JP6253795B2 - ガス状燃料cpox改質器及びcpox改質の方法 - Google Patents
ガス状燃料cpox改質器及びcpox改質の方法 Download PDFInfo
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- JP6253795B2 JP6253795B2 JP2016553235A JP2016553235A JP6253795B2 JP 6253795 B2 JP6253795 B2 JP 6253795B2 JP 2016553235 A JP2016553235 A JP 2016553235A JP 2016553235 A JP2016553235 A JP 2016553235A JP 6253795 B2 JP6253795 B2 JP 6253795B2
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Description
本願は、2013年11月6日に出願された米国仮特許出願第61/900,543号明細書の出願日の優先権と利益を享受し、その開示の全体の内容は、参照により本明細書に組み込まれる。
頑丈な細穴構造を有する発泡モノリスの場合、そのような構造は、全体的に、ガス流路のランダム性を拡大する傾向がある。ホットスポットにより細穴構造への損傷は無視できる或いは存在しないが、CPOX反応の生産性に悪影響を及ぼす散乱する且つ束の間のコールドスポットの問題は、このタイプの発泡モノリスの一つの欠点のままである。
上記に照らして、本教示は、現状の技術の欠陥及び/不利な点の一つ以上を処理できる、例えば、フラッシングが生じる機会や傾向がほとんどない又は全くない、過剰に高いCPOX反応温度が無い、及び/又はガスのストリームの経路指定、ガスの流れのコンポーネント及び通路の全ての全体にわたって低背圧であるガス状燃料CPOX改質器及びガス状燃料のCPOX改質の方法を提供する。
a)スタートアップモードにおいて:
(i)酸素含有ガス及びガス状改質可能燃料を含むガス状CPOX反応混合物を複数の互いに離間されたCPOX反応器ユニットの各々のインレットに導入すること、各反応器ユニットは、ガス状CPOX反応混合物のためのインレット、水素リッチ改質油のためのアウトレット、内表面と外表面を有する壁を備えること、その壁は、中に配置されるCPOX触媒を有する及び/又はそのCPOX触媒の構造体を備える壁の少なくとも一セクションで開口ガス流通路を囲むこと、そのような触媒含有壁セクション及びそれによって囲まれる開口ガス流通路は、ガス相CPOX反応ゾーンを画定すること、触媒含有壁セクションは、CPOX反応状態下で安定でありながら、ガス状CPOX反応混合物を中で拡散させ且つ生産品水素リッチ改質油をそこから拡散させることができるためにガス透過可能であること、
(ii)CPOX反応器ユニットのCPOX反応ゾーン内でガス状CPOX反応混合物のCPOXを開始して、それによって、水素リッチ改質油の生産を開始すること;及び
b)定常状態モードにおいて:
(iii)ガス状CPOX反応混合物をCPOX反応器ユニットのインレットに導入すること、
(iv)CPOX反応器ユニットのCPOX反応ゾーン内でCPOX反応を維持しながら、ステップ(iii)に先行して、又はそのステップ(iii)中に、又はそのステップ(iii)に続いてCPOX開始ステップ(ii)を中断して、それによって、水素リッチ改質油の生産を続けること、を備える。
a)スタートアップモードにおいて:
(i)ガスを複数のCPOX反応器ユニットの各々のインレットに向けて経路指定するためのコンジットに酸素含有ガスを導入すること、コンジットは、酸素含有ガス用のインレット、ガス状改質可能燃料用のインレット及びCPOX反応器ユニットのインレットとガス流連通状態にあるガス状CPOX反応混合物用のアウトレットを備えること、各CPOX反応器ユニットは、ガス状CPOX反応混合物用のインレット、水素リッチ改質油用のアウトレット、内表面及び外表面を有する壁を有する細長いチューブを備えること、その壁は、中に配置されるCPOX触媒を有する及び/又はそのCPOX触媒の構造体を備える壁の少なくとも一セクションで開口ガス流通路を囲むこと、そのような触媒含有壁セクション及びそれによって囲まれる開口ガス流通路は、ガス相CPOX反応ゾーンを画定すること、触媒含有壁セクションは、CPOX反応状態下で安定でありながら、ガス状CPOX反応混合物を中で拡散させ且つ生産品水素リッチ改質油をそこから拡散させることができるためにガス透過可能であること、
