JP4977619B2 - スチームメタン改質方法 - Google Patents
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Description
図1において、本発明の方法を実施するための装置1を示す。装置1は、精油所の廃ガス及び/又は天然ガスを処理するために、本発明の方法の従来のスチームメタン改質方法への統合を図解する。これに関し、図1の精油所の廃ガスは、改質装置への供給物として、一部を天然ガスと置き換えてかかるプロセスで使用されるが、本発明は、前述のように、その炭化水素分のためにスチームメタン改質が問題であるようなる精油所の廃ガス又は他のガス流の改質目的だけに行うことができるし、又は炭化水素の含有量が、従来のスチームメタン改質技術に完全に適合する天然ガス又は他のガス流の精製目的だけにも行うことができることが理解される。処理される他の流れは、除去される好ましくない硫黄分を有していても、いなくてもよい。
上記表1には示されていないが、かかる供給物の硫黄含有量は、約5ppmと約200ppmの間の範囲でよく、硫黄含有物はメルカプタン、チオフェン、及び硫化水素の間に分割される。天然ガスの硫黄含有量は、一般的に約5ppmである。
Claims (16)
- スチームメタン改質方法であって、
オレフィン及び水素を含む供給物流を、600℃未満の温度に加熱するステップと、
供給物流中の水素及びオレフィンを、水素化及び部分酸化反応の両方を促進できる触媒と接触させ、酸素を加えることなく、前記水素をオレフィンと触媒的に反応させて、オレフィンの水素化から形成された飽和炭化水素を含有する中間生成物流を生成させるステップであって、供給物流の加熱が十分であり、及び/又はオレフィンが十分な濃度で供給物流中に存在して、中間生成物流が400℃を超える温度で生成されるステップと、
少なくとも一部は前記中間生成物流及びスチーム流で形成される改質装置供給物流をスチームメタン改質装置内で反応させて、供給物流よりも多いモル量の水素を有し、一酸化炭素、水及び二酸化炭素をも含有する合成ガス生成物流を得るステップとを含み、
水素及びオレフィンの触媒反応が、触媒を含有する反応装置内で、10,000hr−1を超える空間速度において、十分な水素量を用いて行い、改質装置供給物流が乾燥量基準で0.5体積%未満オレフィンのオレフィン含有量を有する方法。 - 前記供給物流が、硫黄化合物も含み、
水素が、触媒反応中に硫黄化合物とも反応して、中間生成物流が硫黄化合物の水素化から形成された硫化水素をも含有し、
中間生成物流を冷却し、処理して、硫化水素を除去し、処理後に中間生成物流が0.1ppm以下の硫化水素を含有するようにし、
前記改質装置供給物流が、少なくとも一部は処理後の中間生成物流によって形成される、
請求項1に記載の方法。 - 前記オレフィンが、供給物流中に乾燥量基準で3体積%以上の量で存在する、請求項1に記載の方法。
- スチームメタン改質方法であって、
乾燥量基準で15体積%以上の少なくとも2個の炭素原子を有する炭化水素及び/又は少なくとも3体積%のオレフィンを含む供給物流を、600℃を超えない温度に加熱するステップと、
供給物流中に含有された炭化水素及び/又はオレフィン、並びに酸素及びスチームを、水素化及び部分酸化反応の両方を促進できる触媒と接触させ、炭化水素及び/又はオレフィン、スチーム及び酸素を、酸素対炭素比が0.25未満、スチーム対炭素比が0.5未満において触媒的に反応させて中間生成物流を生成させるステップと、
少なくとも一部が前記中間生成物流及びスチーム流で形成される改質装置供給物流をスチームメタン改質装置内で反応させて、中間生成物流よりも多いモル量の水素を有し、一酸化炭素、水及び二酸化炭素をも含有する合成ガス生成物流を得るステップとを含み、
触媒反応が、触媒を含有する反応装置内で、10,000hr−1を超える空間速度において、中間生成物流が500℃と860℃の間の温度で生成するのに十分な量の酸素で、かつ、改質装置供給物流が、メタン、乾燥量基準で0.5体積%未満のオレフィン、乾燥量基準で10体積%未満の2個以上の炭素原子を有するアルカン、乾燥量基準で1体積%以下のアルカン及びオレフィン以外の炭化水素からなる炭化水素含有量を有し、残分が水素、一酸化炭素、二酸化炭素及び水蒸気を含むように選択される酸素対炭素比及びスチーム対炭素比で行われる方法。 - スチームメタン改質方法であって、
炭化水素、硫黄化合物及び水素を含む供給物流を、600℃を超えない温度に加熱するステップと、
