JP2010516843A - マイクロチャネルプロセス技術を用いて天然ガスを分子量の高くなった炭化水素に変換するためのプロセスおよび装置 - Google Patents
マイクロチャネルプロセス技術を用いて天然ガスを分子量の高くなった炭化水素に変換するためのプロセスおよび装置 Download PDFInfo
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Abstract
【選択図】図1
Description
CoM1 aM2 bOx
式中、M1は、Fe、Ni、Ru、Re、Osまたはそれらの2つ以上の混合物、
M2は、Li、B、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、Sc、Y、La、Ac、Ti、Zr、CeまたはTh、あるいはそれらの2つ以上の混合物、
aは、ゼロから約0.5の範囲内の数、
bは、ゼロから約0.5の範囲内の数、
xは、存在する元素の原子価要件を満たすために必要な酸素の数、
によって表される組成物を含んでよい。
(A)触媒金属を含む組成物を担体に含浸させて中間触媒生成物を準備する工程、
(B)工程(A)で形成された中間触媒生成物を焼成する工程、
(C)工程(B)で形成された、焼成された中間生成物に触媒金属を含む別の組成物を含浸させて別の中間触媒生成物を準備する工程、および
(D)工程(C)で形成された別の中間触媒生成物を焼成して触媒を提供する工程
によって作ってよい。
H2O+CH4 → CO+3H2
を指してよい。この反応は吸熱性であり、SMR触媒の存在下で行ってよい。CO+H2の生成物混合物を合成ガスまたはシンガス(syn gas)と呼んでよい。この反応を実現させるために必要な熱は、燃料(例えばH2)と酸素または酸素源(例えば空気または酸素富化空気)との混合物の燃焼反応によって提供してよい。燃焼反応は発熱性であり、燃焼触媒の存在下で行ってよい。
nCO+2nH2 → (CH2)n+nH2O
によって表される化学反応を指してよい。この反応は、フィッシャー・トロプシュ触媒の存在下で行ってよい発熱反応である。
CoM1 aM2 bOx
によって表される組成物を含んでよく、式中、M1は、Fe、Ni、Ru、Re、Osまたはそれらの混合物であり、一実施態様ではM1は、RuまたはReあるいはそれらの混合物であり、M2は、Li、B、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、Sc、Y、La、Ac、Ti、Zr、CeまたはTh、あるいはそれらの2つ以上の混合物であり、aは、ゼロから約0.5、一実施態様ではゼロから約0.2の範囲内の数であり、bは、ゼロから約0.5、一実施態様ではゼロから約0.1の範囲の数であり、xは、存在する元素の原子価要件を満たすために必要な酸素の数である。
Claims (47)
- (A)SMR原料をSMRマイクロチャネル反応器の中に流し、1つ以上のSMR触媒と接触させて第1の中間生成物を形成させ、前記SMR原料はメタンおよび水蒸気を含み、前記第1の中間生成物はCOおよびH2を含み;前記SMRマイクロチャネル反応器は複数のSMRプロセスマイクロチャネルおよび複数の燃焼チャネルを含み;前記SMRプロセスマイクロチャネルは前記1つ以上のSMR触媒を含み、前記メタンおよび水蒸気は前記プロセスマイクロチャネルの中の前記1つ以上のSMR触媒と接触し、前記H2の一部を前記第1の中間生成物から分離して第2の中間生成物を形成させ、前記第2の中間生成物はCOおよびH2を含み;前記燃焼チャネルは1つ以上の燃焼触媒を含み、前記分離されたH2は酸素または酸素源と一緒にされて燃焼反応混合物を形成し;前記燃焼反応混合物は前記1つ以上の燃焼触媒と接触し、燃焼反応を行い、熱および燃焼排気を発生し;前記燃焼チャネルから前記SMRプロセスマイクロチャネルへ熱を移動させる工程と、
