogen or a noble gas, when a hydrocarbon, hydrogen, carbon monoxide, carbon dioxide, oxygen, and water are removed, the purification device can be compacted, and the high-priced catalyst can be reduced. The amount of filling can reduce the purification cost. (Means for Solving the Problem) In order to solve the related problems, the first invention is a method for purifying a gas by removing hydrocarbons, hydrogen, carbon monoxide, and dioxins in a raw material gas composed of nitrogen or a rare gas; a method for purifying a gas of oxygen and water, the method comprising the steps of: contacting the raw material gas with a catalyst to react the hydrocarbon, hydrazine and carbon monoxide with an oxidizing gas, thereby generating carbon dioxide and water; a step of contacting the raw material gas after contact with the solvent with the water sorbent to remove water; and contacting the raw material gas after removing the water with the nickel catalyst to remove oxygen of the reaction residue; and removing the foregoing The step of removing the carbon dioxide by contacting the raw material gas after the oxygen with the alumina containing 0.1 to 10% by weight of sodium. According to a second aspect of the invention, in the method for purifying a gas according to the first aspect of the invention, the raw material gas is not contained in a stoichiometry with respect to an amount of a hydrocarbon, hydrogen, and carbon monoxide which are reacted in the catalyst. When the oxidizing gas is oxidized by more than the amount of the oxidizing gas, the raw material gas is supplied to the oxidizing gas until the amount of the hydrocarbon, hydrogen, and carbon monoxide is oxidized by the stoichiometric method, and then the raw material gas is brought into contact with the catalyst. . The method of purifying a gas according to the first or second aspect of the invention, wherein the partial pressure of carbon dioxide in the material gas is 19 Pa or less. The method of purifying the gas according to any one of the first to third aspects of the present invention, wherein the filling amount of the nickel catalyst is Va (L), and the filling amount is converted by the volume of the alumina. In the case of Vb(L), the filling ratio (Va/Vb) is such that Va/Vb<l is satisfied. The method of purifying a gas according to any one of the first to fourth aspects of the present invention, wherein the catalyst is in any one or more of active oxidation|g, shixia, activated carbon, or both The carrier of the composition is supported by any one or more of Pt, Pd, Ru, Ag, Cu, and Μn of 0.011 to 5 wt 7 323444 201217044%. The method of purifying a gas according to any one of the first to fifth invention, wherein the oxidizing gas is oxygen. The method of purifying a gas according to any one of the first to sixth aspects, wherein the hydrocarbon is a decane. According to a eighth aspect of the invention, there is provided a gas purifying apparatus which is a gas purifying apparatus for removing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide, oxygen and water in a material gas composed of nitrogen or a rare gas, the apparatus having a catalytic catalyst filled with a catalyst And a sorbent tower which is provided on the flow side of the catalyst column and which is filled with a water sorbent, a nickel catalyst, and an oxidized sodium containing sodium from the side of the raw material gas inflow side. (Effect of the Invention) The gas purification method of the present invention is a method in which a raw material gas of nitrogen or a rare gas is brought into contact with a catalyst, whereby hydrocarbons, argon, and carbon monoxide in the material gas are reacted with an oxidizing gas to be converted into carbon dioxide. with water. Therefore, unlike the conventional purification method which does not use a catalyst, hydrocarbons in the material gas can be converted into carbon dioxide and water to be removed. The raw material gas after contact with the catalyst is brought into contact with the water sorbent, whereby water in the raw material gas can be removed. Therefore, it is possible to prevent the nickel catalyst disposed on the downstream side of the water sorbent from being degraded by water. Further, since hydrogen and carbon monoxide are reacted with the oxidizing gas, it is only necessary to remove the oxygen of the reaction residue by the nickel catalyst. Therefore, the amount of the nickel catalyst to be filled can be an amount which can remove only the reaction ruin, and the amount of filling can be reduced as compared with the conventional method. In the past, the adsorption of carbon dioxide by zeolite was small, although the Ni catalyst would also be 8 323444 201217044
較多’故Ni觸媒僅需充填吸著氣 幅削減充填量。 氣化轉對二乳化礙的吸著量 著氡所必要之量即可，可大 此結果可減少高價補媒之充填量，增加低價之含有More, so the Ni catalyst only needs to be filled with absorbing gas to reduce the filling amount. The amount of adsorption required for gasification to the second emulsification can be as large as necessary, which can reduce the filling amount of high-priced replenishment and increase the content of low-priced
