200829507 九、發明說明： 【發明所屬之技術領域】 本發明涉及惰性氣體之處理方法和精製方法以及氣體 處理筒，更具體地說，涉及使含有難以除去的烴類雜質的 惰性氣體在加熱的條件下與含金屬鎳和/或氧化鎳的處理 劑接觸，高效容易地除去難除烴類的處理方法，和進一步 使由上述處理所產生的容易除去的雜質與吸氣材料或吸附 劑接觸而除去的精製方法，以及能夠高效率地實施這些方 法的氣體處理筒。 【先前技術】 在半導體工業中，氨氣、氖氣、氬氣、氪氣等稀有氣 體被頻繁使用，而這些氣體要求具有極高的純度。這些氣 體是空氣中僅含微量的稀有氣體，除了從空氣中提取以 外’沒有其他有效的調製方法，例如，氬氣、氪氣可以通 過液體空氣的分餾製得。但是，空氣中存在微量的甲院， 由於甲烷的沸點爲-1 6 4 °C，若藉由分餾從氬氣（沸點：_丨8 $ C )或氣氣（沸點：· 1 5 3 C )中除去甲院至極低濃度，則必須 重複進行多次精餾分離，費用很高，否則很困難。 另外’作爲從如上所述調製的稀有氣體中除去甲院的 方法’有使稀有氣體在加熱的條件下與銷或鈦等吸氣材料 接觸而捕獲除去的方法、在稀有氣體中添加氧氣使甲烷燃 燒轉化成二氧化碳和水，再在常溫下使其與合成沸石接觸 吸附除去二氧化碳和水的方法等。 另外，日本特開平7 - 270067號公報中揭示了使空氣 200829507 冷卻、液化後利用沸點差分離各成分。日本特開平i 〇 — 11 4 5 Ο 8號公報中公開了在極低溫度下除去氬氣流中所含的 氮氣和甲烷。日本特開平2003 — 17001 8號公報中公開了使 含甲烷的氫氣與以锆爲主要成分的吸氣材料在高溫下接觸 而除去甲烷。 【發明內容】 但是，由於使稀有氣體等惰性氣體在加熱的條件下與 吸氣材料接觸的方法除去甲烷的能力（相對於每單位量的 ^ 吸氣材料，甲烷的除去量）較低，且吸氣材料價格昂貴，因 而運行成本高而不適宜。 另外，在稀有氣體等惰性氣體中添加氧氣的方法，相 對於甲烷的含量必須充入過量的氧氣，除了難以調整氧氣 的供給量以外，在甲烷轉化成二氧化碳和水後，還必須與 其一起除去過剩的氧氣’因而吸附劑等的消耗量很大，因 此不適宜。 於是，本發明所要解決的問題是，提供一種低成本且 闻效率地從如上所述含有難去除之雜質甲烷（烴）的稀有氣 體等惰性氣體除去甲烷（烴）的惰性氣體之處理方法、精製 方法以及能夠高效地實施這些方法的氣體處理筒。 本發明人等爲了解決這些問題專心致力地硏究，結果 發現’藉由使含有甲烷等烴類雜質的惰性氣體在加熱的條 件下與金屬鎳和/或氧化鎳，較佳爲與高比表面積的上述鎳 接觸’能夠高效率容易地除去烴類（轉化成容易除去的雜 質）’並且除去能力也很高，從而達成了本發明的惰性氣體 200829507 之處理方法和精製方法以及氣體處理筒。 即，本發明是一種惰性氣體之處理方法，其特徵在於 使含烴類雜質的惰性氣體在加熱的條件下與含金屬鎳和/ 或氧化鎳的處理劑接觸，從該惰性氣體中除去烴類。 另外，本發明是一種惰性氣體之精製方法，其特徵在 於使含烴類雜質的惰性氣體在加熱的條件下與含金屬鎳的 處理劑接觸，然後再使其與吸氣材料接觸。 另外，本發明是一種惰性氣體之精製方法，其特徵在 ® 於使含烴類雜質的惰性氣體在加熱的條件下與含氧化鎳的 處理劑接觸，然後再使其與吸附劑或吸氣材料接觸。 另外，本發明還是一種氣體處理筒，其特徵在於使含 金屬鎳和/或氧化鎳的處理劑與吸氣材料通過間隙或者惰 性塡充材料相互隔離而進行塡充，並裝有用於加熱該處理 劑以及該吸氣材料的加熱器。 本發明的惰性氣體之處理方法和精製方法，由於使用 比吸氣材料更廉價、且能夠期望獲得優良的烴類除去能力 ® (相對於每單位量的處理劑，烴類的除去量）的金屬鎳、氧 化鎳或者含有它們的鎳催化劑作爲除去難以去除之雜質烴 類的處理劑原料，因此可以使運作成本下降。並且，由於 裝置結構簡單，因而能夠高效率地進行烴類的去除處理和 精製處理。 【實施方式】 本發明的惰性氣體之處理方法和精製方法以及氣體處 理筒，適用於從至少含有甲烷等烴類雜質的氮氣、氦氣、 200829507 氖氣、氬氣、氪氣、氤氣等惰性氣體、或者選自這些惰性 氣體的兩種以上混合氣體中至少除去烴類之處理方法、精 製方法以及氣體處理筒。惰性氣體中所含的甲烷等烴類通 常爲200ppm以下。並且’惰性氣體中，與烴類一起還可以 含有氫氣、氧氣、一氧化碳、二氧化碳、水等雜質。 本發明的處理方法、精製方法和氣體處理筒中使用的 處理劑只要含有金屬鎳和/或氧化鎳即可，例如，可以列舉 使以鎳催化劑、鎳的氫氧化物、碳酸鹽、硝酸鹽、有機酸 ® 鹽等容易被氧化還原的鎳化合物爲主要成分的原料氧化或 還原所得的處理劑。另外，作爲鎳以外的金屬成分，還可 以含有少量的鉻、鐵、鈷、銅等金屬。這些原料可以單獨 使用，並且，也可以以載持在催化劑載體等上的載持形式 使用，但從提高鎳表面與氣體的接觸效率之目的等角度出 發，通常以載持在催化劑載體等上的載持形式使用。 作爲使鎳載持在載體上的方法，例如，可以列舉使矽 藻土、礬土、矽鋁、矽酸鋁或者矽酸鈣等載體粉末分散在 ® 鎳鹽的水溶液中，再加鹼使鎳成分沉殿在載體粉末上，然 後過濾並根據需要用水洗滌，將所得濾餅在80〜150°C下乾 燥後，再於300°C以上的溫度下烘焙，然後將該烘焙物粉碎 的方法；或者將NiCCh、Ni(OH)2、Ni(NCh)2等無機鹽、 NiC2〇4、Ni(CH3COO)2等有機鹽烘焙並粉碎後，使其與耐熱 性膠結劑（cement)混合並烘焙的方法。 其通常是通過擠壓成型、壓片成型等製成成型體’將 其直接使用或者根據需要粉碎成適當大小而進行使用。作 200829507 爲成型方法，可以採用乾法或者濕法。此時，還可以使用 少量的水、潤滑劑等。 另外，作爲鎳類催化劑，由於例如N — 1 1 1 (Ni -矽藻 土）（日揮（股）生產）等係在市場上販售，因此也可以從中選 擇使用。總之，只要是使還原鎳、氧化鎳等微細地分散， 使其表面積增大，從而使其與氣體接觸效率高的形式即可。 處理劑的BET比表面積通常爲10〜300m2/g，較佳爲 30〜250m2/g。另外，相對於全部處理劑，金屬鎳和氧化鎳 • 的含量比率通常爲5〜95 wt %，較佳爲20〜95wt%。若鎳的 含量低於5wt%，則烴類的除去能力很低，另外，若高於 95 wt%，則存在由氫還原時發生燒結，而有使活性下降的可 會b 。 在實施本發明的惰性氣體之處理方法時，將上述含金 屬鎳和/或氧化鎳的處理劑、或者鎳催化劑、鎳化合物等處 理劑原料塡充在處理筒中。處理筒中塡充的這些處理劑或 處理劑原料的塡充長度，在實際應用上通常爲1 〇〜 w 2000mm。若塡充長度短於10mm，則存在烴類雜質的去除 率下降的可能性，另外，若長於2000mm，則會出現壓力損 失過大的可能性。 當處理筒中塡充的處理劑原料含有鎳金屬或氧化鎳以 外的鎳化合物時，在烴類的除去處理之前，通常要進行由 氫氣之還原處理、由氧氣之氧化處理、或者在加熱的條件 下通入惰性氣體的活化處理，使其轉化爲處理劑。在進行 這些處理時，例如，可以藉由在3 5 0 °C以下的溫度下，以 -10- 200829507 0.1〜200cm/秒左右，較佳爲1〜50cm/秒的空筒線速度 (LV)，在處理筒中通入氫氣與氮氣的混合氣體、氧氣與氮 氣的混合氣體或者氮氣而進行。 在本發明中，處理對象氣體與處理劑的接觸溫度通常 爲200〜800 °C，較佳爲300〜600 °C。若上述接觸溫度爲200 t以上，則可以使處理對象氣體中的烴類高效地轉化爲氫 氣、二氧化碳、水等，若爲800°C以下，則不會對處理筒產 生過大的負荷。 ® 對氣體與處理劑接觸時的壓力也沒有特別的限制，可 以是常壓、減壓、加壓的任一種處理，但通常在常壓至 l.OMPa的加壓下進行。處理時氣體的空筒線速度（LV)根據 供給的氣體中烴類的濃度和操作條件等而不同，不能一槪 地進行特定，但通常爲100cm/秒以下，較佳爲30cm/秒以 下。 在本發明的處理方法中，通過使例如含甲烷的惰性氣 體在加熱的條件下與金屬鎳接觸，使其捕獲甲烷中的碳， β 並生成氫氣從下游排除。這時，根據處理條件的不同，也 會出現生成微量一氧化碳、二氧化碳並從下游排除的情 況。另外，藉由使例如含甲烷的惰性氣體在加熱的條件下 與氧化鎳接觸，生成二氧化碳和水並從下游排除。但是， 本發明的處理方法可以適合用於，例如，作爲用以供給即 使存在少量氫氣也不會產生不良影響的反應體系之載運氣 體之供給方法。 本發明的惰性氣體精製方法，藉由上述惰性氣體之處 -11 - 200829507 理方法處理的含有氫氣、二氧化碳、水等的惰性氣體進一 步與吸氣材料和/或吸附劑接觸，可以除去氫氣、二氧化 碳、水等。經由將惰性氣體如上進行處理，可以提高每單 位重量吸氣材料的除去能力，並使吸氣材料的使用壽命延 長。另外，在使用吸附劑的體系中，通過將惰性氣體如上 進行處理’可以使惰性氣體中的烴類轉化成二氧化碳和 水，使其可以藉由吸附劑予以除去。 另外，處理前的惰性氣體，除甲烷等烴類以外，即使 還含有氫氣、氧氣、一氧化碳、二氧化碳、水等雜質氣體， 該等也可以很容易地被除去。 在實施本發明的惰性氣體精製方法時，可以與上述金 屬鎳、氧化鎳、鎳催化劑或鎳化合物一起，在處理筒中共 同地塡充吸氣材料作爲其下游，此外，也可以在處理筒的 下游，設置塡充有吸氣材料的精製筒和/或塡充有吸附劑的 吸附筒。另外，作爲吸氣材料，可以列舉例如錐、釩、鐵、 鈦等。另外，作爲吸附劑，可以列舉沸石、活性炭等。在 進行惰性氣體的精製之前，也可以透過在加熱的條件下通 入惰性氣體、或者在加熱的條件下抽真空對吸氣材料和吸 附劑進行活化處理。 在本發明的惰性氣體之精製方法中，當將含有烴類雜 質的惰性氣體在加熱的條件下使其與金屬鎳接觸以除去烴 類時，由於如上所述產生氫氣從下游排除，因而較佳爲設 置用於除去氫氣的吸氣材料。另外，當將含有烴類雜質的 惰性氣體在加熱的條件下使其與氧化鎳接觸以除去烴類 -12- 200829507 時，由於產生二氧化碳和水從下游排除，因而較佳爲設置 用於除去二氧化碳和水的吸附劑或吸氣材料。 精製筒中塡充的吸氣材料之塡充長度和吸附筒中塡充 的吸附劑之概充長度’在實際應用上通常爲10〜2000mm。 另外，精製對象氣體與吸氣材料的接觸溫度通常爲200〜 80(TC，較佳爲300〜600°C，精製對象氣體與吸附劑的接觸 溫度通常爲0〜100°C，較佳爲10〜50°C。另外，對壓力也 沒有特別的限制，可以是常壓、減壓、加壓的任一種精製 m w 處理、吸附處理，但通常在常壓至1 .OMPa的加壓下進行。 另外，在使惰性氣體於加熱的條件下與吸氣材料接觸 除去氫氣雜質時的除去能力，由於與除去甲烷等烴類時的 除去能力相比非常地高，因而本發明使含金屬鎳的處理劑 與吸氣材料組合的精製方法不必擔心會提高運行成本。另 外’在常溫下使惰性氣體與沸石接觸除去作爲雜質的二氧 化碳和水後，在加熱沸石的同時通入再生氣體，使二氧化 0 碳和水脫吸附，可以使沸石再生，因此，本發明使含氧化 鎳的處理劑與吸附劑組合的精製方法，不必擔心會提高運 行成本。 本發明的氣體處理筒是能夠高效率地實施上述方法的 氣體處理裝置，如第1圖（1)和（2)的構造圖例所示，處理筒 (精製筒）的含金屬鎳和/或氧化鎳的處理劑1與吸氣材料2 通過間隙3或惰性塡充材料4相互隔離而塡充，並裝有用 於對處理劑和吸氣材料進行加熱的加熱器5。