(B)前記第2の中間体生成物をフィッシャー・トロプシュマイクロチャネル反応器の中に流し、1つ以上のフィッシャー・トロプシュ触媒と接触させて1つ以上の分子量の高くなった炭化水素を含むフィッシャー・トロプシュ生成物を形成させ;前記フィッシャー・トロプシュマイクロチャネル反応器は、複数のフィッシャー・トロプシュプロセスマイクロチャネルおよび複数の熱交換チャネルを含み;前記フィッシャー・トロプシュプロセスマイクロチャネルは前記1つ以上のフィッシャー・トロプシュ触媒を含み、前記第2の中間生成物は前記フィッシャー・トロプシュプロセスマイクロチャネルの中の前記1つ以上のフィッシャー・トロプシュ触媒と接触し;前記フィッシャー・トロプシュプロセスマイクロチャネルから前記熱交換チャネルの中の熱交換流体へ熱を移動させる工程と
を含むプロセス。 - 工程(B)において形成された前記フィッシャー・トロプシュ生成物は、COおよびH2を含む気体混合物をさらに含み、前記気体混合物は前記フィッシャー・トロプシュ生成物から分離され、前記分離された気体混合物は第3の中間生成物を含む請求項1に記載のプロセスであって、
(C)前記第3の中間体生成物を前記第2のフィッシャー・トロプシュマイクロチャネル反応器の中に流し、1つ以上の第2のフィッシャー・トロプシュ触媒と接触させて1つ以上の分子量の高くなった炭化水素を含む第2のフィッシャー・トロプシュ生成物を形成させ;前記第2のフィッシャー・トロプシュマイクロチャネル反応器は複数の第2のフィッシャー・トロプシュプロセスマイクロチャネルおよび複数の第2の熱交換チャネルを含み;前記第2のフィッシャー・トロプシュプロセスマイクロチャネルは前記1つ以上の第2のフィッシャー・トロプシュ触媒を含み、前記第3の中間生成物は前記第2のフィッシャー・トロプシュプロセスマイクロチャネルの中の前記1つ以上の第2のフィッシャー・トロプシュ触媒と接触し;前記第2のフィッシャー・トロプシュプロセスマイクロチャネルから前記第2の熱交換チャネルの中の熱交換流体へ熱を移動させる工程
をさらに含むプロセス。 - 前記SMR原料は天然ガス原料から誘導され、前記フィッシャー・トロプシュマイクロチャネル反応器の中でテールガスが形成され、前記テールガスの少なくとも一部は前記天然ガス原料と一緒にされる、請求項1から2のいずれか1項に記載のプロセス。
- 前記SMR原料は天然ガス原料から誘導され、前記フィッシャー・トロプシュマイクロチャネル反応器の中でプロセス水が形成され、前記プロセス水の少なくとも一部は前記天然ガス原料と一緒にされる、請求項1から3のいずれか1項に記載のプロセス。
- 前記SMR原料は天然ガス原料から誘導され、前記フィッシャー・トロプシュマイクロチャネル反応器の中でプロセス水が形成され、前記天然ガス原料と一緒にされ、前記フィッシャー・トロプシュマイクロチャネル反応器の中でテールガスが形成され、前記テールガスの少なくとも一部は前記天然ガス原料と一緒にされる、請求項1から4のいずれか1項に記載のプロセス。
- 前記天然ガス原料、プロセス水およびテールガスは飽和装置の中で一緒にされ、前記飽和装置は前記SMRマイクロチャネル反応器の上流にある、請求項5に記載のプロセス。
- 前記SMR原料は天然ガス原料から誘導され、前記第2のフィッシャー・トロプシュマイクロチャネル反応器の中でテールガスが形成され、前記テールガスの少なくとも一部は前記天然ガス原料と一緒にされる、請求項2から6のいずれか1項に記載のプロセス。
- 前記SMR原料は、1つ以上の分子量の高くなった炭化水素を含み、前記プロセスは、前記SMR原料および水蒸気を予備改質装置の中に流して前記SMR原料中の前記分子量の高くなった炭化水素の少なくとも一部をメタンに変換する工程をさらに含み、前記予備改質装置は前記SMRマイクロチャネル反応器の上流にある、請求項1から7のいずれか1項に記載のプロセス。
- 前記SMR原料は、1つ以上の分子量の高くなった炭化水素を含み、前記プロセスは、前記SMR原料および水蒸気を予備改質装置の中に流して前記SMR原料中の前記分子量の高くなった炭化水素の少なくとも一部をメタンに変換する工程をさらに含み、前記予備改質装置は前記SMRマイクロチャネル反応器と一体化され、前記燃焼チャネルからの熱によって加熱される、請求項1から8のいずれか1項に記載のプロセス。