’ _ «。·ΤΧ_冗学計量法上得以氧化的量 以上之氧化性氣體時’則較佳為於前述原料氣體中供給氧 化性氣體^到化學計量法上m化烴類、氫及一氧化 碳以上的里為止。藉此可將原料氣體中的烴類、氫及一氧 化石厌王轉換成二氧化碳及水。因此不需要用以除去氫及 一氧化碳之鎳觸媒，可抑制鎳觸媒充填量之增加。 較佳為除去氧後之原料氣體中，二氧化碳分壓在19Pa 以下。一氧化碳分壓在19Pa以下時，含有鈉之活性氧化 鋁係可較沸石更為有效率的除去二氧化碳。因此可減少含 有鈉之活性氡化鋁的充填量，可實現純化裝置之緻密化。 以鎳觸媒之體積換算充填量為Va(L)、以前述氧化鋁 之體積換算充填量為Vb(L)時，此等之充填量比（Va/Vb)較 佳為滿足Va/Vb<l之關係。藉由使低價之氧化鋁的充填 量較尚價的錄觸媒為多，可降低惰性氣體之製造成本。 觸媒較佳為在活性氧化鋁、矽藻土、活性炭中任一者 或兩者以上所構成之擔體上，使擔載〇· 01至5wt%之Pt、 Pd Ru、Ag、cu、舫之任一者或兩者以上所構成者。藉由 323444 9 201217044 使用此等觸媒，可有效率的使烴類與氧化性氣體反應。 氧化性氣體較佳為氧。氧係低價且易於使用，此外， 與烴類、氫及一氧化碳之反應性優異，故可適宜的進行與 原料氣體的反應。 本發明之氣體純化裝置具有充填觸媒之觸媒塔，可將 原料氣體中之释類除去。此外在觸媒塔的下流侧設置由原 料氣體流入側向流出側依序充填水份吸著劑、錄觸媒、以 及含有納之氧化銘之吸著塔’藉此可依序除去水、反應殘 渣的氧、一氧化碳。因此，錄觸媒僅用來除去反應殘渣的 氧，因此’鎳觸媒之充填量可較以往方法減少。 含有鈉之活性氧化鋁可較以往使用之沸石更有效率的 除去二氧化碳，故不須以Ni觸媒除去二氧化碳，可大幅 減少觸媒量。 因此可抑制高價之錄觸媒的充填量，可降低惰性氣體 之製造成本與實現純化裝置的緻密化。 【實施方式】 以下參照圖面詳細說明有關適用於本發明之純化裝置 1，以及使用其之氣體純化方法。 説明有關本發明之-實施型態之第i圖所示之氣體純 化裝ί1的構成。 此氣體純化裝置1，係用以除去氮氣或稀有氣體所成 原料氣體中之烴類、氫、一氧化碳、二氧化碳、氧及水之 裝置。 氣體純化裝置1係如第i圖所示，具有充填觸媒之觸 323444 10 201217044 媒塔2以及設置於觸媒塔2下流側之吸著塔3A及3B之概 略構成。以下詳細說明各構成。 觸媒塔2係藉由觸媒將原料氣體中所含不純物之烴 類、氫及一氧化碳轉換為水與二氧化碳而除去之單元。更 具體而言，觸媒塔2之上流側設置有原料氣體供給源G1， 由此原料氣體供給源G1經由設置於通路L1之熱交換機4， 將原料氣體供給至觸媒塔2内。此觸媒塔2内充填有觸 媒。在觸媒塔2的外周設置有用以加熱觸媒塔2之加熱器 2a。 原料氣體係如上述由氮氣或稀有氣體構成，包含lppm 至lOppm濃度之烴類、氫、一氧化碳、二氧化碳、氧及水 等不純物。 在此，作為觸媒塔2之處理對象之烴類並無限定。例 如可列舉曱烷、乙烷等烷類及苯等芳香族烴。尤其甲烷在 大氣中的含量多，故常成為處理對象。 觸媒係藉由與原料氣體接觸，使原料氣體中之烴類、 氫、及一氧化碳與氧化性氣體之氧反應而轉換為水與二氧 化碳。 此等觸媒例如在活性氧化鋁、矽藻土、活性炭中任一 者或兩者以上所構成之擔體上，使擔載0. 01至5wt%、較 佳為 0. 1 至 lwt%之 Pt、Pd、Ru、Ag、Cu、Μη 之任一者或 兩者以上者。觸媒並不限於此處所列舉者，只要具有相同 機能則使用其他觸媒亦無妨。藉由使用此等觸媒，可使原 料氣體中之烴類有效率的與氧反應。 11 323444 201217044 於觸媒塔2之上流側設置有氧化性氣體供給源G2。此 等氧化性氣體供給源G2係構成為藉由設置於通路L2之閥 VI的開閉，而可將氧化性氣體供給至原料氣體。相對於原 料氣體中之烴類、氫及一氧化碳的量，原料氣體中未含有 在化學計量法上得以氧化的量以上之氧化性氣體時，係使 氧化性氣體由氧化性氣體供給源G2供給之構成。因此， 即使原料氣體中之氧化性氣體的量不足，亦可供給氧化性 氣體至原料氣體，直到化學計量法上得以氧化原料氣體中 之烴類、氫及一氧化碳以上的量為止。 氧化性氣體只要為可將原料氣體中之烴類完全燃燒的 氣體即無特別限制。此等氣體可舉出例如氧、臭氧等氧之 同素異形體（allotrope)。其中以使用面來看特佳為氧。 吸著塔3A及3B係用以除去由觸媒塔2導出之原料氣 體所含的水、反應殘渣的氧、及二氧化碳之單元。吸著塔 3A與吸著塔3B為相同構成。 更具體而言，吸著塔3A及吸著塔3B内，由原料氣體 流入側（底部）向流出側（上部），以水份吸著劑層6、鏞觸 媒層7、氧化鋁層8之順序積層充填。吸著塔3A及吸著塔 3B係構成為藉由閥V2至V9之開閉，可切換原料氣體以及 由再生氣體供給源G4供給之氫氣的流動。吸著塔3A及吸 著塔3B的外周分別設置有用以加熱吸著塔3A及3B之加熱 器 3c 、 3d 。 水份吸著劑層6係藉由與原料氣體接觸而吸著原料氣 體中的水之水份吸著劑。水份吸著劑可使用例如活性氧化 12 323444 201217044 鋁石夕膠、合成/弗石之任一者或兩者以上。水份吸著劑係 不限定於此處所舉例者，只要具有料原料氣财之水的 機能者，則使用其他水份吸著劑亦無妨。 設置鎳觸媒層7係為了藉由與原料氣體接觸而除去原 料氣體：之反應殘渣的氧。具體而言，在鎳觸媒層7中充 填有可藉由實施氫還原處理而可再使用之鎳觸媒。此等錄 觸媒例如可❹在活絲她、残土、活性碳等擔體 上，擔載有10至斷t%之錄金屬而成之觸媒。更佳為使 用擔載有5G至7Gwt%之錄金屬而成之觸媒。 設置氧化紹詹8係為了藉由與原料氣體接觸而除去原 料氣體中之二氧化碳。具體而言，於氧化銘層8充填含有 〇. 1至ion%鈉之r -氧化銘。更佳為於氧化結層8充填含 有5至7 -氧輪。藉由域含有狀活性氧化 1¾的氧化紹層8’ Ni觸媒僅需充填吸著氧所必要之量 可’可大幅削減充填量。 味鎳觸媒之體積換算充填量為Va(L)、氧化鋁之體積击 异充填量為Vb(L)時，此等之充填量比（Va/Vb)之值為〇 — ^ 1.〇。此外，更佳為0.7至0.9。因氧化銘較錄觸媒;^ 價，故藉由使氧化鋁的充填量較鎳觸媒多，可' Μ置1之製造成本。 將由觸媒塔2導出，且經過熱交換器4及冷卻器5 原料氣體供給至吸著塔3A及3B。此時原料氣體係^ = 至吸著塔3A或3B之任一方之方式構成。以於吸著塔Μ、、’、。 3B之上部侧，氫氣由再生氣體供給源G4經過通路l?= 323444 13 201217044 V10及通路L8，而供給至吸著塔3A或3B的任一方之方式 構成。 於吸著塔3A及3B之上部侧之通路L5設置有惰性氣體 排出部G3，將經吸著塔3A及3B純化後之惰性氣體排出。 以使惰性氣體由通路L5經過通路L8與閥11供給至吸著塔 3A及3B之方式構成。於吸著塔3A及3B之底部側之通路 L6設置有排氣氣體排出部G5，使排氣氣體排出。 第1圖中，吸著塔3A内由底部向上部積層充填水份吸 著劑層6、鎳觸媒層7、及氧化銘層8，但將其配置逆轉使 其順序為由原料氣體流入側向流出側亦無妨。亦即藉由逆 轉吸著塔3A内的配置，使原料氣體流動成為可由吸著塔 3A的上部流向底部之降流（down f low)構造亦無妨。 根據本實施型態之氣體鈍化裝置1，因具備充填有觸 媒之觸媒塔2而可除去原料氣體中的烴類。此外，藉由於 觸媒塔2之下流側設置由原料氣體流入側向流出側依序充 填水份吸著劑、鎳觸媒、以及含有鈉之氧化鋁之吸著塔 3A、3B，可依序除去水、反應殘渣之氧、二氧化碳。因 此，鎳觸媒僅用來除去反應殘渣之氧，鎳觸媒充填量可較 以往方法減少。因含有鈉之活性氧化鋁較以往二氧化碳除 去用吸著劑之沸石可更有效率的除去二氧化碳，故可大幅 減少除去二氧化碳所需觸媒（鎳觸媒）的量。 因此可抑制高價鎳觸媒之充填量、降低惰性氣體之製 造成本、以及實現氣體純化裝置1之緻密化。 接著使用圖式說明本實施型態之氣體純化方法。本實 14 323444 201217044 施型態之氣體純化方法（吸著步驟）係由以下步驟概略構 成：使原料氣體與觸媒接觸而使烴類、氫及一氧化碳與氧 化性氣體反應，藉此生成二氧化礙與水之步驟；使與觸媒 接觸後之原料氣體與水份吸著劑接觸，藉此除去水之步 驟；使除去水後之原料氣體與鎳觸媒接觸，藉此除去反應 殘渣之氧之步驟；以及使除去氧後之原料氣體與含有 至10wt%鈉之氧化銘接觸，藉此除去二氧化竣之步驟。 首先如第1圖所示，由原料氣體供給源G1將原料氣體 導入通路L1。此時原料氣體可使用例如藉由深冷式空氣分 離裝置製造者’或儲藏於冷蒸發器槽（c〇1d evap〇rat〇r tank)(超低溫液化氣體儲槽）者。 在此，相對於原料氣體中之烴類、氫及一氧化碳的 量，原料軋體中未含有在化學計量法上得以氧化的量以上 之氧化性氣體時，較佳為將氧化性氣體導入通路L2。較佳 為供給氧化性氣體，直到化學計量法上得以氧化原料氣體 中之經類、氫及一氧化碳以上的量為止。氧化性氣體較佳 為使用氧。 如此則氧化性氣體與通路L1内之原料氣體混合，經 過熱交換器4，流入以加熱器2a加熱之觸媒塔2。此時若 原料氣體及氧化性氣體之溫度不足時，可藉由熱交換器4 適當加熱。 然後原料氣體與觸媒塔2内之觸媒接觸.，使原料氣體 中之炫類、氫及一氧化碳與氧化性氣體反應。此時過剩之 氧不會反應，成為反應殘渣之氧而留在原料氣體中。藉由 323444 15 201217044 此反應可生成二氧化碳及水。如此則在此階段中，原料氣 體中的不純物僅剩二氧化碳、水及反應殘渣之氧。 其後原料氣體經過設置於通路L3之熱交換器4及冷卻 器5、通路L4、閥2而導入吸著塔3A。若原料氣體的溫度 過高時，可藉由熱交換器4及冷卻器5調整至適宜溫度。 此時將原料氣體導入吸著塔3A與吸著塔3B之任一者皆無 妨，但此處說明原料氣體導入吸著塔3A之情形。 導入吸著塔3A之原料氣體首先流入水份吸著劑層6。 原料氣體與水份吸著劑接觸，將水份吸著、除去。 接著使由水份吸著劑層6流出之原料氣體流入鎳觸媒 層7。原料氣體與鎳觸媒接觸，將反應殘渣之氧吸著、除 去。 接著使由鎳觸媒層7流出之原料氣體流入氧化鋁層 8。原料氣體與含有鈉之活性氧化鋁接觸，將二氧化碳吸 著、除去。在與含有鈉之活性氧化鋁接觸前之階段中，原 料氣體中二氧化碳分壓較佳為0.0001至19Pa，更佳為 0. 001至1. OPa。如第2圖所示，在原料氣體中二氧化碳分 壓為19Pa以下時，含有鈉之活性氧化鋁可較沸石更有效 率的除去二氧化炭。因此，藉由預先使原料氣體中二氧化 碳分壓為19Pa以下，可將二氧化碳有效率的吸著、除 去。第2圖_係比較沸石與氧化銘之二氧化碳吸著量的圖。 此外，第2圖中之二氧化碳吸著量測定，係使用定容量式 氣體吸著量測定裝置，將溫度固定在25°C同時任意設定壓 力下進行。 16 323444 201217044 如此可有效率的去除原料氣體中之二氧化碳，故Ni 觸媒僅需充填吸著氧所需之量即可，可減少Ni觸媒之充 填量。 其後原料氣體經過閥V8、通路L5，藉由惰性氣體排 出部G3作為純化氣體（惰性氣體）導出。此時惰性氣體不 純物（烴、氫、一氧化碳、二氧化碳、氧及水）的濃度為 0. lppb等級以下。 接著說明有關於吸著塔3A之再生步驟。 首先，於吸著塔3A進行吸著步驟後，進行閥V2至V9 之開閉操作而切換原料氣體與氫氣的流動。藉此使吸著塔 3A進入再生步驟，使吸著塔3B進入吸著步驟。 接著由再生氣體供給源G4將氫氣導入通路L7。氫氣 係於通路L8中與純化後惰性氣體的一部分混合，成為氫 氣濃度1至5vol%之混合氣體。接著將前述混合氣體導入 吸著塔3A之上部側。混合氣體係以氧化鋁層8、鎳觸媒層 7、水份吸著劑層6之順序通過。 吸著塔3A係藉由加熱器3c加熱。因此，吸著於氧化 鋁層8之二氧化碳、吸著於鎳觸媒層7之氧、吸著於水份 吸著層6之水份等不純物，藉由以加熱器3c之加熱與混合 氣體之作用而依序脫著。如此則前述不純物與混合氣體混 合，經由通路L6而由排氣氣體排出部G5作為排氣氣體排 出。 結束如此再生之吸著塔3A，成為等待下次吸著步驟之 狀態。 17 323444 201217044 广在吸著塔3A之再生步驟期間，導入於吸著塔犯之原 料氣體係以與前述步驟相同方式使不純物被吸著，且作為 惰性氣體而由惰性氣體排出部G3排出。有關其詳細内容 係與前述吸著塔3A<料步驟相同，故省略說明。 根據本實施型態之氣體純化方法，可使原料氣體盘觸 媒接觸，藉此可預先使原料氣體中之烴類、氫及-氧化碳 與氧化性亂體反應而轉換為二氧化碳與水。因此與不使用 觸媒之以在之純化方法相異，可將原料氣體中的煙類轉換 為一氧化碳及水而除去。 使與觸媒接觸後之原料氣體與水份吸著劑接觸，藉此 可除去原料耽體中的水。因此，可防止設置於水份吸著劑 下流側之錄觸媒因水而降低機能。此外，因使氫及-氧化 碳與氧化性氣體反應，故藉由鎳觸媒僅需除去反應殘渣之 ，。因此，賴叙充填量P、要材除去反應錄之氧的 里即可肖以往之氣體純化方法相較可減少充填量。 相對於在觸媒使之反應之經類、氮及一氧化碳的量， 原料氣體中未含有在化學計量法上得以氧化的量以上之氧 化性氣體時，則於原料氣體中供給氧化性氣體，直到化學 計量法上得以氧化前賴類、氫及―氧化碳以上的量為 止，藉此可將原料氣體中之煙類、氮及一氧化碳全部轉換 為二氧化碳與水。因此不需要用以除去氮及一氧化碳之錄 觸媒。 因此可減少高價鎳觸媒之充填量，且可降低惰性氣體 之製造成本。 323444 18 201217044 使原料氟體中二氧化碳分壓在19Pa以下，即可雜由 含有鈉之活性氧化鋁有效率的除去二氧化碳。因此可減少 N i觸媒之充填量。 藉由以上方式可減少吸著塔3A(3B)内觸媒（鎳觸媒、 含有鈉之活性氧化鋁）的含量。因此可實現氣體純化骏置^ 之緻密化。 (實施例） 以下藉由實施例更詳細說明本發明之氣體純化方法， 但本發明並不僅限於此等實施例。 (實施例1) 於内徑100mm之不鏽鋼製圓桶内充填400mm擔載於氧 化銘之Pd觸媒作為觸媒塔2。於内徑l〇〇mm之不鏽鋼製圓 桶内’由原料氣體流入侧至流出侧依序形成厚度l〇〇mm之 沸石層所成之水份吸著劑層6(MS5A)、厚度50mm之鎳觸媒 層7(N112)、厚度250mm之含鈉重量比為5. 8%的氧化鋁層 8 ’作為吸著塔3A。 首先用以下條件將吸著塔3A的各層再生。 首先將含有氫濃度2vol%之氮以2Nm3/小時之流量， 經過通路L7及通路L8導入吸著塔3A三小時，同時藉由加 熱器3c加熱至20(TC。接著將氮氣以2Nm3/小時之流量流 入吸著塔3A，將吸著塔3A冷卻。 接著進行吸著步驟。 將含有lppm曱烷、lppm氫、lppm —氧化碳、〇· 5ppm 一氧化碳、4ppm氧、2. 6ppm水份之氮作為原料氣體，以 19 323444 201217044 壓力lOOPaG、溫度400°C、流量15Nm3/小時之條件導入觸 媒塔2。