處理劑與吸 氣材料的塡充比率，以重量比計，.通常爲1 :2〜1〇〇〇，較佳 -13- 200829507 爲1:3〜1〇〇。另外，作爲惰性塡充材料，通常可以使用礬 土、矽石、矽鋁、鎂土等陶瓷製塡充材料。另外，處理劑 與吸氣材料的間隙、或者惰性塡充材料的塡充長度，通常 爲2〜1000mm，較佳爲5〜500mm。另外，第1圖中的6表 示溫度感測器。當上述間隙或塡充長度不足2mm時，處理 劑將會與吸氣材料接觸，存在使吸氣材料除去能力下降的 可能性，當超過100〇mm時，將導致氣體處理筒變得很大 而不適宜。 ^ 本發明的氣體處理筒的形狀通常爲圓筒形，其大小通 常內徑爲10〜500mm ’長度爲20〜2500 mm。氣體處理筒中 塡充的處理劑和吸氣材料的合計塡充長度，通常爲丨〇〜 2000mm，較佳爲50〜1000mm。另外，作爲構成氣體處理筒 的材料，可以列舉例如碳鋼、錳鋼、鉻鋼、鉬鋼、不銹鋼、 鎳鋼等，其中，較佳爲SUS316、SUS316L等不銹鋼。 以下，經由實施例對本發明進行更具體的說明，但是 本發明並不局限於這些實施例。 β [實施例1] (處理劑的調製） 將採用市售的鎳催化劑（含有金屬鎳和氧化鎳，Ni : 45 〜47wt%，Cr: 2 〜3wt%，Cu: 2 〜3wt%，砂藻土 ： 27 〜29wt%， 石墨：4〜5wt%，比表面積：15 0m2/g，直徑5mm、高4.5mm 的成型體）用作爲處理劑的原料。該鎳催化劑是在還原後進 行輕度氧化使其能夠處理成在空氣中不著火的狀態之穩定 化鎳催化劑。將粉碎至8〜1 0網目的該鎳催化劑塡充在內 -14- 200829507 徑爲23mm、長度爲1000mm的不銹鋼製處理筒中，塡充長 度爲200mm。將該處理筒的加熱器進行加熱，使催化劑（處 理劑）的溫度達到420°C，同時，以2500ml/分鐘的流量通入 氫氣，進行3小時還原處理後，冷卻至常溫。 (甲烷的除去處理） 然後，將處理筒的加熱器進行加熱後，以3 300ml/分鐘 的流量通入含有150ppm甲烷雜質的氬氣，進行甲烷的除去 處理。另外，在除去處理過程中，氬氣與處理劑的接觸溫 ^ 度維持在約420°C。在此期間，對從處理筒排除的氣體的一 部分進行取樣，通過氣相層析法測定甲烷是否被除去，結 果，即使在經過1000小時的時候，也可以除去甲烷，其除 去能力（每lg處理劑甲烷的除去量）爲358cc/g劑以上。 [實施例2] (處理劑的調製） 將與實施例1同樣的市售的穩定化鎳催化劑粉碎至8 〜10網目，與實施例1同樣地塡充至處理筒中，使塡充長 度爲20 0mm。將該處理筒的加熱器進行加熱，使處理劑的 溫度達到420°C，同時，以3300ml/分鐘的流量通入氧氣與 氬氣的混合氣體，些許地增加氧氣的濃度，使其由起初的 20%增至結束時的100%的濃度，進行8小時氧化處理後， 冷卻至常溫。 (甲烷的除去處理） 然後，將處理筒的加熱器進行加熱後，以3 300ml/分鐘 的流量通入含有150ppm甲烷雜質的氬氣，進行甲烷的除去 -15- 200829507 處理。另外，在除去處理過程中，氬氣與處理劑的接觸溫 度維持在約420°C。在此期間，對從處理筒排除的氣體的一 部分進行取樣，藉由氣相層析法測定甲烷是否被除去，結 果，即使在經過1 000小時的時候，也可以除去甲烷，其除 去能力（每lg處理劑甲烷的除去量）爲35 8cc/g劑以上。 [比較例1 ] (吸氣材料的調製） 採用锆海綿體與塊狀的釩（純度爲95 %以上），以鉻 ® 70wt%、釩3〇wt%進行混合後，在高頻感應加熱爐中進行熔 煉’得到約5kg的合金。將該合金用氬氣環境下的球磨機 進行粉碎，篩選14〜20網目者作爲吸氣材料。將其塡充在 內徑爲23 mm、長度爲1 000 mm的不銹鋼製精製筒中，塡充 長度爲220mm。將該精製筒的加熱器進行加熱，使吸氣材 料的溫度達到500°C，同時，以3300ml/分鐘的流量通入氬 氣’進行6小時的活化處理後，冷卻至常溫。 • (甲烷的除去處理） 然後’將精製筒的加熱器進行加熱後，以3300ml/分鐘 的流量通入含有150ppm甲烷雜質的氬氣，進行甲烷的除去 處理。另外，在除去處理過程中，氬氣與吸氣材料的接觸 溫度維持在約420 °C。在此期間，對從精製筒排除的氣體的 一部分進行取樣，通過氣相層析法測定甲烷是否被除去， '結果’經過1 60小時後，便不能再除去甲烷，其除去能力（每 lg吸氣材料甲烷的除去量）爲14 8cc/g材。 另外，將含260ppm氫氣雜質的氬氣，與上述同樣地通 -16- 200829507 入精製筒中，同樣地進行氫氣的除去處理，結果，氫氣的 除去能力爲85cc/g材。 [比較例2 ] 在實施例1的甲烷的除去處理中，除了使含有甲烷雜 質的氬氣在常溫（約25 °C )的溫度下與處理劑（經還原處理） 接觸外，與實施例1同樣地進行甲烷的除去處理。其結果 是，處理劑的除去能力（每lg處理劑甲烷的除去量）爲lcc/g 劑以下。 ® [比較例3] 在實施例2的甲烷的除去處理中，除了使含有甲烷雜 質的氬氣在常溫（約25 °C )的溫度下與處理劑（經氧化處理） 接觸外，與實施例2同樣地進行甲烷的除去處理。其結果 是，處理劑的除去能力（每lg處理劑甲烷的除去量）爲lcc/g 劑以下。 實施例3 (氣體處理筒之製作） 在內徑爲37.lmm、長度爲1000mm的不銹鋼製（SUS316L) 的處理筒的上游，塡充與實施例1同樣地粉碎後的市售的 穩定化鎳催化劑，塡充長度爲100mm。並且，間隔20mm 的間隙，在下游塡充與比較例1同樣調製的吸氣材料，塡 充長度爲220mm，製作出如第1圖（1)所示的氣體處理筒。 將該氣體處理筒的加熱器進行加熱，使處理劑的溫度 達到500 °C，同時，從下游以8400ml /分鐘的流量通入氬氣， 進行6小時活化處理後’冷卻至常溫。 -17- 200829507 (氬氣的精製處理） 接著使氣體處理筒的加熱器進行加熱至約4 2 0。(：後，從 氣體處理筒的入口處（上游）以84〇〇ml/分鐘的流量通入含有 作爲雜質的氫氣、氧氣、一氧化碳、二氧化碳、水各l〇ppm 和甲烷50ppm的氬氣，進行氬氣的精製處理。在此期間， 對從氣體處理筒排除的氣體的一部分進行取樣，藉由大氣 壓質譜儀（API — MS)測定氬氣中所含的雜質（氫氣、氧氣、 一氧化碳、二氧化碳、水），經長時間（500小時）後，不能 ^ 檢測出這些雜質。另外，精製的氬氣添加雜質後使其再次 循環使用。 [實施例4] (氣體處理裝置的製作） 將市售之相當於5 A的合成沸石（吸附劑）塡充在內徑爲 3 7 · 1 m m、長度爲8 0 0 m m的不錄鋼製吸附筒內，使塡充長度 爲100mm。然後，將澳實施例1同樣製作的處理筒（其中， _ 內徑爲37.1mm，塡充長度爲100mm)(上游）與該吸附筒2個 筒（下游），以與吸附筒並列的方式連接起來，並使各筒可 以分別進行氧化處理、活化處理。在處理筒中，與實施例 2同樣地進行處理劑的氧化處理，在吸附筒中，將吸附劑 的溫度加熱至350°C，同時，以8400ml/分鐘的流量通入氬 氣，進行8小時的活化處理，然後將各筒冷卻至室溫。 (氬氣的精製處理） 使處理筒的加熱器進行加熱至約420°C後，將含有作爲 雜質的氫氣、氧氣、一氧化碳、二氧化碳、水各lOppm和 -18- 200829507 甲院50p pm的Μ氣，以8400ml /分鐘的流量通入處理筒及其 一側的吸附筒，進行氬氣的精製處理。在此期間，對從吸 附筒排除的氣體的一部分進行取樣，藉由大氣壓質譜儀 (API — MS)測定氬氣中所含的雜質（氫氣、氧氣、一氧化碳、 二氧化碳、水、甲烷），經2 0小時後，無法檢測出這些雜 質。 然後，將吸附筒切換至另一側，繼續進行氬氣的精製 處理，同時，對所用吸附筒的吸附劑通過活化進行再生， 20小時後，再次將吸附筒進行切換。通過反復進行這種操 作，進行氬氣的精製處理，經長時間（500小時）後，不能檢 測出雜質（氫氣、氧氣、一氧化碳、二氧化碳、水、甲院）。 另外，精製的氬氣添加雜質後使其再次循環使用。 [實施例5] 在實施例3、4的氬氣精製處理中，除了使用含有氫 氣、氧氣、一氧化碳、二氧化碳、水各1〇ρριη和甲烷5〇ppm 的氮氣、氨氣、氖氣作爲精製處理對象的惰性氣體以外， 與實施例3、4同樣地進行精製處理。其結果是，任意一種 場合經長時間（5 00小時）後均不能檢測出雜質。 由以上可知，本發明實施例的處理方法、精製方法以 及氣體處理裝置能夠以優良的除去能力高效率容易地除去 惰性氣體中所含之難以除去的甲烷雜質。 【圖式簡單說明】 第1圖（1)、（2)係顯示本發明氣體處理筒的一個實例之 構造圖。 -19· 200829507 【主要元件符號說明】 1 處理劑 2 吸氣材料 3 間隙 4 惰性塡充材料 5 加熱器 6 溫度感測器BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inert gas treatment method and a purification method, and a gas treatment cylinder, and more particularly to an inert gas containing a hydrocarbon impurity which is difficult to remove under heating conditions. Contact with a treatment agent containing metal nickel and/or nickel oxide, efficiently and easily remove the difficult-to-remove hydrocarbon treatment method, and further remove the easily-removed impurities generated by the above treatment and contact with the getter material or the adsorbent The refining method and the gas processing cartridge capable of implementing these methods efficiently. [Prior Art] In the semiconductor industry, rare gases such as ammonia, helium, argon, and helium are frequently used, and these gases are required to have extremely high purity. These gases are rare gases containing only traces of air, and there are no other effective preparation methods