- 前記SMR原料は、1つ以上の分子量の高くなった炭化水素を含み、前記プロセスは、前記SMR原料および水蒸気を前記SMRプロセスマイクロチャネルの中に前記SMRプロセスマイクロチャネルの第1の部分の中の第1の温度で流して前記SMR原料の中の前記分子量の高くなった炭化水素の少なくとも一部をメタンに変換し、前記結果として得られた生成物はメタンを含む改変されたSMR原料を含み、前記改変されたSMR原料を前記SMRプロセスマイクロチャネルの第2の部分の中に第2の温度で流して前記改変されたSMR原料を前記第1の中間生成物に変換する工程をさらに含む、請求項1から9のいずれか1項に記載のプロセス。
- 前記燃焼チャネルに隣接して段階添加チャネルが配置され、酸素の前記酸素源は前記段階添加チャネルを通って前記燃焼チャネルの中へ流れる、請求項1から10のいずれか1項に記載のプロセス。
- 前記燃焼排気は蒸気および液体を含み、前記蒸気は蒸気−液体分離装置の中で前記液体から分離され、前記液体は水を含む、請求項1から11のいずれか1項に記載のプロセス。
- 前記SMR原料は天然ガス原料から誘導され、前記フィッシャー・トロプシュマイクロチャネル反応器の中でテールガスが形成され、前記テールガスはH2、CO、CO2および1つ以上の炭化水素を含み、前記テールガスはH2分離装置を通って流れて炭素豊富テールガスおよびH2豊富テールガスを提供し、前記炭素豊富テールガスは前記天然ガス原料と一緒にされ、前記H2豊富テールガスは燃料として用いられる、請求項1から12のいずれか1項に記載のプロセス。
- 前記フィッシャー・トロプシュマイクロチャネル反応器の中でテールガスが形成され、前記テールガスはN2を含み、前記テールガスは窒素分離装置を通って流れ、そこで前記テールガスからN2が分離される、請求項1から13のいずれか1項に記載のプロセス。
- 前記SMR原料は天然ガス原料から誘導され、前記フィッシャー・トロプシュマイクロチャネル反応器の中でテールガスが形成され、前記テールガスはH2、N2、CO、CO2および1つ以上の炭化水素を含み、前記テールガスはH2分離装置を通って流れて炭素豊富テールガスおよびH2豊富テールガスを提供し、前記炭素豊富テールガスはN2を含み、前記炭素豊富テールガスは窒素分離装置を通って流れ、そこで前記炭素豊富テールガスからN2が分離され、前記炭素豊富テールガスは前記天然ガス原料と一緒にされ、前記H2豊富テールガスは燃料として用いられる、請求項1から14のいずれか1項に記載のプロセス。
- 前記第2のフィッシャー・トロプシュプロセスマイクロチャネルの中の前記圧力は、前記フィッシャー・トロプシュプロセスマイクロチャネルの中の前記圧力と異なる、請求項2から15のいずれか1項に記載のプロセス。
- 前記第2の中間生成物は、工程(B)の前に圧縮される、請求項1から16のいずれか1項に記載のプロセス。
- 前記SMR原料は天然ガス原料から誘導され、前記フィッシャー・トロプシュマイクロチャネル反応器の中でテールガスが形成され、前記テールガスの少なくとも一部は前記天然ガス原料と一緒にされ、前記テールガスの前記少なくとも一部は前記天然ガス原料と一緒にされる前に圧縮される、請求項1から17のいずれか1項に記載のプロセス。
- 前記熱交換チャネルの中の前記熱交換流体は、前記熱交換チャネルの中で少なくとも部分的に蒸発する、請求項1から18のいずれか1項に記載のプロセス。
- 前記フィッシャー・トロプシュ生成物は、約5から約100の炭素原子の1つ以上のパラフィンおよび/または1つ以上のオレフィンを含む、請求項1から19のいずれか1項に記載のプロセス。
- 前記フィッシャー・トロプシュ生成物はオレフィンおよびパラフィンを含み、パラフィンに対するオレフィンの前記比は約0.01から約0.8の範囲内である、請求項1から20のいずれか1項に記載のプロセス。
- 前記フィッシャー・トロプシュ生成物は、水素化分解法、水素化異性化法または脱ロウ法を用いてさらに処理される、請求項1から21のいずれか1項に記載のプロセス。
- 前記SMR原料の前記形成において天然ガスが用いられ、前記天然ガスの中の炭素に対する前記フィッシャー・トロプシュ生成物の中の炭素の前記パーセントは、約50から約70%の範囲内である、請求項1から22のいずれか1項に記載のプロセス。
- 前記SMR原料の前記形成において天然ガスが用いられ、前記天然ガスの中の炭素に対する前記第1および第2のフィッシャー・トロプシュ生成物の中の炭素の前記合計パーセントは、少なくとも約75%である、請求項2から23のいずれか1項に記載のプロセス。