其後藉由熱交換器4及冷卻器5,將原料氣體之溫 度冷卻至25°C並導入吸著塔3A。 原料氣體開始導入吸著塔3A後，於經過50小時之時 點檢測氧作為第1突破（break through)成份。 (實施例2) 於内徑100mm之不鏽鋼製圓桶内充填4〇〇mm擔载於氧 化鋁之Pd觸媒作為觸媒塔2。於内徑i〇〇mm之不鏽鋼製圓 桶内，從上方由原料氣體流入側至流出側依序形 100mm之沸石層所成之水份吸著劑層6(MS5A)、y、厚度 之鎳觸媒層7(N112)、厚度25〇mffl之含鈉重量f度5〇_ 氧化㈣8,作為吸著塔3A。 里比為戰 接著以與實施例1相同之條件將吸著塔3A 與實施例1相同之條件進行吸著步驟。 '^生後’以 原料氣體開始導入觸媒塔2及吸著塔 49小時之日__氧作為第丨突破成份之氣。★’於經過 (比較例1) 於内徑lOOrom之不鏽鋼製圓桶内，從 流入側至流出側依序形成厚度1()_之彿由原料氣體 吸著劑層_5A)、厚度細賴之鎳觸媒 ^成之水份 25〇娜之含納重量比為5.8%的氧化麵層δ 112)、厚度 3Α。接著以以下條件進行再生步驟。 ，作為吸著塔 將加熱至2〇(TC之氣濃度2ν〇1%之氣 流量，經過通路L7及通路L8流入吸著 2NmV小時之 小時。接著 323444 20 201217044 將氮加熱至200°C ’以2Nm3/小時之流量流入吸著塔3A三 . 小時。 其後將含有lppm甲烷、Ippm氫、1卯m 一氧化碳、 0. 5ppm二氧化碳、4ppm氧、2. 6ρρπι水份之氮作為原料氣 體，以壓力1 OOPaG、溫度25 °C、流速（空塔之速度） 26. 5cm/秒、流量15Nm3/小時之條件導入吸著塔3A。 導入開始之後即檢測出lppm甲烷，復於經過47小時 之時點檢測氫作為第1突破成份。 (比較例2) 於内徑100mm之不鏽鋼製圓桶内，充填400mm擔载於 氧化銘之Pd觸媒作為觸媒塔2。於内徑100丽之不鏽鋼製 圓桶内’由原料氣體流入侧至流出側依序形成厚度5〇咖 之鎳觸媒層6(N112)、厚度100mm之沸石層所成之水份吸 著劑層7(MS5A)、厚度250mm之含鈉重量比為5. 8%的氧化 在呂層8，作為吸著塔3A。 以與實施例1相同之條件將吸著塔3A再生後，將與實 施例」相同組成之原料氣體，以相同之條件導入觸媒塔2 及吸著塔3A。原料氣體開始導人觸媒塔2及吸著塔3A後， 於經過4G小時之時點檢測氧作為第1突破成份。 (比較例3) 於内徑100随之不鏽鋼製圓桶内，充填4〇〇mm擔载於 之p_媒作為觸媒塔2。於内徑100mm之不鏽鋼製 ，從上方由原料氣體流入侧至流出側依序形成 100職之彿石層所成水份吸著劑層6(·)、厚度501ηιης 323444 21 201217044 鎳觸媒層7(N112)、厚度250mm之氧化鋁層8，作為吸著塔 3A ° 以與實施例1相同之條件將吸著塔3A再生後，將與實 施例1相同組成之原料氣體，以相同之條件導入觸媒塔2 及吸著塔3A。原料氣體開始導入觸媒塔2及吸著塔3A後， 於經過27小時之時點檢測二氧化碳作為第1突破成份。 將各實施例、比較例之觸媒/吸著劑的充填量，以及 由實驗檢出之突破成份與突破時間整理於表1。 22 323444 201217044 比較例3 Pd/氧化鋁 ^ Ξ § 謹湧 J 〇 LO <=> οα ^ S «ί J3 SZ CO CD οα _c 1 比較例2 Pd/氧化鋁 Ξ 園曰盖 ◦ 曰 S n o CM 球 s 璩 JZ X： CO Ο s| 墙β •—吹 之些： 比較例1 m i s s <=> s c=) LO e-^t O r—i Ξ =墙 ^ ^ urf SZ X： CO CO s 〇 無法完全除去 CH4 實施例2 ； 1 Pt/氧化鋁 白 曰圍君 Ξ C3 <=» LO CS5 s 墙球 w; 遝与 瘦 S： JZ CO <=5 o涅 實施例1 Pd/氧化鋁 白 s 昌 盖 ^ s - w? 氍与 樂· ·<~ι J= JZ CO Q g g ^ LO 貴金屬/擔體 /*~N /-Ν /—\ — 03 CO V-/ s-x v^/ EE 减g 突破成分 突破時間 附註 吸著塔 充填順序 從氣體入口 觸媒條件 吸著塔條件 再生條件 突破結果 23 323444 201217044 脑rΛ實施例1與比較例1可知，以觸媒塔2之觸媒將煙 頰I甲烷）、虱、一氧化碳與氧反應，藉此除去甲烷。復於 觸媒塔2預切原料氣狀應，使_媒之貞荷僅剩氧，、 幅減低鎳觸媒之充填量。比較例1 +，因錦觸媒負 :著氫、一氧化碳、氧，故即使鎳觸媒充填量為4倍，但 氫係於47小時開始突破。 σ 一 ,、此外由實施例丨與比較例2可知，將水份吸著劑層6 形成於鎳觸媒層7之上流側，可增加鎳觸媒層7之氧吸著 量。 此外由實施例1與比較例3可知，若使甩含有納之氧 化鋁，則可大幅減少氧化铭的充填量，惰性氣體中亦未檢 出二氧化碳。 (實施例3) 於一乳化$反分壓lPa之條件下’改變納含量而測定氧 化鋁之二氧化碳吸著量。結果，鈉含量為〇. lwt%、h 6wt %、5. 8wt%、9.8wt%之氧化鋁之二氧化碳吸著量分別為 38、50、60、65mmol/kg，相對於此，鈉含量為〇· lwt%以 下之氧化紹之'一氧化被吸者里分別為28πιπιο 1 / kg。此結果 示於第3圖，橫軸為納含量、縱軸為二氧化碳吸著量。第 3圖表示之二氧化碳吸著量的測定，係使用定容量式氣體 吸著量測定裝置（使用13. 2Pa全標度（fuii scaie)之 Baratron靜電容量式壓力計Uks公司製），可測定數pa以 下之氣體吸著量），設定於溫度25Ϊ、壓力IPa進行。 由第3圖之圖表可判斷：含有鈉之氧化紹之二氧化碳 323444 24 201217044 吸著能力，較不含鈉之氧化鋁為高。 - (產業上之利用性） _ 根據本發明，在除去烴類、氬、一氧化碳、二氧化 碳、氧及水以純化由氮氣或稀有氣體所成之原料氣體時， 可將純化裝置緻密化、可降低高價觸媒之充填量、且可降 低純化成本。 【圖式簡單說明】 第1圖係表示本發明之氣體純化裝置之一例之概略構 成圖。 第2圖係表示沸石與本發明之氧化鋁在低分壓下之二 氧化碳吸著量的比較圖。 第3圖係表示本發明之氧化鋁所含鈉的含量與二氧化 碳吸著量的圖。 【主要元件符號說明】 1 氣體純化裝置 2 觸媒塔 2a 加熱器 3A、3B 吸著塔 3c > 3d 加熱器 4 熱交換機 5 冷卻器 6 水份吸著劑層 7 錄觸媒層 8 氧化鋁層 25 323444 201217044 G1 原料氣體供給源 G2 氧化性氣體供給源 G3 惰性氣體排出部 G4 再生氣體供給源 G5 排氣氣體排出部 LI 至 L8 通路 VI 至 Vll 閥 26 323444’ _ «. ΤΧ ΤΧ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . Thereby, hydrocarbons, hydrogen, and oxidized stone in the material gas can be converted into carbon dioxide and water. Therefore, a nickel catalyst for removing hydrogen and carbon monoxide is not required, and an increase in the amount of nickel catalyst charged can be suppressed. Preferably, the raw material gas after removing oxygen has a partial pressure of carbon dioxide of 19 Pa or less. When the partial pressure of carbon monoxide is below 19 Pa, the active aluminum oxide containing sodium can remove carbon dioxide more efficiently than zeolite. Therefore, the filling amount of the activated aluminum halide containing sodium can be reduced, and the densification of the purification apparatus can be achieved. When the filling amount of the nickel catalyst is Va (L) and the filling amount of the alumina is Vb (L), the filling ratio (Va/Vb) preferably satisfies Va/Vb<; l relationship. By making the filling amount of the low-priced alumina more expensive than the recording medium, the manufacturing cost of the inert gas can be reduced. Preferably, the catalyst is supported on a support composed of one or more of activated alumina, diatomaceous earth, and activated carbon, and supports Pt, Pd Ru, Ag, cu, and 舫 of 01 to 5 wt%. Any one or more of them. By using these catalysts, 323444 9 201217044 can efficiently react hydrocarbons with oxidizing gases. The oxidizing gas is preferably oxygen. Oxygen is inexpensive and easy to use, and is excellent in reactivity with hydrocarbons, hydrogen, and carbon monoxide, so that it can be suitably reacted with a material gas. The gas purifying apparatus of the present invention has a catalytic catalyst column filled with a catalyst, and the release of the raw material gas can be removed. In addition, on the downstream side of the catalyst column, a water sorbent, a recording medium, and a sorption column containing the oxidation of the raw material are sequentially filled from the side of the raw material gas to the lateral outflow side, thereby sequentially removing water and reacting. Residual oxygen, carbon monoxide. Therefore, the recording medium is only used to remove oxygen from the reaction residue, so that the amount of nickel catalyst can be reduced compared with the conventional method. The activated alumina containing sodium can remove carbon dioxide more efficiently than the zeolite used in the prior art, so that it is not necessary to remove carbon dioxide by the Ni catalyst, and the amount of catalyst can be greatly reduced. Therefore, the filling amount of the high-priced recording medium can be suppressed, the manufacturing cost of the inert gas can be reduced, and the densification of the purification apparatus can be realized. [Embodiment] Hereinafter, a purification