JP2008031413A - 天然ガスハイドレートからメタンガスを回収する方法 - Google Patents
天然ガスハイドレートからメタンガスを回収する方法 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
【解決手段】天然ガスハイドレートに窒素と二酸化炭素との混合ガスを加えて前記混合ガスとメタンガスを置換する工程を含む、天然ガスハイドレートからメタンガスを回収する方法。天然ガスハイドレート層を崩壊させることなく、従来の方法よりもメタンガスを高い収率で回収でき、窒素と二酸化炭素との混合ガスとして排ガスを使用することができる。
【選択図】図1
Description
本発明者の論文に開示された方法によって、天然ガスハイドレートをラマン(Raman)実験用高圧セル(cell)に安置させた(参照: Sloan、Jr.E.D.、Clathrate Hydrates of Natural Gases、2nd ed.、Marcel Dekker、New York、1998)。その後、前記高圧セル内部の初期温度を0℃に維持しつつ、同じ温度を維持した窒素と二酸化炭素を8:2(モル比)で含む混合ガスを前記高圧セル内部に120気圧の圧力になるまで注入して、天然ガスハイドレート中のメタンガスを混合ガスに置換する反応を23時間行なったが、23時間経過した時点で高圧セル内部の温度は1.1℃を示した。次いで、反応時間の経過に伴って前記天然ガスハイドレートから回収されたメタンガスの量を測定し、天然ガスハイドレート中に含まれたメタンガスの量と比較してメタンガスの回収率を算出した。この際、メタンガスの量はラマン分光器(RFS-100S FT-Raman Spectrometer、Bruker、USA)を用いて測定し、対照群として混合ガスの代りに二酸化炭素ガスだけを用いた実験群を使用した(参照: 図2)。図2は二酸化炭素ガス(対照群)及び窒素と二酸化炭素との混合ガス(実験群)を用いて天然ガスハイドレートからメタンガスを回収する場合、経時的なメタンガスの回収率の変化を示すグラフであって、(●)は対照群を示し、(■)は実験群を示す。
これらの結果から、混合ガスを用いた場合、純粋な二酸化炭素ガスを注入してメタンガスを回収する場合とは異なり、小さいケージに捕集されているメタンガスが窒素ガスにより置換されるので、さらに多量のメタンガスを天然ガスハイドレートから回収できるものと考えられた。
実施例1から分かるように、窒素と二酸化炭素との混合ガスを用いる場合、従来の二酸化炭素だけを使う場合よりも多量のメタンガスを回収できる。混合ガスに含まれる窒素と二酸化炭素との混合比によって、メタンガスの回収率が変わる否かを確認した。すなわち、窒素と二酸化炭素がそれぞれ0:10、1:9、2:8、3:7、4:6、5:5、6:4、7:3、8:2又は9:1(モル比)の比率で混合されたガスを使用し、20時間反応させることを除き、前記実施例1と同様な方法でメタンガスの回収率を測定した(参照: 表1)。
従って、様々な混合比で窒素と二酸化炭素の混合ガスを使用する場合、従来の二酸化炭素ガスのみを使用する場合に比べてメタンガスを効率よく回収できることが確認できた。
前記実施例1及び2の結果から、全ての窒素と二酸化炭素との混合ガスを用いることが可能なことが確認された。そこで、多様な混合比率の窒素と二酸化炭素を含む排ガスを使って天然ガスハイドレートからメタンガスを回収できるか否かを確認した。
混合ガスに代えてコンビナートに存在する10箇所の工場から排出される排ガスを用いることを除いて、前記実施例1と同様の方法によりメタンガスの回収率を測定した(参照: 表2)。
混合ガスの圧力条件を決定するため、窒素と二酸化炭素が8:2(モル比)の比率で混合されたガスを使用して20時間反応させ、混合ガスの圧力をそれぞれ10、20、30、40、50、80、120、160、及び200気圧で加えることを除いて、前記実施例1と同様の方法によりメタンガスの回収率を測定した(参照: 表3)。
従って、天然ガスハイドレートに混合ガスを30ないし200気圧で加える場合、混合ガスによるメタンガスの置換反応が効率的に行われることが確認された。
Claims (6)
- 天然ガスハイドレートに窒素と二酸化炭素との混合ガスを加えて前記混合ガスとメタンガスを置換する工程を含む、天然ガスハイドレートからメタンガスを回収する方法。
- 混合ガスが窒素と二酸化炭素が1:9ないし9:1(モル比)で混合されることを特徴とする請求項1に記載の天然ガスハイドレートからメタンガスを回収する方法。
- 混合ガスが窒素と二酸化炭素が4:6ないし9:1(モル比)で混合されることを特徴とする請求項1に記載の天然ガスハイドレートからメタンガスを回収する方法。
- 混合ガスが窒素と二酸化炭素が8:2(モル比)で混合されることを特徴とする請求項1に記載の天然ガスハイドレートからメタンガスを回収する方法。