- 各SMRプロセスマイクロチャネルは少なくとも1つの伝熱壁を有し、前記SMRマイクロチャネル反応器内の熱交換のための前記熱流束は、前記伝熱壁の表面積の平方センチメートルあたり約0.01から約500ワットの範囲内である、請求項1から24のいずれか1項に記載のプロセス。
- 各SMRプロセスマイクロチャネルは、前記温度が約150から約400℃の範囲内にある第1の部分、および前記温度が約600から約1000℃の範囲内にある、第1の部分の下流にある第2の部分を有する、請求項1から25のいずれか1項に記載のプロセス。
- 各フィッシャー・トロプシュプロセスマイクロチャネルは少なくとも1つの伝熱壁を有し、前記フィッシャー・トロプシュマイクロチャネル反応器内の熱交換のための前記熱流束は、前記伝熱壁の表面積の平方センチメートルあたり約0.01から約500ワットの範囲内にある、請求項1から26のいずれか1項に記載のプロセス。
- 1つ以上の複数流式熱交換器が前記SMR原料と第1の中間生成物との間、および前記燃焼反応混合物の前記H2および前記酸素または酸素源と前記燃焼排気との間の熱交換を提供する、請求項1から27のいずれか1項に記載のプロセス。
- 温度スイング吸着法、圧力スイング吸着法、膜法、またはそれらの2つ以上の組み合わせを用いて前記第1の中間生成物からH2が分離される、請求項1から28のいずれか1項に記載のプロセス。
- 前記炭素豊富テールガスを前記H2豊富テールガスから分離するために温度スイング吸着法、圧力スイング吸着法、膜法、またはそれらの2つ以上の組み合わせが用いられる、請求項13に記載のプロセス。
- 前記N2を前記テールガスから分離するために温度スイング吸着法、圧力スイング吸着法、膜法、またはそれらの2つ以上の組み合わせが用いられる、請求項14記載のプロセス。
- 前記テールガスからH2を分離するためおよび前記炭素豊富テールガスからN2を分離するために温度スイング吸着法、圧力スイング吸着法、膜法、またはそれらの2つ以上の組み合わせが用いられる、請求項15に記載のプロセス。
- 前記SMR触媒は、La、Pt、Fe、Ni、Ru、Rh、In、Ir、W、および/またはそれらの酸化物、またはそれらの2つ以上の混合物を含む、請求項1から32のいずれか1項に記載のプロセス。
- 前記SMR触媒は、MgO、Al2O3、SiO2、TiO2、またはそれらの2つ以上の混合物をさらに含む、請求項33に記載のプロセス。
- 前記燃焼触媒は、Pd、Pr、Pt、Rh、Ni、Cu、および/またはそれらの酸化物、あるいはそれらの2つ以上の混合物を含む、請求項1から34のいずれか1項に記載のプロセス。
- 前記燃焼触媒は、Al2O3、SiO2、MgO、またはそれらの2つ以上の混合物をさらに含む、請求項35に記載のプロセス。
- 前記フィッシャー・トロプシュ触媒は、Co、Fe、Ni、Ru、Re、Os、および/またはそれらの酸化物の1つ以上、あるいはそれらの2つ以上の混合物を含む、請求項1から36のいずれか1項に記載のプロセス。
- 前記フィッシャー・トロプシュ触媒は、周期律表のIA族、IIA族、IIIB族またはIIB族からの1つ以上の金属および/またはそれらの酸化物、ランタニド金属および/またはその酸化物、アクチニド金属および/またはその酸化物、あるいはそれらの2つ以上の混合物を含む、請求項1から37のいずれか1項に記載のプロセス。
- 前記SMR触媒、燃焼触媒および/またはフィッシャー・トロプシュ触媒は、固体粒子の前記形である、請求項1から38のいずれか1項に記載のプロセス。
- 前記SMR触媒、燃焼触媒および/またはフィッシャー・トロプシュ触媒は、前記チャネルの内壁上に被覆されるか、前記チャネルの内壁上に成長するか、またはフィン構造体上に被覆される、請求項1から39のいずれか1項に記載のプロセス。
- 前記SMR触媒、燃焼触媒および/またはフィッシャー・トロプシュ触媒は、側流構成、貫流構成または蛇行構成を有する担持構造体上に担持されている、請求項1から40のいずれか1項に記載のプロセス。