apparatus 1 applicable to the present invention and a gas purification method using the same will be described in detail with reference to the drawings. The configuration of the gas purifying device ί1 shown in Fig. i of the embodiment of the present invention will be described. The gas purifying device 1 is a device for removing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide, oxygen and water in a raw material gas of nitrogen or a rare gas. The gas purifying apparatus 1 has a schematic configuration of a catalyst-filled contact 323444 10 201217044 medium tower 2 and sorbent towers 3A and 3B provided on the downstream side of the catalyst tower 2, as shown in Fig. i. Each configuration will be described in detail below. The catalyst column 2 is a unit which removes hydrocarbons, hydrogen and carbon monoxide which are impurities contained in the material gas into water and carbon dioxide by a catalyst. More specifically, the source gas supply source G1 is provided on the upstream side of the catalyst column 2, whereby the source gas supply source G1 supplies the source gas into the catalyst column 2 via the heat exchanger 4 provided in the passage L1. The catalyst column 2 is filled with a catalyst. A heater 2a for heating the catalyst column 2 is provided on the outer circumference of the catalyst column 2. The raw material gas system is composed of nitrogen or a rare gas as described above, and contains impurities such as hydrocarbons, hydrogen, carbon monoxide, carbon dioxide, oxygen, and water in a concentration of 1 ppm to 10 ppm. Here, the hydrocarbon to be treated by the catalyst column 2 is not limited. For example, an alkane such as decane or ethane or an aromatic hydrocarbon such as benzene can be cited. In particular, methane is often contained in the atmosphere and is often used as a treatment target. The catalyst is converted into water and carbon dioxide by reacting a hydrocarbon, hydrogen, and carbon monoxide in the material gas with oxygen of an oxidizing gas by contact with a material gas. 01至该重量的的。 The catalyst, for example, on a carrier of the active alumina, the diatomaceous earth, the activated carbon, or a mixture of the two or more, such as 0. 01 to 5wt%, preferably 0.1 to lwt% Any one or more of Pt, Pd, Ru, Ag, Cu, and Μη. The catalyst is not limited to those listed here, and it is also possible to use other catalysts as long as they have the same function. By using these catalysts, the hydrocarbons in the raw material gas can be efficiently reacted with oxygen. 11 323444 201217044 An oxidizing gas supply source G2 is provided on the flow side of the catalyst column 2 . The oxidizing gas supply source G2 is configured to supply the oxidizing gas to the source gas by opening and closing the valve VI provided in the passage L2. When the amount of the hydrocarbons, hydrogen, and carbon monoxide in the material gas does not contain an amount of the oxidizing gas that is oxidized by the stoichiometric method, the oxidizing gas is supplied from the oxidizing gas supply source G2. Composition. Therefore, even if the amount of the oxidizing gas in the material gas is insufficient, the oxidizing gas can be supplied to the material gas until the amount of hydrocarbons, hydrogen, and carbon monoxide in the material gas is oxidized by stoichiometry. The oxidizing gas is not particularly limited as long as it is a gas which can completely burn the hydrocarbons in the material gas. Examples of such a gas include an allotrope of oxygen such as oxygen or ozone. Among them, oxygen is particularly preferred from the viewpoint of use. The sorption towers 3A and 3B are units for removing water contained in the raw material gas derived from the catalyst column 2, oxygen of the reaction residue, and carbon dioxide. The sorption tower 3A has the same configuration as the sorption tower 3B. More specifically, in the adsorption tower 3A and the adsorption tower 3B, the raw material gas inflow side (bottom) to the outflow side (upper portion), the moisture adsorbent layer 6, the tantalum catalyst layer 7, and the aluminum oxide layer 8 The sequence is filled in layers. The suction tower 3A and the suction tower 3B are configured to be capable of switching the flow of the source gas and the hydrogen gas supplied from the regeneration gas supply source G4 by opening and closing the valves V2 to V9. Heaters 3c, 3d for heating the suction towers 3A and 3B are provided on the outer circumferences of the suction tower 3A and the suction tower 3B, respectively. The moisture sorbent layer 6 is a moisture sorbent which absorbs water in the raw material gas by contact with the material gas. As the moisture sorbent, for example, either active oxidation 12 323444 201217044 aluminite, synthetic/fussite or both or more may be used. The water sorbent is not limited to the ones exemplified herein, and any other water sorbent may be used as long as it has the function of the raw material. The nickel catalyst layer 7 is provided to remove oxygen of the reaction residue of the raw material gas by contact with the material gas. Specifically, the nickel catalyst layer 7 is filled with a nickel catalyst which can be reused by performing a hydrogen reduction treatment. Such a recording medium can be carried, for example, on a live wire, a residual soil, an activated carbon or the like, and carries a catalyst of 10 to 12% of the recorded metal. More preferably, it is a catalyst which is loaded with a metal of 5G to 7Gwt%. The oxidized Saujan 8 system is provided to remove carbon dioxide in the raw material gas by contact with the material gas. Specifically, the oxidized layer 8 is filled with r-oxidation containing 〇. 1 to ion% sodium. More preferably, the oxide layer 8 is filled with a 5 to 7 - oxygen wheel. The amount of the 8' Ni catalyst used in the oxidation-containing layer of the active oxidation of the domain is only required to be filled with the amount necessary for absorbing oxygen. The amount of filling can be drastically reduced. When the volume conversion filling amount of the nickel-catalyst is Va(L), and the volume of the aluminum oxide is Vb(L), the ratio of the filling amount (Va/Vb) is 〇— ^ 1.