JP6979945B2 - 受動的NOx吸着体 - Google Patents
受動的NOx吸着体 Download PDFInfo
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- JP6979945B2 JP6979945B2 JP2018517312A JP2018517312A JP6979945B2 JP 6979945 B2 JP6979945 B2 JP 6979945B2 JP 2018517312 A JP2018517312 A JP 2018517312A JP 2018517312 A JP2018517312 A JP 2018517312A JP 6979945 B2 JP6979945 B2 JP 6979945B2
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- Prior art keywords
- catalyst
- region
- substrate
- molecular sieve
- absorber
- Prior art date
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- 239000003463 adsorbent Substances 0.000 title description 16
- 239000003054 catalyst Substances 0.000 claims description 285
- 239000000758 substrate Substances 0.000 claims description 111
- 239000002808 molecular sieve Substances 0.000 claims description 110
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 110
- 239000006096 absorbing agent Substances 0.000 claims description 87
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 77
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 64
- 239000007789 gas Substances 0.000 claims description 60
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 50
- 239000001301 oxygen Substances 0.000 claims description 50
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- 239000011232 storage material Substances 0.000 claims description 40
- 239000011148 porous material Substances 0.000 claims description 39
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 7
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 5
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- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 101001007348 Arachis hypogaea Galactose-binding lectin Proteins 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
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- 238000002485 combustion reaction Methods 0.000 description 3
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Description
貴金属と貴金属を含有するモレキュラーシーブとを含むモレキュラーシーブ触媒;
酸素吸蔵材料;及び
入口端と出口端とを有する基材
を含む。
(a)20から95重量%のセリウムの酸化物及び/又はマンガン化合物、好ましくはセリウムの酸化物(例えばCeO2)、及び
(b)5から80重量%の第2の酸化物
から本質的になる。
(a)第2の領域上に配置又は担持され、及び/又は
(b)基材上に直接配置され[すなわち第1の領域は基材の表面と接触している]、及び/又は
(c)第2の領域と接触している[すなわち第1の領域は第2の領域に隣接又は当接する]。
(a)第1の温度範囲で、排気ガスを本発明のNOx吸収体触媒と接触させて、NOxを吸蔵する工程;及び