- 前記SMR触媒、燃焼触媒および/またはフィッシャー・トロプシュ触媒は、発泡体、フェルト、詰め物、フィン、またはそれらの2つ以上の組み合わせの前記構成を有する担持構造体上に担持されている、請求項1から41のいずれか1項に記載のプロセス。
- 前記SMR触媒、燃焼触媒および/またはフィッシャー・トロプシュ触媒は、少なくとも1つのフィンを含むフィンアセンブリの前記形の担持構造体上に担持されている、請求項1から42のいずれか1項に記載のプロセス。
- 前記フィッシャー・トロプシュ生成物および/または第2のフィッシャー・トロプシュ生成物は、前記フィッシャー・トロプシュマイクロチャネル反応器および/または第2のフィッシャー・トロプシュマイクロチャネル反応器と直列に動作している水素化分解装置の中で水素化分解される、請求項1から43のいずれか1項に記載のプロセス。
- SMR槽の中に配置された複数のSMRマイクロチャネル反応器を含む装置であって、各SMRマイクロチャネル反応器は、複数のSMRプロセスマイクロチャネル、複数の燃焼チャネルおよび複数の段階添加チャネルを含み、各燃焼チャネルは、少なくとも1つの段階添加チャネルに隣接しており、
前記SMR槽は、SMR原料を前記SMRプロセスマイクロチャネルに流すためのマニホルド、前記SMRプロセスマイクロチャネルからSMR生成物を流すためのマニホルド、燃料を前記燃焼チャネルへ流すためのマニホルド、酸素または酸素源を前記段階添加チャネルに流すためのマニホルド、および前記燃焼チャネルから燃焼排気を流すためのマニホルドを備えている
装置。 - フィッシャー・トロプシュ槽の中に配置された複数のフィッシャー・トロプシュマイクロチャネル反応器を含む装置であって、各フィッシャー・トロプシュマイクロチャネル反応器は、複数のフィッシャー・トロプシュプロセスマイクロチャネルおよび複数の熱交換チャネルを含み、
前記フィッシャー・トロプシュ槽は、フィッシャー・トロプシュ原料を前記フィッシャー・トロプシュプロセスマイクロチャネルに流すためのマニホルド、前記フィッシャー・トロプシュプロセスマイクロチャネルからフィッシャー・トロプシュ生成物を流すためのマニホルド、熱交換流体を前記熱交換チャネルに流すためのマニホルドおよび前記熱交換チャネルから熱交換流体を流すためのマニホルドを備えている
装置。 - 約5から約100の炭素原子のオレフィンとパラフィンとの混合物を含み、パラフィンに対するオレフィンの前記モル比は約0.01から約0.8の範囲内である組成物。
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Publication number | Publication date |
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JP5383508B2 (ja) | 2014-01-08 |
CN101657524B (zh) | 2013-02-13 |
WO2008089376A3 (en) | 2009-03-19 |
US7829602B2 (en) | 2010-11-09 |
US20080210596A1 (en) | 2008-09-04 |
CA2675816C (en) | 2015-09-01 |
CN101657524A (zh) | 2010-02-24 |
BRPI0806807A2 (pt) | 2011-09-13 |
WO2008089376A9 (en) | 2008-09-12 |
AU2008206147A1 (en) | 2008-07-24 |
AU2008206147B2 (en) | 2012-05-17 |
EP2111438B1 (en) | 2014-08-06 |
RU2009131483A (ru) | 2011-03-10 |
EP2111438A2 (en) | 2009-10-28 |
RU2461603C2 (ru) | 2012-09-20 |
EP2447339A1 (en) | 2012-05-02 |
WO2008089376A2 (en) | 2008-07-24 |
CA2675816A1 (en) | 2008-07-24 |
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