〇 . Further, it is preferably from 0.7 to 0.9. Since the oxidation is better than the recording medium; therefore, by making the amount of alumina filled more than the nickel catalyst, the manufacturing cost of the device can be set. It is led out of the catalyst column 2, and is supplied to the adsorption towers 3A and 3B through the heat exchanger 4 and the cooler 5 raw material gas. At this time, the raw material gas system ^ = is constituted by one of the adsorption towers 3A or 3B. In order to suck the tower,, ',. On the upper side of 3B, hydrogen is supplied from the regeneration gas supply source G4 to either one of the adsorption towers 3A or 3B via the passages ?? 323444 13 201217044 V10 and the passage L8. The passage L5 on the upper side of the suction towers 3A and 3B is provided with an inert gas discharge portion G3, and the inert gas purified by the adsorption towers 3A and 3B is discharged. The inert gas is configured to be supplied from the passage L5 through the passage L8 and the valve 11 to the suction towers 3A and 3B. The exhaust gas discharge portion G5 is provided in the passage L6 on the bottom side of the suction towers 3A and 3B to discharge the exhaust gas. In the first drawing, the water sorbent layer 6, the nickel catalyst layer 7, and the oxidized layer 8 are filled in the sorbent column 3A from the bottom to the upper portion, but the arrangement is reversed so that the order is from the raw material gas inflow side. It does not matter to the outflow side. That is, by reversing the arrangement in the sorption tower 3A, it is possible to make the material gas flow to a down f low structure which can flow from the upper portion of the sorption tower 3A to the bottom portion. According to the gas passivation apparatus 1 of the present embodiment, hydrocarbons in the material gas can be removed by providing the catalyst column 2 filled with the catalyst. In addition, the sorbent columns 3A and 3B which are sequentially filled with the water sorbent, the nickel catalyst, and the alumina containing sodium by the raw material gas flowing into the lateral outflow side are provided by the flow side of the catalyst column 2, and can be sequentially The water, the oxygen of the reaction residue, and carbon dioxide are removed. Therefore, the nickel catalyst is only used to remove oxygen from the reaction residue, and the amount of nickel catalyst charged can be reduced compared with the conventional method. Since the activated alumina containing sodium can remove carbon dioxide more efficiently than the conventional carbon dioxide removal catalyst using a sorbent, the amount of catalyst (nickel catalyst) required for carbon dioxide removal can be greatly reduced. Therefore, the filling amount of the high-priced nickel catalyst can be suppressed, the manufacturing cost of the inert gas can be reduced, and the densification of the gas purifying apparatus 1 can be realized. Next, the gas purification method of this embodiment mode will be described using a schematic diagram.本实14 323444 201217044 The gas purification method (sucking step) of the embodiment is roughly constituted by the following steps: contacting a raw material gas with a catalyst to react a hydrocarbon, hydrogen and carbon monoxide with an oxidizing gas, thereby generating a dioxide a step of obstructing water; a step of contacting the raw material gas after contact with the catalyst with the water sorbent, thereby removing water; contacting the raw material gas after removing the water with the nickel catalyst, thereby removing oxygen of the reaction residue And the step of removing the cerium oxide by contacting the raw material gas after removing oxygen with the oxidizing agent containing up to 10% by weight of sodium. First, as shown in Fig. 1, the material gas is introduced into the passage L1 by the source gas supply source G1. At this time, the material gas can be used, for example, by a cryogenic air separation device manufacturer or in a cold evaporator tank (cryogenic liquefied gas tank). Here, when the amount of the hydrocarbon, hydrogen, and carbon monoxide in the material gas does not contain an amount of the oxidizing gas which is stoichiometrically oxidized in the raw material rolling body, it is preferable to introduce the oxidizing gas into the passage L2. . It is preferred to supply an oxidizing gas until the amount of hydrogen, carbon monoxide or more in the material gas is oxidized by stoichiometry. The oxidizing gas is preferably oxygen. Thus, the oxidizing gas is mixed with the material gas in the passage L1, passes through the heat exchanger 4, and flows into the catalyst column 2 heated by the heater 2a. At this time, if the temperature of the material gas and the oxidizing gas is insufficient, the heat exchanger 4 can be appropriately heated. Then, the material gas is brought into contact with the catalyst in the catalyst column 2 to cause the stimuli, hydrogen and carbon monoxide in the material gas to react with the oxidizing gas. At this time, excess oxygen does not react and becomes oxygen in the reaction residue and remains in the material gas. This reaction produces carbon dioxide and