other than extraction from air. For example, argon and helium can be obtained by fractional distillation of liquid air. However, there is a trace amount of A in the air, because the boiling point of methane is -1 6 4 ° C, if by fractional distillation from argon (boiling point: _ 丨 8 $ C) or gas (boiling point: · 1 5 3 C) In order to remove the A to very low concentration, it is necessary to repeat the rectification separation several times, which is very expensive, otherwise it is very difficult. Further, 'the method of removing the courtyard from the rare gas prepared as described above' has a method of capturing and removing a rare gas in contact with a getter material such as a pin or titanium under heating, and adding oxygen to the rare gas to methane. A method in which combustion is converted into carbon dioxide and water, and then contacted with a synthetic zeolite at room temperature to adsorb carbon dioxide and water. Further, Japanese Laid-Open Patent Publication No. Hei 7-270067 discloses that air 200829507 is cooled and liquefied, and each component is separated by a difference in boiling point. Nitrogen and methane contained in the argon gas stream are removed at an extremely low temperature as disclosed in Japanese Laid-Open Patent Publication No. Hei. Japanese Laid-Open Patent Publication No. 2003-17001 discloses that methane-containing hydrogen gas is brought into contact with a gettering material containing zirconium as a main component at a high temperature to remove methane. SUMMARY OF THE INVENTION However, the ability to remove methane (the amount of removal of methane per unit amount of getter material) is low because a method of bringing an inert gas such as a rare gas into contact with a getter material under heating conditions is low, and The getter material is expensive and therefore expensive to operate. In addition, in the method of adding oxygen to an inert gas such as a rare gas, it is necessary to charge an excess amount of oxygen with respect to the content of methane, and in addition to difficulty in adjusting the supply amount of oxygen, after methane is converted into carbon dioxide and water, excess must be removed together with it. The oxygen's consumption of the adsorbent and the like is therefore large, and thus it is not suitable. Accordingly, the problem to be solved by the present invention is to provide a method and a method for treating an inert gas which removes methane (hydrocarbon) from an inert gas such as a rare gas containing a difficult impurity methane (hydrocarbon) as described above at low cost and with high efficiency. Methods and gas processing cartridges capable of efficiently implementing these methods. In order to solve these problems, the inventors of the present invention have intensively studied and found that 'by using an inert gas containing a hydrocarbon impurity such as methane under heating conditions with metallic nickel and/or nickel oxide, preferably with a high specific surface area. The above nickel contact 'can efficiently remove hydrocarbons (converted into easily removable impurities) efficiently and has high removal ability, thereby achieving the treatment method and purification method of the inert gas 200829507 of the present invention and the gas treatment cylinder. That is, the present invention is a method for treating an inert gas, characterized in that an inert gas containing a hydrocarbon-containing impurity is contacted with a treatment agent containing nickel metal and/or nickel oxide under heating, and a hydrocarbon is removed from the inert gas. . Further, the present invention is a method for purifying an inert gas characterized in that an inert gas containing a hydrocarbon-containing impurity is brought into contact with a metal nickel-containing treating agent under heating, and then brought into contact with a gettering material. Further, the present invention is a method for purifying an inert gas characterized by: contacting an inert gas containing a hydrocarbon-containing impurity with a treatment agent containing nickel oxide under heating, and then bringing it into contact with an adsorbent or a getter material contact. In addition, the present invention is also a gas treatment cartridge characterized in that a treatment agent containing metal nickel and/or nickel oxide is mixed with a getter material through a gap or an inert charge material, and is charged for heating the treatment. And a heater for the getter material. The inert gas treatment method and purification method of the present invention are metal which is cheaper than the getter material and which can be expected to obtain an excellent hydrocarbon removal ability (relative to the