JP2018537264A - 燃焼タービンで使用するためのゾーニングされたアンモニアスリップ触媒 - Google Patents
燃焼タービンで使用するためのゾーニングされたアンモニアスリップ触媒 Download PDFInfo
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- JP2018537264A JP2018537264A JP2018516048A JP2018516048A JP2018537264A JP 2018537264 A JP2018537264 A JP 2018537264A JP 2018516048 A JP2018516048 A JP 2018516048A JP 2018516048 A JP2018516048 A JP 2018516048A JP 2018537264 A JP2018537264 A JP 2018537264A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 552
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 52
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 222
- 230000003647 oxidation Effects 0.000 claims abstract description 220
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 33
- 230000004323 axial length Effects 0.000 claims abstract description 31
- 239000010970 precious metal Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 67
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 52
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 52
- 239000011248 coating agent Substances 0.000 claims description 50
- 238000000576 coating method Methods 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 8
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- -1 Cu-CHA) Chemical compound 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
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- 229910010271 silicon carbide Inorganic materials 0.000 description 4
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- 239000003638 chemical reducing agent Substances 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
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- 229910052642 spodumene Inorganic materials 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide 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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Abstract
Description
4NO+4NH3+O2→4N2+6H2O
2NO2+4NH3+O2→3N2+6H2O
NO+NO2+2NH3→2N2+3H2O
様々な構成において、組成物は、第1のSCR触媒または第1のSCR触媒および第2のSCR触媒を含むことができる。
酸化触媒は、貴金属またはその混合物を含むことができる。好ましくは、貴金属は、金、銀、白金、パラジウム、ルテニウムまたはロジウム、またはそれらの組み合わせである。より好ましくは、貴金属は、白金またはパラジウムまたは白金とパラジウムとの組み合わせである。
実施例1
チタニア、タングステナ、バナジア、および適切な結合剤を含有する押出成形されたSCR触媒を作製した。SCR触媒のセル密度は、140セル/平方インチ(cpsi)であった。
2層のアンモニアスリップ触媒(ASC)を、セラミック230cpsi基材上に作製した。基材の全長に沿って連続的なアルミナウォッシュコート層を有する第1の層をコーティングした。次いで、Ptが、硝酸白金溶液からウォッシュコートアルミナ層に、5g/ft3のPtの充填量まで含浸された。結合剤と混合されたCu含浸CHAゼオライトを含有する第2のウォッシュコートを、Ptアルミナ層の100%を覆う連続層で塗布した。
ゾーニングされたASC/酸化触媒(OC)を、セラミック230cpsi基材上に作製した。基材の全長に沿って連続的なアルミナウォッシュコート層を有する第1の層をコーティングした。次いで、Ptが、硝酸白金溶液からウォッシュコートアルミナ層に、5g/ft3のPtの充填量まで含浸された。結合剤と混合されたCu含浸CHAゼオライトを含有する第2のウォッシュコートを、Ptアルミナ層の前部85%を覆う連続層で塗布した。
ゾーニングされたASC/OCを、セラミック230cpsi基材上に作製した。基材の全長に沿って連続的なアルミナウォッシュコート層を有する第1の層をコーティングした。次いで、Ptが、硝酸白金溶液からウォッシュコートアルミナ層に、5g/ft3のPtの充填量まで含浸された。結合剤と混合されたCu含浸CHAゼオライトを含有する第2のウォッシュコートを、Ptアルミナ層の前部70%を覆う連続層で塗布した。
実施例1〜4の触媒を実験室規模の反応器中で種々の組み合わせで試験した。触媒に供給されたガス組成は、50ppmのCO、24ppmのNO、6ppmのNO2、30pmのNH3、15%のO2、8%の水、3%のCO2であり、残りはN2であった。CO、NOx、およびNH3の転化率が、200〜450℃の範囲の定常状態温度点に保持された反応器で測定された。