前記水素を酸素無しで炭化水素及び硫黄化合物と触媒的に反応させることにより中間生成物を生成させるステップであって、中間生成物流が、炭化水素及び硫黄化合物の水素化によってそれぞれ形成される、飽和炭化水素及び硫化水素を含有し、供給物流の加熱及び/又は炭化水素の水素化が、中間生成物流を、400℃を超える温度で生成するのに十分であるステップ、或いは、酸素、スチーム及び供給物流内に含有されている炭化水素、水素及び硫黄化合物を触媒的に反応させることにより中間生成物を生成させるステップであって、中間生成物流が追加の水素、並びに酸素、スチーム及び炭化水素の反応によって生成された一酸化炭素、並びに硫黄化合物の転換によって生成された硫化水素を含有し、中間生成物流が、500℃と860℃の間の温度で生成されるよう、十分な量の酸素が存在し、スチーム対炭素比及び酸素対炭素比は、生成された追加の水素のモル量を制御するために、それぞれ0.5未満及び0.25未満に選択されるステップと、
水素、炭化水素及び硫黄化合物、或いは、酸素、スチーム、炭化水素及び硫黄化合物の触媒反応は、水素化と部分的酸化反応の両方を促進できる触媒との接触を通じて、両方の触媒反応に対して同じである反応容器内で行われ、触媒反応は、10,000hr−1を超える空間速度において行われ、
前記中間生成物流を冷却するステップと、
硫化水素を除去することにより前記中間生成物流を処理し、処理後の中間生成物流が0.1ppm以下の硫化水素を含むステップと、
少なくとも一部分は前記中間生成物流で形成される改質装置供給物流とスチーム流を、スチームメタン改質装置内で反応させて、供給物流及び中間生成物流よりも多いモル量の水素を有し、一酸化炭素、水及び二酸化炭素をも含有する合成ガス生成物流を得るステップとを含む方法。 - 前記供給物流が、乾燥量基準で、15体積%以上の少なくとも2個の炭素原子を有する炭化水素及び/又は少なくとも3体積%のオレフィンを含有し、
水素、炭化水素及び硫黄化合物の触媒反応中に、前記水素が供給物流内に存在するオレフィンのいずれかとも反応して、飽和炭化水素をも生成し、かつ、十分な水素が存在して、乾燥量基準で0.5体積%未満である改質供給物流中のオレフィン含有量が得られ、
酸素、スチーム、炭化水素及び硫黄化合物の触媒反応が、メタン、乾燥量基準で0.5体積%未満のオレフィン、乾燥量基準で10体積%未満の、2個以上の炭素原子を有するアルカン、乾燥量基準で1体積%以下の、アルカン及びオレフィン以外の炭化水素からなる炭化水素含有量が改質装置供給物流内で得られるように、酸素対炭素比及びスチーム対炭素比が選択されて行われる、請求項5に記載の方法。 - 両方の触媒反応中に、スチームメタン改質装置が不変の焼成速度で運転され、酸素、スチーム、炭化水素及び硫黄化合物の触媒反応中に生成される追加の水素が、合成ガス生成物流中の水素のモル量を、酸素の添加無しで、水素、炭化水素及び硫黄化合物を触媒反応させるときに生成する量よりも増加させる、請求項5又は6に記載の方法。
- 酸素、スチーム、炭化水素及び硫黄化合物の触媒反応中に、スチームメタン改質装置が、水素、炭化水素及び硫黄化合物の触媒反応中におけるよりも低い焼成速度で運転される、請求項5又は6に記載の方法。
- 接触水素化状態の運転中に、スチームを反応装置に導入して、炭化水素の改質反応に関与させて、これによって更に追加の水素及び一酸化炭素を中間生成物流中に生成させるステップを更に含む、請求項1、5又は6に記載の方法。
- 水素を、天然ガス流に加え、前記天然ガス流を、そこに含有される硫黄化合物を硫化水素へと水素化し、硫化水素を除去することによって処理し、天然ガス流が処理後に乾燥量基準で0.1ppm(体積)未満の硫化水素を含有するようにし、
改質装置供給物流が、一部は天然ガス流を中間生成物流と一緒にすることによって形成される、請求項1、2、4又は6に記載の方法。 - 前記供給物流が天然ガスを更に含む、請求項1、2、4又は6に記載の方法。
- 前記供給物流が、FCC廃ガス、コーカー廃ガス、又はスイート精油所ガスである、請求項4又は6に記載の方法。
- 前記供給物流が、スチームメタン改質装置の運転圧力よりも、3×10 4 Pa(5psi)から7×10 5 Pa(100psi)上回る圧力に圧縮されている、請求項1、2、4、5又は6に記載の方法。
- 前記供給物流が、50ppm未満の硫黄含有量を有する、請求項1、5又は6に記載の方法。
- 前記触媒が、金属製モノリス上に担持されたVIII族金属触媒である、請求項1、4、5又は6に記載の方法。
- 前記中間生成物流が、亜鉛酸化物又は銅酸化物吸着剤と接触することで処理される、請求項1、4、5又は6に記載の方法。
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