amount of the treatment agent per unit amount of the hydrocarbon) Nickel, nickel oxide or a nickel catalyst containing the same can be used as a raw material for treating a difficult-to-remove impurity hydrocarbon, so that the operating cost can be lowered. Further, since the apparatus has a simple structure, the hydrocarbon removal treatment and the purification treatment can be performed efficiently. [Embodiment] The inert gas treatment method, purification method, and gas treatment cylinder of the present invention are suitable for use from nitrogen, helium, 200829507 helium, argon, helium, neon, etc., which contain at least hydrocarbon impurities such as methane. A treatment method, a purification method, and a gas treatment cylinder in which at least a hydrocarbon is removed from a gas or two or more mixed gases selected from the above-mentioned inert gases. The hydrocarbon such as methane contained in the inert gas is usually 200 ppm or less. Further, in the inert gas, impurities such as hydrogen, oxygen, carbon monoxide, carbon dioxide, and water may be contained together with the hydrocarbon. The treatment method, the purification method, and the treatment agent used in the gas treatment cartridge of the present invention may contain metal nickel and/or nickel oxide, and examples thereof include a nickel catalyst, a hydroxide of nickel, a carbonate, a nitrate, and an organic solvent. A treatment agent obtained by oxidizing or reducing a raw material which is a main component of a nickel compound which is easily redoxed, such as an acid salt. Further, as a metal component other than nickel, a small amount of a metal such as chromium, iron, cobalt or copper may be contained. These materials may be used singly or in the form of a support carried on a catalyst carrier or the like. However, from the viewpoint of improving the contact efficiency between the surface of the nickel and the gas, it is usually carried on a catalyst carrier or the like. Used in the form of carrier. As a method of supporting nickel on a carrier, for example, a carrier powder such as diatomaceous earth, alumina, strontium aluminum, aluminum citrate or calcium ruthenate may be dispersed in an aqueous solution of a nickel salt, and then alkali may be added to the nickel. The component is suspended on the carrier powder, then filtered and washed with water as needed, and the obtained filter cake is dried at 80 to 150 ° C, then baked at a temperature of 300 ° C or higher, and then the baked product is pulverized; Or an inorganic salt such as NiCCh, Ni(OH) 2, or Ni(NCh) 2 , or an organic salt such as NiC 2 〇 4 or Ni (CH 3 COO 2 ) is baked and pulverized, and then mixed with a heat resistant cement and baked. method. It is usually formed into a molded body by extrusion molding, tablet molding, or the like, and it is used as it is or pulverized to an appropriate size as needed. For the molding method, the dry method or the wet method can be used. At this time, a small amount of water, lubricant, or the like can also be used. Further, as the nickel-based catalyst, for example, N - 1 1 1 (Ni - diatomaceous earth) (produced by Nikko Co., Ltd.) is commercially available, and therefore it can be selected and used. In short, as long as the reduced nickel, nickel oxide, or the like is finely dispersed, the surface area thereof is increased, and the contact efficiency with the gas is high. The BET specific surface area of the treating agent is usually from 10 to 300 m 2 /g, preferably from 30 to 250 m 2 /g. Further, the content ratio of metallic nickel to nickel oxide is usually from 5 to 95% by weight, preferably from 20 to 95% by weight, based on the total of the treating agent. When the content of nickel is less than 5% by weight, the ability to remove hydrocarbons is low, and if it is more than 95% by weight, sintering may occur upon reduction by hydrogen, and the activity may be lowered. In carrying out the method for treating an inert gas of the present invention, the above-mentioned treatment agent containing metal nickel and/or nickel oxide, or a processing agent raw material such as a nickel catalyst or a nickel compound is filled in a treatment cylinder. The length of these treatments or treatment materials to be filled in the treatment tank is usually 1 〇 w w 2000 mm in practical applications. If the charging length is shorter than 10 mm, there is a possibility that the removal rate of hydrocarbon impurities is lowered, and if it is longer than 2000 mm, the pressure loss may be excessively large. When the processing agent charged in the treatment tank contains a nickel compound other than nickel metal or nickel oxide, it is usually subjected to reduction treatment