- 天然ガスハイドレートに混合ガスを0ないし5℃の温度を維持しつつ30ないし200気圧になるまで加えて9ないし20時間反応させることを特徴とする請求項1に記載の天然ガスハイドレートからメタンガスを回収する方法。
- 天然ガスハイドレートに窒素と二酸化炭素を含む排ガスを0ないし5℃の温度の範囲で30ないし200気圧になるまで加えて、9ないし20時間前記混合ガスとメタンガスを置換する工程を含む、天然ガスハイドレートからメタンガスを回収する方法。
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KR1020060071835A KR100735841B1 (ko) | 2006-07-31 | 2006-07-31 | 천연가스 하이드레이트로부터 메탄가스를 회수하는 방법 |
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JPH0671161A (ja) * | 1992-07-30 | 1994-03-15 | Chiyoda Corp | 炭酸ガス固定化方法 |
JP2000061293A (ja) * | 1998-08-18 | 2000-02-29 | Toshiba Corp | メタンハイドレートを燃料として利用するシステム |
JP2002069466A (ja) * | 2000-06-08 | 2002-03-08 | Korea Advanced Inst Of Sci Technol | ハイドレート促進剤を用いたガス成分の分離方法 |
JP2006045128A (ja) * | 2004-08-05 | 2006-02-16 | National Institute Of Advanced Industrial & Technology | メタンハイドレートの分解方法及び分解装置 |
JP2006096779A (ja) * | 2004-09-28 | 2006-04-13 | National Institute Of Advanced Industrial & Technology | 窒素によるメタンハイドレートの分解方法及び分解装置 |
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US7222673B2 (en) * | 2004-09-23 | 2007-05-29 | Conocophilips Company | Production of free gas by gas hydrate conversion |
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JPH0671161A (ja) * | 1992-07-30 | 1994-03-15 | Chiyoda Corp | 炭酸ガス固定化方法 |
JP2000061293A (ja) * | 1998-08-18 | 2000-02-29 | Toshiba Corp | メタンハイドレートを燃料として利用するシステム |
JP2002069466A (ja) * | 2000-06-08 | 2002-03-08 | Korea Advanced Inst Of Sci Technol | ハイドレート促進剤を用いたガス成分の分離方法 |
JP2006045128A (ja) * | 2004-08-05 | 2006-02-16 | National Institute Of Advanced Industrial & Technology | メタンハイドレートの分解方法及び分解装置 |
JP2006096779A (ja) * | 2004-09-28 | 2006-04-13 | National Institute Of Advanced Industrial & Technology | 窒素によるメタンハイドレートの分解方法及び分解装置 |
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JP2013119063A (ja) * | 2011-12-07 | 2013-06-17 | Jfe Engineering Corp | 気体分離方法及び装置そして気体処理方法及び装置 |
JP2015081346A (ja) * | 2013-10-22 | 2015-04-27 | 韓国科学技術院Korea Advanced Institute Of Science And Technology | 二酸化炭素と空気との混合ガスを注入する方法を用いたガスハイドレートの生産方法 |
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US7988750B2 (en) | 2011-08-02 |
JP4668933B2 (ja) | 2011-04-13 |
KR100735841B1 (ko) | 2007-07-06 |
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