JP6695283B2 - 高いNOx‐SCR変換率及び低いSOx変換率 - Google Patents
高いNOx‐SCR変換率及び低いSOx変換率 Download PDFInfo
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- JP6695283B2 JP6695283B2 JP2016569931A JP2016569931A JP6695283B2 JP 6695283 B2 JP6695283 B2 JP 6695283B2 JP 2016569931 A JP2016569931 A JP 2016569931A JP 2016569931 A JP2016569931 A JP 2016569931A JP 6695283 B2 JP6695283 B2 JP 6695283B2
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Classifications
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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Description
酸化バナジウム(II)(一酸化バナジウム)、VO;
酸化バナジウム(III)(三酸化二バナジウム又は三酸化バナジウム)、V2O3;
酸化バナジウム(IV)(二酸化バナジウム)、VO2;及び
酸化バナジウム(V)(五酸化バナジウム)、V2O5
である。
スプレーコーティングしたバナジウム酸/モリブデン酸物品の調製
酸化チタン(アナターゼ)(112g)をメタバナジン酸アンモニウム(130gの水中、3.7091gのNH4VO3)の溶液と約60℃で合わせ、懸濁液を得た。ヘプタモリブデン酸アンモニウム四水和物(30gの水中、0.8715gの(NH4)6Mo7O24・4H2O)の溶液を、約40℃で加え、その後、コロイド状シリカ分散液(40%の分散、52.50g)及びアルミナ繊維(7.0g)を加え、懸濁液をよく混合した。得られた水性のウォッシュコート(400g)は35%(112g)の全固形分を有し、そのうち触媒は80%であり、シリカ分散液は15%であり、アルミナ繊維は5%である。触媒は、TiO2上に0.6重量%のVOx及び2.7重量%のMoO3を含んでいた。
積層されたバナジウム酸/モリブデン酸物品の調製
チタニアを熱モノエタノールアミンに溶解したメタバナジン酸アンモニウムの混合物と合わせ、混合物を混練してペーストを形成することによって、TiO2上に0.6重量%のVOx及び2.7重量%のMoO3を含んだ触媒を調製した。結晶性のヘプタモリブデン酸アンモニウム四水和物をペーストに直接加え、混合物をさらに混練した。
各触媒ストリップを6.5mmの間隔で反応管に垂直に取り付け、合成ガス混合物を反応管に通過させた。NOx試験用の合成ガス混合物は、SOx試験用の合成混合物とは異なっていた。合成ガス混合物の組成は以下に提示される。
4つの触媒ストリップを6.5mm間隔で反応管に垂直に取り付け、合成ディーゼル排ガス混合物を反応管に通過させた。反応管への入口における合成排ガス混合物の組成は、約400ppmのNO、400ppmのNH3、5%のO2、10%のH2O、500ppmのSO2、及び残部のガスはN2であった。これは、還元体として使用したアンモニアを含んでいる。以下の情報はガス流に関する:全流量:74.0L/分;公称領域速度:55.5m/時間;公称直線速度:1.71m/秒;公称空間速度:15400時間−1.等温条件下、320℃、350℃、又は382℃においてNOx変換を決定した。
各触媒ストリップを反応管に垂直に取り付け、合成排ガス混合物を反応管に通過させた。反応管への入口におけ排ガス混合物の組成は、0ppmのNO、0ppmのNH3、5%のO2、10%のH2O、500ppmのSO2、及び残部のガスはN2であった。以下の情報はガス流に関する: 全流量:16.6L/分;公称領域速度:12.5m/時間;公称直線速度:0.39m/秒;公称空間速度:3470時間−1。SOx変換を、等温条件下、400℃で決定した。
kSOx=−(Q/Vc)ln(1−XSO2)
及び
kNOx=−AV ln(1−XNOx)
式中、Qは全流量(m3/h)であり、Vcは全触媒容積(m3)であり、XSO2はSO2の部分変換であり、AVは、AV = Q/(Vca)として定義される領域速度(m/h)であり;ここで式中、aは単位容積あたりの幾何学的表面積(m2/m3)であり及びXNOxはNOxの部分変換である。kNOxは触媒の幾何学的表面積(m2/m3)を考慮して算出され、一方、kSOxは触媒容積(m3)に基づいて算出される。kNOxの値はm/時間を単位として報告され、kSOxの値は時間−1を単位として報告される。
スプレーコーティングしたバナジウム酸/タングステン酸物品の調製
メタバナジン酸アンモニウム及び10%のWO3を含むチタニアを水(約315g)に懸濁し、高剪断条件下でコロイド状シリカ分散液(40%の分散、69.30g)及びアルミナ繊維(9.25g)と合わせた。得られた水性のウォッシュコート(500g)は37%の固形分及び3.35のpHを有する。ウォッシュコート内の固体はTiO2上に1.7重量%の分散したメタバナジウム酸及び10重量%のWO3を含む。
NOx試験:
温度:382℃;公称領域速度:74.0m/時間;公称空間速度:15,400時間−1。