of hydrogen, oxidation treatment by oxygen, or heating under the condition of removal of hydrocarbons. It is converted into a treating agent by an activation treatment of an inert gas. In carrying out these treatments, for example, an idler linear velocity (LV) of about -10-200829507 0.1 to 200 cm/sec, preferably 1 to 50 cm/sec, may be employed at a temperature of 305 ° C or lower. It is carried out by introducing a mixed gas of hydrogen and nitrogen, a mixed gas of oxygen and nitrogen, or nitrogen into the treatment cylinder. In the present invention, the contact temperature of the treatment target gas with the treatment agent is usually 200 to 800 ° C, preferably 300 to 600 ° C. When the contact temperature is 200 t or more, the hydrocarbons in the gas to be treated can be efficiently converted into hydrogen gas, carbon dioxide, water, or the like. If the temperature is 800 ° C or less, an excessive load is not applied to the treatment cylinder. The pressure at which the gas is brought into contact with the treating agent is not particularly limited, and may be any one of normal pressure, reduced pressure, and pressurization, but it is usually carried out under normal pressure to a pressure of 1.0 MPa. The linear velocity (LV) of the gas at the time of the treatment differs depending on the concentration of the hydrocarbons in the supplied gas, the operating conditions, and the like, and cannot be specified at a glance, but is usually 100 cm/sec or less, preferably 30 cm/sec or less. In the treatment method of the present invention, carbon, m, and hydrogen are trapped from the downstream by contacting, for example, an inert gas containing methane with metal nickel under heating. At this time, depending on the processing conditions, it is also possible to generate trace amounts of carbon monoxide, carbon dioxide and to remove them from the downstream. Further, carbon dioxide and water are generated and removed from the downstream by bringing, for example, an inert gas containing methane into contact with nickel oxide under heating. However, the treatment method of the present invention can be suitably used, for example, as a supply method of a carrier gas for supplying a reaction system which does not adversely affect even if a small amount of hydrogen is present. In the method for purifying an inert gas of the present invention, the inert gas containing hydrogen, carbon dioxide, water or the like treated by the above-mentioned inert gas -11 - 200829507 method is further contacted with the getter material and/or the adsorbent to remove hydrogen and carbon dioxide. , water, etc. By treating the inert gas as above, the removal ability of the getter material per unit weight can be improved, and the service life of the getter material can be extended. Further, in the system using the adsorbent, the hydrocarbon in the inert gas can be converted into carbon dioxide and water by treating the inert gas as above, so that it can be removed by the adsorbent. Further, the inert gas before the treatment can be easily removed by removing impurities such as hydrogen, oxygen, carbon monoxide, carbon dioxide or water, in addition to hydrocarbons such as methane. In carrying out the inert gas refining method of the present invention, together with the above metal nickel, nickel oxide, nickel catalyst or nickel compound, the getter material may be collectively filled as a downstream thereof in the treatment cylinder, or may be downstream of the treatment cylinder. A refining cylinder filled with a getter material and/or an adsorbent cylinder filled with an adsorbent are provided. Further, examples of the getter material include a cone, vanadium, iron, titanium, and the like. Further, examples of the adsorbent include zeolite, activated carbon, and the like. The gettering material and the adsorbent may also be activated by introducing an inert gas under heating or by vacuuming under heating conditions before purifying the inert gas. In the method for purifying an inert gas of the present invention, when an inert gas containing a hydrocarbon impurity is brought into contact with metallic nickel under heating to remove hydrocarbons, since hydrogen gas is eliminated from the downstream as described above, it is preferred. To set the getter material for removing hydrogen. Further, when an inert gas containing a hydrocarbon impurity is brought into contact with nickel oxide under heating to remove hydrocarbons-12-200829507, since carbon dioxide and water are eliminated from the downstream, it is preferably provided for carbon dioxide removal. And water adsorbents or getter materials. The length of the charge of the getter material in the refining cylinder and the