(ii)ガス状改質可能燃料をコンジットに導入すること、ガス状改質可能燃料は、ステップ(i)からの酸素含有ガスと組み合わさってガス状CPOX反応混合物を提供すること、
(iii)ステップ(ii)からのガス状CPOX反応混合物をCPOX反応器ユニットのインレットに導入すること、及び
(iv)CPOX反応器ユニットのCPOX反応ゾーン内で前記ガス状CPOX反応混合物のCPOXを開始して、それによって、水素リッチ改質油の生産を開始すること;及び
b)定常状態モードにおいて:
(v)酸素含有ガスをコンジットに導入すること、
(vi)ガス状改質可能燃料をコンジットに導入すること、ガス状改質可能燃料は、ステップ(v)からの酸素含有ガスと組み合わさってガス状CPOX反応混合物を提供すること、
(vii)ステップ(vi)からのガス状CPOX反応混合物をCPOX反応器ユニットのインレットに導入すること、及び
(viii)CPOX反応器ユニットのCPOX反応ゾーン内でCPOX反応を維持しながら、ステップ(vii)に先行して、又はそのステップ(vii)中に、又はそのステップ(vii)に続いてCPOX開始ステップ(iv)を中断して、それによって、水素リッチ改質油の生産を続けることを含むことができる。
目標のガス圧とガス流の大部分、例えば、目標のガス圧とガス流の約60%から約90%までを提供するために遠心ブロワーシステムのような相互接続された一連のブロワーにおける一つ以上のブロワーユニットを制御することによって、目標のガス圧とガス流の残りの部分がそのシステムの一つ以上の他のブロワーユニットによって提供されることができる。目標のガス流とガス圧をCPOX改質器へ提供するタスクを、デュアル遠心ブロワーシステムのような少なくとも二つの一体化された、即ち、相互接続された遠心ブロワー間でスプリットすることの結果は、そのような流れと圧力が単一の遠心ブロワーユニットで可能であるものよりも短い時間で且つより大きな精度で達成されることになる。加えて、電力引込みとノイズレベルは、ブロワーインペラーがそれらの動作のために高いrpmを必要としないので、遠心ブロワーシステムにおいて低くなり得る。
Claims (14)
- ガス状燃料CPOX改質器であって、
互いに離間されたCPOX反応器ユニットのアレイであって、各CPOX反応器ユニットが、内表面と外表面を有するガス透過可能壁を有する細長いチューブを備え、前記ガス透過可能壁が、開口ガス流通路を囲むと共に前記CPOX反応器ユニットのインレットとアウトレットを画定し、前記開口ガス流通路は、前記CPOX反応器ユニットの前記インレットから前記アウトレットに延伸する中空穴であり、
一つのCPOX反応器ユニットが、前記アレイの少なくとも隣のCPOX反応器ユニット(単数又は複数)と熱連通状態にあり、
前記ガス透過可能壁の少なくとも一つのセクションが、CPOX触媒を備える、互いに離間されたCPOX反応器ユニットのアレイと、
少なくとも一つのCPOX反応器ユニットのCPOX触媒を備える前記ガス透過可能壁の少なくとも一つのセクションと熱連通状態の点火器と
を備えるガス状燃料CPOX改質器。 - 水素バリアが、一つのCPOX反応器ユニットの少なくとも前記CPOX触媒含有壁セクションの前記外表面に関連付けられている請求項1に記載のガス状燃料CPOX改質器。
- 隣り合うCPOX反応器ユニット間の最大距離は、CPOX反応が、動作中のCPOX反応器ユニットにおけるCPOX反応からの熱によって隣のCPOX反応器ユニットで開始されることに失敗しないこと及び/又は動作の定常状態モード中に、互いに離間されたCPOX反応器ユニットの前記アレイの温度が所定の最小アレイ温度未満に低下しない距離であり;隣り合うCPOX反応器ユニット間の最小距離は、CPOX反応器ユニットのアウトレットでの温度が所定の最大温度を超えることがない距離であり、
前記所定の最小アレイ温度は、前記動作中のCPOX反応器ユニットの動作の定常状態モードを維持するために所要な最小温度であり、