SOx試験:
公称領域速度:16.6m/時間;公称直線速度:0.38m/秒;公称空間速度:3450時間−1。
Claims (13)
- 窒素酸化物(NOx)及び還元体を含むガス中の窒素酸化物の変換を触媒するための物品の製造方法であって、
物品が
(a)基材;及び
(b)基材上に堆積された、VOx、MoO3又はWO3、及びTiO2を含む触媒膜;
を備え、
(a)(i)(A)VOx又はVOx前駆体、(ii)MoO3、MoO3前駆体、WO3、WO3前駆体又はそれらの混合物、及び(iii)TiO2又はTiO2前駆体、(B)添加剤、及び(C)水、を含むウォッシュコート懸濁液で基材をスプレーコーティングすることであって、触媒及び水を含むウォッシュコート懸濁液中の固体分が20から60重量%の範囲内であり、ウォッシュコート懸濁液中の水が80から40重量%の範囲内である、スプレーコーティングすること、及び
(b)コーティングされた基材をか焼すること、
により、基材上に触媒膜を形成することを含む、方法。 - 基材が基材上の使用済み触媒であり、
基材と、基材上の使用済み触媒から微粒子を除去する、工程(a)の前の追加の工程を含む、請求項1に記載の方法。 - 膜が、0.1から5重量%のVOx、0.5から20重量%のMoO3 若しくはWO3、又はそれらの混合物、及び75から99.4重量%のTiO2を含む、請求項1又は2に記載の方法。
- 膜が、0.5から2重量%のVOx又はVOx前駆体、1から10重量%のMoO3、MoO3前駆体、WO3、WO3前駆体又はそれらの混合物、及び88から98.5重量%のTiO2又はTiO2前駆体を含む、請求項1又は2に記載の方法。
- 膜が約20μmから約500μmまで、好ましくは約50μmから約150μmまでの厚さを有する、請求項1から4のいずれか一項に記載の方法。
- 基材がモノリス又はプレートである、請求項1から5のいずれか一項に記載の方法。
- 基材が穿孔される、請求項1から6のいずれか一項に記載の方法。
- 基材が鋼を含む、請求項1から7のいずれか一項に記載の方法。
- コーティングされた基材のか焼が400℃から1200℃の範囲内の温度で行われる、請求項1から8のいずれか一項に記載の方法。
- 添加材が、ガラス粒子、アルミナ、シリカ、シリカ−アルミナ、セラミック、モレキュラーシーブ、ゼオライト、粘土、無機酸化物、鉱物及びポリマーから選択される、請求項1から9のいずれか一項に記載の方法。
- 触媒固体が50から99重量%の触媒膜を含み、添加剤が1から50重量%の触媒膜を含む、請求項1から10のいずれか一項に記載の方法。
- 請求項1から11のいずれか一項に記載の物品の製造方法の後に、物品の存在下で窒素酸化物を含むガス状混合物を還元体、好ましくはアンモニアと接触させる工程を含む、ガス状混合物中の窒素酸化物を選択的に還元する方法を含む、方法。
- 物品の存在下で窒素酸化物を含むガス状混合物を還元体と接触させる工程が、100℃から650℃の範囲内の温度で行われる、請求項12に記載の方法。
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US201462006482P | 2014-06-02 | 2014-06-02 | |
US62/006,482 | 2014-06-02 | ||
PCT/US2015/033460 WO2015187525A1 (en) | 2014-06-02 | 2015-06-01 | Coated articles with high rate of nox-scr conversion and low sox conversion rate |
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JP2016569931A Expired - Fee Related JP6695283B2 (ja) | 2014-06-02 | 2015-06-01 | 高いNOx‐SCR変換率及び低いSOx変換率 |
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EP (1) | EP3148679B1 (ja) |
JP (1) | JP6695283B2 (ja) |
KR (1) | KR20170010838A (ja) |
CN (1) | CN106457145B (ja) |
DE (1) | DE102015209988A1 (ja) |
DK (1) | DK3148679T3 (ja) |
GB (2) | GB2529927A (ja) |
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CN111468102B (zh) * | 2019-01-23 | 2021-06-25 | 中国科学院过程工程研究所 | 一种废弃scr脱硝催化剂循环利用的方法 |
US20220258135A1 (en) * | 2019-07-16 | 2022-08-18 | Kuk Il Inntot Co. , Ltd. | Catalytic reaction apparatus comprising coating composition for catalyst and coating method |
JP7240673B2 (ja) * | 2019-12-23 | 2023-03-16 | 株式会社デンソー | 成膜方法 |