(b)第2の温度範囲で、NOxをNOx吸収体触媒から放出する工程
を含み、
第2の温度範囲が第1の温度範囲より高い(例えば第2の温度範囲の中間点は、第1の温度範囲の中間点より高い)
方法である。
本明細書で用いられる「領域」という用語は、基材上のウオッシュコートのエリアを指す。例えば、「領域」は、基材上に「層」又は「ゾーン」として配置又は担持されうる。基材上のウオッシュコートのエリア又は配置は一般に、基材にウオッシュコートを塗布する工程の間、制御される。一般に、「領域」は、明確な境界又は縁を有する(すなわち一般的な分析技術を用いて、1つの領域を別の領域から区別することが可能である)。
(a)基材の入口チャネルの閉塞端(例えば遮断端又は塞栓端)よりも入口チャネルの入口端(例えば開放端)に近いゾーン、及び/又は
(b)基材の出口チャネルの出口端(例えば開放端)よりも出口チャネルの閉塞端(例えば遮断端又は塞栓端)に近いゾーン。
(a)基材の出口チャネルの閉塞端(例えば遮断端又は塞栓端)よりも出口チャネルの出口端(例えば開放端)に近いゾーン、及び/又は
(b)基材の入口チャネルの入口端(例えば開放端)よりも入口チャネルの閉塞端(例えば遮断端又は塞栓端)に近いゾーン。
材料に関して、典型的には領域、層又はゾーンの含量の文脈において本明細書で用いられる表現「実質的に含まない」とは、例えば≦5重量%、好ましくは≦2重量%、さらに好ましくは≦1重量%といった、少量の材料を意味する。表現「〜を実質的に含まない」は、表現「〜を含まない」を包含する。
CHA構造を有する小細孔ゼオライトのスラリーに硝酸Pdを加え、攪拌した。アルミナバインダーを加え、その後、確立されたコーティング技術を用いて1平方インチ当たり400セルの構造を有するコーディエライトフロースルーモノリスにスラリーを塗布した。コーティングを乾燥させ、500℃で焼成した。Pd交換ゼオライトを含有するコーティングが得られた。このコーティングのPdローディングは、80g ft−3であった。
CHA構造を有する小細孔ゼオライトのスラリーに硝酸Pdを加え、攪拌した。アルミナバインダーを加え、その後、確立されたコーティング技術を用いて1平方インチ当たり400セルの構造を有するコーディエライトフロースルーモノリスにスラリーを塗布した。コーティングを乾燥させ、500℃で焼成した。Pd交換ゼオライトを含有するコーティングが得られた。このコーティングのPdローディングは、80g ft−3であった。
実施例1及び2の触媒はそれぞれ、ベンチに載せた1.6リットルのディーゼルエンジンに取り付けられた。このエンジンを動かして、模擬的な乗用車の世界統一排出ガス試験法(simulated World Harmonised Light Duty Test Cycles)(WLTC)を実施した。排出は、触媒前後で測定した。各触媒のNOx吸収性能は、触媒前の累積NOx放出と触媒後の累積NOx排出の差として決定された。触媒前後の累積NOx排出量の差は、触媒によって吸収されたNOxに起因すると考えられる。最初の試験は、フレッシュな状態の触媒で行った。
AEI構造を有する小細孔ゼオライトのスラリーに硝酸Pdを加え、攪拌した。アルミナバインダーを加え、その後、確立されたコーティング技術を用いて1平方インチ当たり400セルを有するコーディエライトフロースルーモノリスにスラリーを塗布した。コーティングを乾燥させ、500℃で焼成した。Pd交換ゼオライトを含有するコーティングが得られた。このコーティングのPdローディングは、80g ft−3であった。
AEI構造を有する小細孔ゼオライトのスラリーに硝酸Pdを加え、攪拌した。アルミナバインダーを加え、その後、確立されたコーティング技術を用いて1平方インチ当たり400セルを有するコーディエライトフロースルーモノリスにスラリーを塗布した。コーティングを乾燥させ、500℃で焼成した。Pd交換ゼオライトを含有するコーティングが得られた。このコーティングのPdローディングは、80g ft−3であった。
AEI構造を有する小細孔ゼオライトのスラリーに硝酸Pdを加え、攪拌した。アルミナバインダーを加え、その後、確立されたコーティング技術を用いて1平方インチ当たり400セルを有するコーディエライトフロースルーモノリスにスラリーを塗布した。コーティングを乾燥させ、500℃で焼成した。Pd交換ゼオライトを含有するコーティングが得られた。このコーティングのPdローディングは、80g ft−3であった。
実施例3、4及び5の触媒を、10%水を用いて750℃で15時間、水熱劣化させた。ベンチに取り付けたディーゼルエンジンを使用して、模擬WLTC排出サイクルで、これらを性能試験した。排出は、触媒前後で測定した。各触媒のNOx吸着性能は、触媒前の累積NOx放出と触媒後の累積NOx排出との差として決定された。触媒前後の累積NOx排出量の差は、触媒によって吸着されたNOxに起因すると考えられる。
Claims (14)
- リーンバーンエンジンからの排ガスを処理するためのNOx吸収体触媒であって、
貴金属と貴金属を含有する小細孔モレキュラーシーブとを含むモレキュラーシーブ触媒であって、貴金属がパラジウムを含む、モレキュラーシーブ触媒;