length of the adsorbent of the adsorbent in the cartridge are usually 10 to 2000 mm in practical use. Further, the contact temperature of the gas to be purified and the gettering material is usually 200 to 80 (TC, preferably 300 to 600 ° C, and the contact temperature of the gas to be purified and the adsorbent is usually 0 to 100 ° C, preferably 10 The pressure is not particularly limited, and may be any of the refining mw treatment and the adsorption treatment under normal pressure, reduced pressure, and pressurization, but it is usually carried out under normal pressure to 1.0 MPa. Further, the removal ability when the inert gas is brought into contact with the gettering material under the heating condition to remove the hydrogen impurities is extremely high in comparison with the removal ability when removing hydrocarbons such as methane, and thus the present invention allows the treatment of the nickel-containing metal. The method of refining the combination of the agent and the getter material does not have to worry about increasing the running cost. In addition, after the inert gas is contacted with the zeolite at room temperature to remove carbon dioxide and water as impurities, the regeneration gas is introduced while the zeolite is heated to make the oxidation. The desorption of carbon and water can regenerate the zeolite. Therefore, the present invention provides a method for purifying a nickel oxide-containing treatment agent in combination with an adsorbent without fear of increasing the running cost. The gas treatment cylinder is a gas treatment apparatus capable of efficiently performing the above-described method, and the treatment of the metal-containing nickel and/or nickel oxide of the treatment cylinder (purification cylinder) as shown in the structural drawings of Figs. 1 (1) and (2). The agent 1 and the getter material 2 are separated from each other by the gap 3 or the inert charge material 4, and are equipped with a heater 5 for heating the treatment agent and the getter material. The charge ratio of the treatment agent to the getter material In terms of weight ratio, usually 1:2~1〇〇〇, preferably -13-200829507 is 1:3~1〇〇. In addition, as an inert filling material, bauxite, vermiculite, or A ceramic filler material such as aluminum or magnesium, and the gap between the treatment agent and the getter material or the charge length of the inert charge material is usually 2 to 1000 mm, preferably 5 to 500 mm. 6 denotes a temperature sensor. When the gap or the length of the gap is less than 2 mm, the treating agent will be in contact with the getter material, and there is a possibility that the ability to remove the getter material is lowered, when it exceeds 100 〇 mm, It will cause the gas treatment cylinder to become large and unsuitable. ^ The gas of the present invention The shape of the body treatment cylinder is generally cylindrical, and its size is usually 10 to 500 mm in inner diameter and 20 to 2500 mm in length. The total length of the treatment agent and the getter material in the gas treatment cylinder is usually 丨〇. The material constituting the gas treatment cylinder may, for example, be carbon steel, manganese steel, chrome steel, molybdenum steel, stainless steel or nickel steel. Among them, SUS316, SUS316L, etc. are preferable. The present invention will be more specifically described below by way of examples, but the present invention is not limited to these examples. [Example 1] (Preparation of treating agent) A commercially available nickel catalyst (containing metallic nickel and Nickel oxide, Ni: 45 to 47 wt%, Cr: 2 to 3 wt%, Cu: 2 to 3 wt%, diatomaceous earth: 27 to 29 wt%, graphite: 4 to 5 wt%, specific surface area: 15 0 m 2 /g, diameter 5 mm A molded body having a height of 4.5 mm is used as a raw material for the treating agent. The nickel catalyst is a stabilized nickel catalyst which is subjected to mild oxidation after reduction to be treated in a state of not igniting in air. The nickel catalyst which was pulverized to a size of 8 to 10 mesh was filled in a stainless steel processing cylinder having a diameter of 23 mm and a length of 1000 mm, and the filling length was 200 mm. The heater of the treatment tube was heated to bring the temperature of the catalyst (treatment agent) to 420 ° C, and hydrogen gas was introduced at a flow rate of 2,500 ml / minute, and the reduction treatment was carried out for 3 hours, followed by cooling to normal temperature. (Methane removal treatment) Then, after heating the heater of the treatment cylinder, argon gas containing 150 ppm of methane impurities was introduced at a flow rate of 3,300 ml/min to carry out methane removal treatment. Further, the