water by 323444 15 201217044. Thus, at this stage, the impurities in the raw material gas are only oxygen, carbon dioxide, and oxygen of the reaction residue. Thereafter, the material gas is introduced into the absorbing tower 3A through the heat exchanger 4, the cooler 5, the passage L4, and the valve 2 provided in the passage L3. When the temperature of the material gas is too high, it can be adjusted to a suitable temperature by the heat exchanger 4 and the cooler 5. At this time, it is possible to introduce the material gas into either of the adsorption tower 3A and the adsorption tower 3B, but the case where the material gas is introduced into the adsorption tower 3A will be described here. The material gas introduced into the sorption tower 3A first flows into the moisture sorbent layer 6. The material gas is brought into contact with the water sorbent to sorb and remove the water. Next, the material gas flowing out of the moisture sorbent layer 6 is caused to flow into the nickel catalyst layer 7. The material gas is brought into contact with the nickel catalyst, and the oxygen of the reaction residue is sucked and removed. Next, the material gas flowing out of the nickel catalyst layer 7 is caused to flow into the aluminum oxide layer 8. The raw material gas is brought into contact with the activated alumina containing sodium to adsorb and remove carbon dioxide. 001至1. OPa。 The partial pressure of the carbon dioxide in the raw material gas is preferably from 0.0001 to 19 Pa, more preferably from 0.001 to 1. OPa. As shown in Fig. 2, when the partial pressure of carbon dioxide in the material gas is 19 Pa or less, the activated alumina containing sodium can remove carbon dioxide more efficiently than the zeolite. Therefore, by previously making the partial pressure of carbon dioxide in the material gas to 19 Pa or less, carbon dioxide can be efficiently sucked and removed. Figure 2 is a graph comparing the amount of carbon dioxide absorbed by zeolite and oxidized. Further, the measurement of the amount of carbon dioxide absorbed in Fig. 2 was carried out by using a constant-capacity gas absorption amount measuring device, and fixing the temperature at 25 ° C while arbitrarily setting the pressure. 16 323444 201217044 This can effectively remove the carbon dioxide in the raw material gas, so the Ni catalyst only needs to be filled with the amount required to absorb oxygen, which can reduce the filling amount of the Ni catalyst. Thereafter, the material gas passes through the valve V8 and the passage L5, and is led out as a purified gas (inert gas) by the inert gas discharge portion G3. The concentration of the inert gas (hydrocarbon, hydrogen, carbon monoxide, carbon dioxide, oxygen, and water) is 0. lppb or less. Next, the regeneration step of the sorption tower 3A will be described. First, after the suction step is performed in the suction tower 3A, the opening and closing operations of the valves V2 to V9 are performed to switch the flow of the material gas and the hydrogen gas. Thereby, the sorption tower 3A is brought into the regeneration step, and the sorption tower 3B is brought into the sorption step. Then, hydrogen gas is introduced into the passage L7 by the regeneration gas supply source G4. Hydrogen is mixed with a part of the purified inert gas in the passage L8 to form a mixed gas having a hydrogen gas concentration of 1 to 5 vol%. Then, the mixed gas is introduced into the upper side of the sorption tower 3A. The mixed gas system passes in the order of the aluminum oxide layer 8, the nickel catalyst layer 7, and the water sorbent layer 6. The sorption tower 3A is heated by the heater 3c. Therefore, the carbon dioxide adsorbed on the aluminum oxide layer 8, the oxygen adsorbed to the nickel catalyst layer 7, the moisture adsorbed on the moisture absorbing layer 6, and the like are heated by the heater 3c and the mixed gas. Acting and taking off in sequence. In this manner, the impurities are mixed with the mixed gas, and are discharged as exhaust gas by the exhaust gas discharge portion G5 via the passage L6. The sorption column 3A thus regenerated is terminated in a state of waiting for the next sorption step. 17 323444 201217044 During the regeneration step of the sorption tower 3A, the raw material gas system introduced into the sorption tower causes the impurities to be sucked in the same manner as the above-described steps, and is discharged as an inert gas from the inert gas discharge portion G3. The details are the same as those of the sorption column 3A <the material step, and therefore the description thereof is omitted. According to the gas purifying method of the present embodiment, the raw material gas disk can be contacted with the catalyst, whereby hydrocarbons, hydrogen and carbon monoxide in the material gas can be converted into carbon dioxide and water by reacting with oxidizing disorder. Therefore, the smoke in the material gas can be converted into carbon monoxide and water to be removed, unlike the purification method in which the catalyst is not used. The raw material gas after contact with the catalyst is brought into contact with the water sorbent, whereby the water in the raw material body can be removed. Therefore, it is possible to prevent the recording medium disposed on the downstream side of the water sorbent from being degraded by water. Further, since hydrogen and carbon monoxide are reacted with the oxidizing gas, it is only necessary to remove the reaction residue by the nickel catalyst. Therefore, the filling amount of Lai, the material to be removed from the oxygen recorded in the reaction can reduce the filling amount compared with the conventional gas purification method. When the amount of nitrogen, carbon monoxide and carbon monoxide reacted by the catalyst does not contain an amount of oxidizing gas which is stoichiometrically oxidized in the raw material gas, the oxidizing gas is supplied to the raw material gas until the chemical The amount of smoke, nitrogen, and carbon monoxide in the material gas can be converted into carbon dioxide and water by measuring the amount of the former, hydrogen, and carbon oxide. Therefore, a recording medium for removing nitrogen and carbon monoxide is not required. Therefore, the filling amount of the high-priced nickel catalyst can be reduced, and the manufacturing cost of the inert gas can be reduced. 