モレキュラーシーブ触媒を保護するための酸素吸蔵材料;及び
入口端と出口端とを有する基材
を含み、
第1の層と第2の層とを含み、第1の層が酸素吸蔵材料を含み、第2の層がモレキュラーシーブ触媒を含み、かつ、第1の層が第2の層の上に配置されている、
NOx吸収体触媒。 - 小細孔モレキュラーシーブが、ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG、ZON、及びこれらのいずれか2つ以上の混合物又は連晶からなる群より選択される骨格型を有する、請求項1に記載のNOx吸収体触媒。
- 小細孔モレキュラーシーブがAEI又はCHAである骨格型を有する、請求項2に記載のNOx吸収体触媒。
- 小細孔モレキュラーシーブが、アルミノシリケート骨格を有し、10から200のシリカのアルミナに対するモル比を有する、請求項1から3のいずれか一項に記載のNOx吸収体触媒。
- モレキュラーシーブ触媒を保護するための酸素吸蔵材料が、セリウム及び/又はマンガン化合物の酸化物を含み、マンガン化合物がマンガン又はマンガンアルミネートの酸化物を含む、請求項1から4のいずれか一項に記載のNOx吸収体触媒。
- 酸素吸蔵材料がセリウムの酸化物を含む、請求項5に記載のNOx吸収体触媒。
- 酸素吸蔵材料が、セリウムの酸化物に担持されたパラジウム及び任意選択的に白金を含む、請求項6に記載のNOx吸収体触媒。
- リーンNOxトラップ(LNT)領域をさらに含む、請求項1から7のいずれか一項に記載のNOx吸収体触媒。
- 基材がフロースルーモノリス又はフィルターモノリスである、請求項1から8のいずれか一項に記載のNOx吸収体触媒。
- 請求項1から9のいずれか一項に記載のNOx吸収体触媒とエミッションコントロールデバイスとを備える排気システム。
- エミッションコントロールデバイスが、ディーゼル微粒子フィルター(DPF)、リーンNOxトラップ(LNT)、リーンNOx触媒(LNC)、選択的触媒還元(SCR)触媒、ディーゼル酸化触媒(DOC)、触媒化スートフィルター(CSF)、選択的触媒還元フィルター(SCRFTM)触媒、アンモニアスリップ触媒(ASC)及びこれらの2種以上の組み合わせからなる群より選択されるエミッションコントロールデバイスからなる群より選択される、請求項10に記載の排気システム。
- リーンバーンエンジンと、請求項1から9のいずれか一項に記載のNOx吸収体触媒又は請求項10又は請求項11に記載の排気システムとを備える車両。
- リーンバーンエンジンが、≦50ppmの硫黄を含むディーゼル燃料で作動するように構成されている、請求項12に記載の車両。
- リーンバーンエンジンからの排気ガスを処理する方法であって、排気ガスを請求項1から9のいずれか一項に記載のNOx吸収体触媒と接触させること、又は排気ガスを請求項10又は請求項11に記載の排気システムに通過させることを含む、方法。
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BR112019020349B1 (pt) * | 2017-03-30 | 2023-01-10 | Johnson Matthey Public Limited Company | Artigo catalisador |
US10711674B2 (en) * | 2017-10-20 | 2020-07-14 | Umicore Ag & Co. Kg | Passive nitrogen oxide adsorber catalyst |
GB2572396A (en) * | 2018-03-28 | 2019-10-02 | Johnson Matthey Plc | Passive NOx adsorber |
WO2020039074A1 (en) * | 2018-08-24 | 2020-02-27 | Umicore Ag & Co. Kg | Method for the preparation of a molecular sieve of the cha-type |
CN109306886A (zh) * | 2018-11-22 | 2019-02-05 | 江苏海事职业技术学院 | 一种海洋船舶内燃机循环燃烧系统 |
BR112022011365A2 (pt) * | 2019-12-13 | 2022-08-23 | Basf Corp | Sistema de tratamento de emissão de redução de nox em uma corrente de exaustão de um motor de queima pobre e método para reduzir nox em uma corrente de exaustão de um motor de queima pobre |
CN111001436A (zh) * | 2019-12-14 | 2020-04-14 | 中触媒新材料股份有限公司 | 一种具有aei/kfi结构共生复合分子筛及其制备方法和scr应用 |
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