実施例1および実施例2を、直列(実施例1のSCR触媒が、比較例2のASCの上流)に反応器に挿入し、SCR+ASCの全体積にわたるガス毎時空間速度(GHSV)が80,000hr−1であるような流速で、上記の手順に従って試験した。
実施例1および実施例3を、直列(実施例1のSCR触媒が、実施例3のASCの上流)に反応器に挿入し、ゾーニングされたASC/OC触媒のSCR+ASC部分におけるGHSVが80,000hr−1であり、ゾーニングされたASC/OCのOC部分におけるGHSVが1,040,115hr−1であるような流速で、上記の手順に従って試験した。
実施例1および実施例4を、直列(実施例1のSCR触媒が、実施例4のASCの上流)に反応器に挿入し、ゾーニングされたASC/OC触媒のSCR+ASC部分におけるGHSVが80,000hr−1であり、ゾーニングされたASC/OCのOC部分におけるGHSVが480Khr−1であるような流速で、上記の手順に従って試験した。
Claims (20)
- 燃焼タービンからのNOx、炭化水素、CO、SOxおよびアンモニアのうちの1つ以上を含む排ガス流を処理するための触媒物品であって、
(a)軸方向長さを定める入口端部および出口端部を有する基材と、
(b)1種以上の貴金属を含む酸化触媒を含む酸化層であって、前記基材上に配置され、前記基材の前記軸方向長さを覆う酸化層と、
(c)SCR触媒を含むSCR層であって、前記酸化層上に配置され、前記酸化層の一部分と重なっており、前記一部分が100%未満である、SCR層と
を含む触媒物品。 - (i)前記SCR層が、前記入口端部から前記出口端部に向かって延びる、(ii)前記SCR層が、前記出口端部から前記入口端部に向かって延びる、または(iii)前記SCR層が、前記入口端部から前記出口端部に向かって、かつ前記出口端部から前記入口端部に向かって延びる、請求項1に記載の触媒物品。
- 前記SCR層が、第1のSCR触媒および第2のSCR触媒を含み、前記第1のSCR触媒が、前記第2のSCR触媒とは異なっており、前記第1のSCR触媒が、前記第2のSCR触媒に対して前記触媒物品の入口側に配置されている、請求項1または2に記載の触媒物品。
- 前記第1のSCR触媒および前記第2のSCR触媒が、SCR触媒の充填量について異なる、請求項3に記載の触媒物品。
- 前記第2のSCR触媒の充填量が、前記第1のSCRよりも多い、請求項3または4に記載の触媒物品。
- 前記第1のSCR触媒および前記第2のSCR触媒が、異なる触媒種を含む、請求項3から5のいずれか一項に記載の触媒物品。
- 前記酸化層が、第1の酸化触媒および第2の酸化触媒を含み、前記第1の酸化触媒が、前記第2の酸化触媒とは異なっており、前記第1の酸化触媒が、前記第2の酸化触媒に対して前記触媒物品の入口側に配置されている、請求項1から6のいずれか一項に記載の触媒物品。
- 前記第1の酸化触媒および前記第2の酸化触媒が、酸化触媒の充填量について異なる、請求項7に記載の触媒物品。
- 酸化触媒の充填量が、前記第1の酸化触媒におけるよりも前記第2の酸化触媒において多い、請求項7または8に記載の触媒物品。
- 前記第1の酸化触媒および前記第2の酸化触媒が、異なる触媒種を含む、請求項7から9のいずれか一項に記載の触媒物品。
- 第3の触媒コーティングをさらに含み、前記第3の触媒コーティングが、前記出口端部から前記入口端部に向かって延び、第1の触媒コーティングが、第2の触媒コーティングによっても前記第3の触媒コーティングによってもコーティングされていない領域を含む、請求項2から10のいずれか一項に記載の触媒物品。
- 前記第3の触媒コーティングが、前記第2の触媒コーティングにおけるSCR触媒とは異なるSCR触媒を含む、請求項11に記載の触媒物品。
- SCRゾーンが、前記基材の前記軸方向長さの90%以下を覆う、請求項1から12のいずれか一項に記載の触媒物品。
- 前記酸化層が、SCR触媒をさらに含み、前記酸化層中の前記酸化触媒および前記SCR触媒が、ブレンドとして存在する、請求項1から13のいずれか一項に記載の触媒物品。
- 請求項1から14のいずれか一項に記載の触媒物品を備える排気システム。
- 請求項15に記載の排気システムを備える燃焼タービン。
- 燃焼タービンの排ガス中の一酸化炭素(CO)および炭化水素(HC)の転化率を高める方法であって、COおよびHCを含む排ガスを、請求項1から14のいずれか一項に記載の触媒物品と接触させることを含む、方法。
- 燃焼タービンの排ガス中のアンモニアスリップを低減する方法であって、アンモニアを含む排ガスを、請求項1から14のいずれか一項に記載の触媒物品と接触させることを含む、方法。
- 燃焼タービンの排ガス中のCOおよびHCの転化率を高め、かつアンモニアスリップを低減する方法であって、CO、HCおよびアンモニアを含む排ガスを、請求項1から14のいずれか一項に記載の触媒物品と接触させることを含む、方法。
- 硫黄を含む排ガスを、請求項1から14のいずれか一項に記載の触媒物品であって、前記SCR層が前記出口端部から前記入口端部に向かって延びている触媒物品と、接触させることによって、燃焼タービンからの前記排ガス中の触媒物品の硫黄耐性を増加させる方法。
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BR112018006283B1 (pt) | 2023-02-14 |
JP6793723B2 (ja) | 2020-12-02 |
KR102543002B1 (ko) | 2023-06-14 |
KR20180063176A (ko) | 2018-06-11 |
EP3356659B1 (en) | 2020-06-10 |
BR112018006283A2 (pt) | 2018-10-16 |
WO2017055857A1 (en) | 2017-04-06 |
CN108138624A (zh) | 2018-06-08 |
CN108138624B (zh) | 2021-06-11 |
US10105692B2 (en) | 2018-10-23 |
HK1254724A1 (zh) | 2019-07-26 |
DK3356659T3 (da) | 2020-08-17 |
EP3356659A1 (en) | 2018-08-08 |
US20170087541A1 (en) | 2017-03-30 |
RU2742183C1 (ru) | 2021-02-03 |
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