323444 18 201217044 The partial pressure of carbon dioxide in the raw material fluorine is below 19 Pa, so that the activated carbon containing sodium can efficiently remove carbon dioxide. Therefore, the filling amount of the N i catalyst can be reduced. By the above method, the content of the catalyst (nickel catalyst, sodium-containing activated alumina) in the adsorption tower 3A (3B) can be reduced. Therefore, the densification of the gas purification can be achieved. (Examples) Hereinafter, the gas purification method of the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. (Example 1) A stainless steel drum having an inner diameter of 100 mm was filled with 400 mm of a Pd catalyst supported on Oxygen as a catalyst column 2. In a stainless steel drum having an inner diameter of l〇〇mm, a water sorbent layer 6 (MS5A) having a thickness of 10 mm from the inflow side of the raw material gas to the outflow side is sequentially formed, and the thickness is 50 mm. The nickel catalyst layer 7 (N112) and the sodium-containing weight ratio of the thickness of 250 mm are 5.8% of the aluminum oxide layer 8' as the adsorption tower 3A. First, each layer of the sorption tower 3A was regenerated under the following conditions. First, nitrogen having a hydrogen concentration of 2 vol% is introduced into the sorption column 3A through the passage L7 and the passage L8 at a flow rate of 2 Nm 3 /hour for three hours while being heated to 20 (TC by the heater 3c. Then, nitrogen is brought to 2 Nm 3 /hour. The flow rate flows into the sorption tower 3A, and the sorption column 3A is cooled. Next, the sorption step is performed. As the nitrogen containing 1 ppm of decane, 1 ppm of hydrogen, 1 ppm of carbon oxide, 〇·5 ppm of carbon monoxide, 4 ppm of oxygen, and 2. 6 ppm of water, The raw material gas is introduced into the catalyst column 2 under the conditions of 19 323 444 201217044 pressure 100 PaG, temperature 400 ° C, flow rate 15 Nm 3 /hour. Thereafter, the temperature of the material gas is cooled to 25 ° C by the heat exchanger 4 and the cooler 5 . And the sorption tower 3A is introduced. After the raw material gas is introduced into the sorption tower 3A, oxygen is detected as a first break through component at a time of 50 hours. (Example 2) In a stainless steel drum having an inner diameter of 100 mm Filled with 4 〇〇mm Pd catalyst supported on alumina as the catalyst column 2. In a stainless steel drum having an inner diameter of i〇〇mm, a zeolite of 100 mm in sequence from the inflow side of the raw material gas to the outflow side Water sorbent layer 6 (MS5A), y, thickness Nickel catalyst layer 7 (N112), thickness 25 〇mffl, sodium content weight f 5 〇 oxidized (4) 8 as sorption column 3A. Ribbi followed by sorption column 3A under the same conditions as in Example 1. The adsorption step was carried out under the same conditions as in Example 1. After the "after birth", the raw material gas was introduced into the catalyst column 2 and the adsorption tower for 49 hours. _ Oxygen was used as the gas for the breakthrough component. Example 1) In a stainless steel drum having an inner diameter of 100 μm, a thickness of 1 ()_ from the inflow side to the outflow side is sequentially formed by a raw material gas sorbent layer _5A), and a nickel catalyst having a thickness of a small amount is formed. The moisture content of the water is 25%, the oxidation surface layer is δ 112), and the thickness is 3Α. The regeneration step is then carried out under the following conditions. , as the sorption tower will be heated to 2 〇 (TC gas concentration 2 〇 〇 1% of the gas flow, through the passage L7 and the passage L8 into the sorption 2NmV hours of hours. Then 323444 20 201217044 to heat the nitrogen to 200 ° C ' The flow rate of 2 Nm 3 /hour flows into the sorption tower 3A for three hours. Thereafter, nitrogen containing 1 ppm of methane, 1 ppm of hydrogen, 1 卯m of carbon monoxide, 0.5 ppm of carbon dioxide, 4 ppm of oxygen, and 2. 6 ρρπι of water is used as a raw material gas under pressure. 1 OOPaG, temperature 25 ° C, flow rate (speed of the empty tower) 26. 5 cm / sec, flow rate 15 Nm3 / hr into the sorption tower 3A. After the start of the introduction, 1 ppm of methane was detected, and the time point was detected after 47 hours. Hydrogen was used as the first breakthrough component. (Comparative Example 2) In a stainless steel drum with an inner diameter of 100 mm, 400 mm of Pd catalyst supported on Oxygen was used as the catalyst tower 2. The inner diameter of 100 stainless steel drum The water sorbent layer 7 (MS5A) and the thickness of 250 mm are formed by sequentially forming a nickel catalyst layer 6 (N112) having a thickness of 5 Å from the inflow side of the raw material gas to the outflow side, and a zeolite layer having a thickness of 100 mm. The sodium weight ratio was 5.8% of the oxidation in the layer 8 as the sorption column 3A. After the adsorption column 3A was regenerated under the