前記所定の最大温度は、前記CPOX反応器ユニットのアウトレットと熱連通状態及び流体連通状態にある燃料セルスタックのインレットによって許容できる温度である請求項1又は2に記載のガス状燃料CPOX改質器。 - 一つ以上の点火器を備え、各点火器は、少なくとも一つのCPOX反応器ユニットのCPOX触媒を備える前記ガス透過可能壁の少なくとも一セクションと熱連通状態に配置される請求項1乃至3のいずれか一項に記載のガス状燃料CPOX改質器。
- 前記CPOX触媒は、前記CPOX反応器ユニットの前記壁内に配置される、又は前記CPOX反応器ユニットの前記壁の内表面上に配置される、又は前記CPOX反応器ユニットの前記壁の構造体を部分的に又は全体的に形成する又はこれらの組合せである請求項1乃至4のいずれか一項に記載のガス状燃料CPOX改質器。
- 前記CPOX触媒含有壁セクションは、セラミックを含む請求項1乃至5のいずれか一項に記載のガス状燃料CPOX改質器。
- 前記水素バリアは、加圧流体を含む請求項2乃至6のいずれか一項に記載のガス状燃料CPOX改質器。
- 請求項1の前記ガス状燃料CPOX改質器を使用してガス状改質可能燃料を水素リッチ改質油にCPOX改質する方法であって、前記方法は:
ガス状改質可能燃料を含むガス状CPOX反応混合物を前記改質器のCPOX反応器ユニットのインレットに導入すること;
少なくとも一つのCPOX反応器ユニットにおいて水素リッチ改質油の生産を開始するために前記ガス状CPOX反応混合物の触媒部分酸化を開始することであって、前記少なくとも一つのCPOX反応器ユニットの前記ガス透過可能CPOX触媒含有壁セクションは、ガス状CPOX反応混合物が前記壁セクション中に拡散すること及び生産品水素リッチ改質油の前記壁セクションからの拡散を可能にすること;及び
前記少なくとも一つのCPOX反応器ユニット中に前記ガス状CPOX反応混合物の触媒部分酸化を維持することを含む方法。 - 水素バリアが、一つのCPOX反応器ユニットの少なくとも前記CPOX触媒含有壁セクションの前記外表面に関連付けられている請求項8に記載の方法。
- 触媒部分酸化を開始する前記ステップにおいて、前記ガス状CPOX反応混合物の酸素対炭素のモル比は、燃料希薄CPOX反応混合物のそれに対応し、且つガス状CPOX反応混合物の触媒部分酸化を維持する前記ステップにおいて、前記ガス状CPOX反応混合物の酸素対炭素のモル比は、燃料リッチCPOX反応混合物のそれに対応する請求項8又は9に記載の方法。
- 互いに隣接するCPOX反応器ユニット間の最大距離は、CPOX反応が動作中のCPOX反応器ユニットにおけるCPOX反応からの熱によって隣の一つのCPOX反応器ユニットにおいて開始することに失敗すること及び/又は動作の定常状態モード中にCPOX反応器ユニットの温度が所定の最小アレイ温度未満に低下することが無い距離であり、及び互いに隣接するCPOX反応器ユニット間の最小距離は、CPOX反応器ユニットのアウトレットの前記温度が所定の最大温度を超えることが無い距離であり、
前記所定の最小アレイ温度は、前記動作中のCPOX反応器ユニットの動作の定常状態モードを維持するために所要な最小温度であり、
前記所定の最大温度は、前記CPOX反応器ユニットのアウトレットと熱連通状態及び流体連通状態にある燃料セルスタックのインレットによって許容できる温度である請求項8乃至10のいずれか一項に記載の方法。 - 触媒部分酸化を開始することは:
少なくとも一つのCPOX反応器ユニットでCPOX反応を開始すること;及び
中でCPOX反応を開始するために、前記少なくとも一つのCPOX反応器ユニットにおける前記CPOX反応からの熱を少なくとも一つの他のCPOX反応器ユニットに伝達することを含む請求項8乃至11のいずれか一項に記載の方法。 - 前記CPOX反応を開始することは、前記CPOX反応器ユニットの各々において前記ガス状CPOX反応混合物の触媒部分酸化を開始するために二つ以上の点火器を始動することを含み、点火器の数は、CPOX反応器ユニットの数未満である請求項8乃至12のいずれか一項に記載の方法。
- 前記ガス状燃料CPOX改質器の動作中に、前記ガス状CPOX反応混合物の酸素対炭素の比率を変化させることを含む請求項8乃至13のいずれか一項に記載の方法。
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