CN112832889B (zh) * | 2021-01-08 | 2022-05-13 | 广西玉柴机器股份有限公司 | 一种发动机使用高硫柴油的诊断方法及相关装置 |
CN113060733B (zh) * | 2021-04-01 | 2022-08-19 | 华能洋浦热电有限公司 | 一种氮掺杂碳化钒及其制备方法和应用 |
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DE3805564A1 (de) | 1988-02-23 | 1989-08-31 | Siemens Ag | Katalysator zur minderung der stickoxide und verfahren zu seiner herstellung |
US5166122A (en) | 1988-09-19 | 1992-11-24 | Babcock-Hitachi Kabushiki Kaisha | Process for producing a denitration catalyst |
JP2725800B2 (ja) * | 1988-09-19 | 1998-03-11 | バブコツク日立株式会社 | 脱硝触媒の製造方法 |
US5409681A (en) | 1991-11-27 | 1995-04-25 | Babcock-Hitachi Kabushiki Kaisha | Catalyst for purifying exhaust gas |
JP3229324B2 (ja) | 1994-05-30 | 2001-11-19 | シーメンス アクチエンゲゼルシヤフト | 流動媒体中の窒素酸化物を低減させる触媒及びその製造方法 |
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DE19749607C1 (de) * | 1997-11-10 | 1999-03-18 | Siemens Ag | Verfahren und Einrichtung zur Verminderung der Anzahl von Partikeln in einem Abgas |
GB9802504D0 (en) | 1998-02-06 | 1998-04-01 | Johnson Matthey Plc | Improvements in emission control |
GB9808876D0 (en) | 1998-04-28 | 1998-06-24 | Johnson Matthey Plc | Combatting air pollution |
WO2000013775A1 (fr) | 1998-09-09 | 2000-03-16 | Babcock-Hitachi Kabushiki Kaisha | Structure catalytique permettant de reguler les emissions d'echappement et dispositif s'y rapportant |
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DE102007003155A1 (de) * | 2007-01-22 | 2008-07-24 | Süd-Chemie AG | Katalysatorzusammensetzung zur Reduktion von Stickoxiden |
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- 2015-06-01 US US14/726,719 patent/US20150343422A1/en not_active Abandoned
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RU2016151666A (ru) | 2018-07-10 |
DK3148679T3 (da) | 2020-07-13 |
CN106457145B (zh) | 2020-02-14 |
DE102015209988A1 (de) | 2015-12-03 |
JP2017518875A (ja) | 2017-07-13 |
GB2529927A (en) | 2016-03-09 |
US20150343422A1 (en) | 2015-12-03 |
US20180021724A1 (en) | 2018-01-25 |
US10618000B2 (en) | 2020-04-14 |
WO2015187525A1 (en) | 2015-12-10 |
EP3148679B1 (en) | 2020-05-13 |
CN106457145A (zh) | 2017-02-22 |
GB201509440D0 (en) | 2015-07-15 |
GB2541337B (en) | 2021-03-03 |
GB201620535D0 (en) | 2017-01-18 |
KR20170010838A (ko) | 2017-02-01 |
GB2541337A (en) | 2017-02-15 |
EP3148679A1 (en) | 2017-04-05 |
RU2016151666A3 (ja) | 2018-11-14 |
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