same conditions as in Example 1, the raw material gas having the same composition as in the Example was introduced into the catalyst column 2 and the adsorption column 3A under the same conditions. The raw material gas started to guide the catalyst column 2 After absorbing the column 3A, oxygen was detected as the first breakthrough component at the time of 4G hours. (Comparative Example 3) In the inner diameter of 100, the stainless steel drum was filled with 4 mm in the p-media. It is used as a catalyst tower 2. It is made of stainless steel having an inner diameter of 100 mm, and a water sorbent layer 6 (·) and a thickness of 501 η η ς 323444 21 are formed in order from the inflow side of the raw material gas to the outflow side. 201217044 Nickel catalyst layer 7 (N112), alumina layer 8 having a thickness of 250 mm, as the adsorption tower 3A °, after the adsorption column 3A was regenerated under the same conditions as in Example 1, the raw material gas having the same composition as in Example 1 was used. The catalyst column 2 and the adsorption tower 3A were introduced under the same conditions. After the raw material gas was introduced into the catalyst column 2 and the adsorption column 3A, carbon dioxide was detected as the first breakthrough component at the time of 27 hours. The amount of catalyst/sorbent filled in the comparative example, and the experimentally detected Breakthrough ingredients and breakthrough time are compiled in Table 1. 22 323444 201217044 Comparative Example 3 Pd/Alumina^ Ξ § 涌 J & LO <=> οα ^ S «ί J3 SZ CO CD οα _c 1 Comparative Example 2 Pd/ Alumina Ξ Garden ◦ 曰 S no CM Ball s 璩 JZ X: CO Ο s| Wall β • - Blowing Some: Comparative Example 1 miss <=> sc=) LO e-^t O r—i Ξ = wall ^ ^ urf SZ X: CO CO s 〇 can not completely remove CH4 Example 2; 1 Pt / alumina white 曰 Ξ Ξ C3 <=» LO CS5 s squash w; 遝 and thin S: JZ CO <=5 o Nie Example 1 Pd / alumina white s Chang Gai ^ s - w? 氍 and Le · · <~ι J= JZ CO Q gg ^ LO Precious metal / support / * ~ N / - Ν /—\ — 03 CO V-/ sx v^/ EE minus g Breakthrough component breakthrough time note sorption tower filling sequence from gas inlet catalyst condition sorption tower condition regeneration condition breakthrough result 23 323444 201217044 Brain rΛ Example 1 and comparison In Example 1, it is understood that methane is removed by reacting the buccal I methane), hydrazine, and carbon monoxide with oxygen by the catalyst of the catalyst column 2. The catalyst tower 2 is pre-cut to the raw material gas, so that only the oxygen is left in the charge of the medium, and the filling amount of the nickel catalyst is reduced. Comparative Example 1 +, because of the negative catalyst: hydrogen, carbon monoxide, and oxygen, even if the nickel catalyst loading amount is 4 times, the hydrogen system starts to break in 47 hours. Further, from Example 丨 and Comparative Example 2, it is understood that the water sorbent layer 6 is formed on the upstream side of the nickel catalyst layer 7, and the oxygen absorbing amount of the nickel catalyst layer 7 can be increased. Further, as is apparent from the first embodiment and the comparative example 3, if the cerium is contained in the cerium, the amount of oxidizing is greatly reduced, and carbon dioxide is not detected in the inert gas. (Example 3) The amount of carbon dioxide adsorbed by the aluminum oxide was measured by changing the nano content under the condition of one emulsification of $anti-partial pressure lPa. As a result, the carbon dioxide sorption amounts of alumina having a sodium content of 〇. lwt%, h 6wt%, 5.8 wt%, and 9.8 wt% are 38, 50, 60, and 65 mmol/kg, respectively, and the sodium content is 〇. · lwt% or less of the oxidation of the 'one oxidation is absorbed in the 28πιπιο 1 / kg. The results are shown in Fig. 3, in which the horizontal axis represents the nano-content and the vertical axis represents the carbon dioxide adsorption amount. The measurement of the carbon dioxide sorption amount shown in Fig. 3 is carried out by using a fixed-capacity gas sorption amount measuring device (manufactured by Baraxon electrostatic capacity type pressure gauge Uks, which uses a 13.2 Pa full scale (fuii scaie)). The gas absorption amount below pa is set at a temperature of 25 Torr and a pressure IPa. From the chart in Figure 3, it can be judged that the carbon dioxide containing sodium oxide is 323444 24 201217044. The sorption capacity is higher than that of sodium-free alumina. - (Industrial Applicability) _ According to the present invention, when a hydrocarbon, argon, carbon monoxide, carbon dioxide, oxygen, and water are removed to purify a raw material gas formed of nitrogen or a rare gas, the purification device can be densified and reduced. The high amount of catalyst is filled and the purification cost can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a schematic configuration of an example of a gas purifying apparatus of the present invention. Fig. 2 is a graph showing the comparison of the amount of carbon dioxide adsorbed by the zeolite and the alumina of the present invention at a low partial pressure. Fig. 3 is a graph showing the content of sodium contained in the alumina of the present invention and the amount of carbon dioxide adsorbed. [Main component symbol description] 1 Gas purification unit 2 Catalyst tower 2a Heater 3A, 3B Suction tower 3c > 3d Heater 4 Heat exchanger 5 Cooler 6 Moisture sorbent layer 7 Recording medium layer 8 Alumina Layer 25 323444 201217044 G1 Raw material gas supply source G2 Oxidizing gas supply source G3 Inert gas discharge unit G4 Regenerative gas supply source G5 Exhaust gas discharge unit LI to L8 Path VI to V11 Valve 26 323444