contact temperature of the argon gas with the treating agent was maintained at about 420 ° C during the removal treatment. During this period, a part of the gas removed from the treatment cylinder was sampled, and whether methane was removed by gas chromatography was measured. As a result, methane was removed even after 1000 hours, and the removal ability (per lg treatment) The amount of methane removed was 358 cc / g or more. [Example 2] (Preparation of treatment agent) A commercially available stabilized nickel catalyst similar to that of Example 1 was pulverized to 8 to 10 mesh, and was charged into a treatment cylinder in the same manner as in Example 1 to have a charge length of 20 0mm. The heater of the treatment cylinder is heated to bring the temperature of the treatment agent to 420 ° C. At the same time, a mixed gas of oxygen and argon gas is introduced at a flow rate of 3300 ml/min, and the concentration of oxygen is slightly increased to make it from the beginning. 20% was increased to a concentration of 100% at the end, and after 8 hours of oxidation treatment, it was cooled to normal temperature. (Methane removal treatment) Then, after heating the heater of the treatment cylinder, argon gas containing 150 ppm of methane impurities was introduced at a flow rate of 3,300 ml/min to carry out methane removal -15 - 200829507. Further, the contact temperature of the argon gas with the treating agent was maintained at about 420 ° C during the removal treatment. During this period, a portion of the gas removed from the treatment cylinder was sampled, and whether methane was removed by gas chromatography, as a result, methane was removed even after 1,000 hours passed, and its removal ability (per The amount of methane removed by the lg treating agent was 35 8 cc / g or more. [Comparative Example 1] (Preparation of getter material) A zirconium sponge and a bulk vanadium (purity of 95% or more) were mixed with chromium® 70 wt% and vanadium 3 wt%, and then subjected to a high frequency induction heating furnace. The smelting is carried out to obtain an alloy of about 5 kg. The alloy was pulverized by a ball mill under an argon atmosphere, and 14 to 20 mesh were selected as a getter material. It was filled in a stainless steel refining cylinder with an inner diameter of 23 mm and a length of 1 000 mm, and the filling length was 220 mm. The heater of the refining cylinder was heated to bring the temperature of the getter material to 500 ° C, and argon gas was introduced at a flow rate of 3,300 ml / min for activation treatment for 6 hours, and then cooled to normal temperature. (Methane removal treatment) Then, the heater of the purification cylinder was heated, and then argon gas containing 150 ppm of methane impurities was introduced at a flow rate of 3,300 ml/min to carry out methane removal treatment. In addition, the contact temperature of the argon gas with the getter material was maintained at about 420 °C during the removal process. During this period, a part of the gas removed from the refining cylinder was sampled, and whether methane was removed by gas chromatography was determined. After 1 60 hours, methane could not be removed, and its removal ability (per lg absorption) The amount of methane removed by the gas material was 14 8 cc / g. In addition, argon gas containing 260 ppm of hydrogen impurities was passed through a purification cylinder in the same manner as above, and the hydrogen removal treatment was carried out in the same manner. As a result, the hydrogen removal ability was 85 cc / g. [Comparative Example 2] In the removal treatment of methane of Example 1, except that argon gas containing methane impurities was brought into contact with a treatment agent (reduced treatment) at a temperature of normal temperature (about 25 ° C), and Example 1 The methane removal treatment was carried out in the same manner. As a result, the removal ability of the treatment agent (the amount of removal of methane per lg treatment agent) was 1 cc / g or less. ® [Comparative Example 3] In the removal treatment of methane of Example 2, except that argon gas containing methane impurities was brought into contact with a treating agent (oxidized treatment) at a normal temperature (about 25 ° C), 2 The methane removal treatment was carried out in the same manner. As a result, the removal ability of the treatment agent (the amount of removal of methane per lg treatment agent) was 1 cc / g or less. Example 3 (Production of a gas processing cylinder) A commercially available stabilized nickel which was pulverized in the same manner as in Example 1 was prepared upstream of a processing cylinder made of stainless steel (SUS316L) having an inner diameter of 37.l mm and a length of 1000 mm. Catalyst, the length of the charge is 100mm. Further, the getter material prepared in the same manner as in Comparative Example 1 was filled in the gap at intervals of 20 mm, and the charge length was 220 mm, and a gas treatment cylinder as shown in Fig. 1 (1) was produced. The heater of the gas processing cylinder was heated to bring the temperature of the treating agent to 500 ° C, and argon gas was introduced from the downstream at a flow rate of 8400 ml / minute, and after activation treatment for 6 hours, it was cooled to normal temperature. -17- 200829507 (Refining treatment of argon gas) Next, the heater of the gas processing cylinder is heated to about 4 2 0. (: After that, argon gas containing hydrogen, oxygen, carbon monoxide, carbon dioxide, water, and methane 50 ppm as impurities was introduced from the inlet (upstream) of the gas treatment cylinder at a flow rate of 84 〇〇ml/min. A refining treatment of argon gas. During this period, a part of the gas removed from the gas treatment cylinder is sampled, and impurities (hydrogen, oxygen, carbon monoxide, carbon dioxide, and impurities contained in the argon gas are measured by an atmospheric pressure mass spectrometer (API-MS). Water), after a long period of time (500 hours), these impurities were not detected. Further, the purified argon gas was added to the impurities and recycled again. [Example 4] (Production of gas treatment device) Commercially available The synthetic zeolite (adsorbent) equivalent to 5 A is filled in a non-recording steel adsorption cylinder with an inner diameter of 3 7 · 1 mm and a length of 800 mm, so that the length of the crucible is 100 mm. The processing cylinder prepared in the same manner as in Example 1 (wherein, the inner diameter is 37.1 mm, the charging length is 100 mm) (upstream) and the two cylinders (downstream) of the adsorption cylinder are connected in parallel with the adsorption cylinder, and each Can be separately Oxidation treatment and activation treatment were carried out. In the treatment cylinder, the treatment agent was oxidized in the same manner as in Example 2, and the temperature of the adsorbent was heated to 350 ° C in the adsorption cylinder, and argon was introduced at a flow rate of 8,400 ml/min. The gas was subjected to an activation treatment for 8 hours, and then each cylinder was cooled to room temperature. (Refrosion treatment of argon gas) After heating the heater of the treatment cylinder to about 420 ° C, hydrogen, oxygen, carbon monoxide as an impurity was contained. , carbon dioxide, water, lOppm and -18- 200829507 A 50p pm helium gas is introduced into the treatment cylinder and the adsorption cylinder on one side at a flow rate of 8400ml / minute for argon gas refining treatment. A part of the gas removed by the adsorption tube is sampled, and impurities (hydrogen, oxygen, carbon monoxide, carbon dioxide, water, methane) contained in the argon gas are measured by an atmospheric pressure mass spectrometer (API-MS), and cannot be detected after 20 hours. These impurities are then transferred. Then, the adsorption cartridge is switched to the other side, and the argon gas refining treatment is continued, and at the same time, the adsorbent of the adsorption cartridge used is regenerated by activation, 20 small After that, the adsorption tube is switched again. By repeating this operation, the argon gas is purified, and after a long time (500 hours), impurities (hydrogen, oxygen, carbon monoxide, carbon dioxide, water, and a hospital) cannot be detected. In addition, the purified argon gas is added to the impurities and then recycled. [Example 5] In the argon gas refining treatment of Examples 3 and 4, in addition to hydrogen, oxygen, carbon monoxide, carbon dioxide, and water, 1 〇ρριη In the same manner as in Examples 3 and 4, nitrogen gas, ammonia gas, and helium gas of 5 〇 ppm of methane were used as the inert gas to be subjected to the purification treatment. As a result, in any case, after a long period of time (500 hours) No impurities could be detected. As described above, the treatment method, the purification method, and the gas treatment apparatus according to the examples of the present invention can easily remove methane impurities which are difficult to remove contained in the inert gas with high efficiency and excellent removal efficiency. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (1) and (2) are structural views showing an example of a gas processing cartridge of the present invention. -19· 200829507 [Explanation of main component symbols] 1 Treatment agent 2 Suction material 3 Clearance 4 Inert filling material 5 Heater 6 Temperature sensor