JP2018538122A - 煙道及び排出ガス中の窒素酸化物の除去のための、ハニカム触媒及びその調製方法 - Google Patents
煙道及び排出ガス中の窒素酸化物の除去のための、ハニカム触媒及びその調製方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title description 12
- 239000007789 gas Substances 0.000 title description 4
- 239000012792 core layer Substances 0.000 claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 14
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000004927 clay Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000005909 Kieselgur Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000011162 core material Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 group of pyropyrite Chemical compound 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/22—Vanadium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/58—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9202—Linear dimensions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
4NO+4NH3+O2−4N2+6H2O
NO+NO2+2NH3−2N2+3H2O
各波形シートが、波形シートの各々の両面に粘土材料で被覆された交絡不織繊維(entangled non-woven fiber)を含む内側コア層と、
内側コア層の両面に支持され、SCR触媒組成物を含む最外層と、を備える波形シートであり、内側コア層が、経路の壁厚の50%〜95%を占める、ハニカムSCR触媒を提供する。
(a)交絡不織繊維のシートを準備する工程と、
(b)シートを波形にする工程と、
(c)工程(b)で得られた波状シートを積み重ねることで、ハニカム構造基板を形成する工程と、
(d)ハニカム構造基板の波形シートを粘土材料で被覆することで、波形シートの各々の内に内部コア層を得る工程、並びにハニカム構造基板を乾燥する工程及び/又は焼成する工程と、
(e)SCR触媒組成物又はその前駆体を含む触媒被覆層で、ハニカム構造基板内の波形シートのそれぞれの内側コア層の各面を被覆する工程と、
(f)工程(e)の被覆されたハニカム構造基板を焼成することで、ハニカムSCR触媒を得る工程と、を含む、方法である。
工程(b)で得られた各波形シートを、積み重ねる前にライナーで裏打ちすること、
不織繊維を、ガラス繊維とすること、
内側コア材料が更に珪藻土を含むこと、
触媒被覆層の膜厚を、0.05mm〜0.3mmとすること、
内側コア層の膜厚を、0.6mm〜1.2mmとすること、
SCR触媒組成物が、チタニア及びバナジウムの酸化物を含むこと、
バナジウムの酸化物を、五酸化バナジウムとし、最外層において1重量%〜5重量%の量で適用し、並びに
SCR触媒組成物が、タングステンの酸化物を更に含むこと、
すべての特徴及び態様において、粘土材料は、カオリンの群、含水アルミナケイ酸塩、緑泥石の群、ピロピライトの群、ベントナイト又はそれらの混合物から選択され得ること。
図1に、波形ガラス繊維紙に支持された触媒層全体を有する公知のハニカムSCR触媒と比較した、コア層の各々の両面で、内部コア層厚さが0.7mm、及び触媒外層厚さが0.15mmの、本発明によるハニカムSCR触媒の、SO2酸化についての活性に対するDeNOx活性の比を示す。両方の比は、全触媒層の値に正規化されている。理想的には、SO2酸化活性に対するDeNOx活性の比が、高くいものとなる。
Claims (20)
- 複数の波形シートを互いに積み重ねて、複数の流通経路を形成して構成されるハニカムSCR触媒であって、
各波形シートが、前記波形シートの各々の両面に粘土材料で被覆された交絡不織繊維を含む内側コア層と、
前記内側コア層の両面に支持され、SCR触媒組成物を含む最外層と、を備える波形シートであり、前記内側コア層が、前記経路の壁厚の50%〜95%を占める、ハニカムSCR触媒。 - 前記不織繊維が、ガラス繊維である、請求項1に記載のハニカム触媒。
- 前記内側コア材料が、珪藻土を更に含む、請求項1又は2に記載のハニカム触媒。
- 前記最外層の層厚が、0.05mm〜0.6mmである、請求項1〜3のいずれか一項に記載のハニカム触媒。
- 前記内側コア層の層厚が、0.6mm〜1.2mmである、請求項1〜4のいずれか一項に記載のハニカム触媒。
- 前記SCR触媒組成物が、チタニア及びバナジウムの酸化物を含む、請求項1〜5のいずれか一項に記載のハニカム触媒。
- 前記バナジウムの酸化物が、1重量%〜5重量%の量の五酸化バナジウムである、請求項6に記載のハニカム触媒。
- タングステンの酸化物を更に含む、請求項6又は7に記載のハニカム触媒。
- 前記波形シートの各々に配置されたライナーを更に含む、請求項1〜8のいずれか一項に記載のハニカム触媒。
- 前記内側コア層が、珪藻土を更に含む、請求項1〜9のいずれか一項に記載のハニカム触媒。
- 複数の流通経路によるハニカムSCR触媒を調製する方法であって、
(a)交絡不織繊維のシートを準備する工程と、
(b)前記シートを波形にする工程と、
(c)工程(b)で得られた波状シートを積み重ねることで、ハニカム構造基板を形成する工程と、
(d)前記ハニカム構造基板の前記波形シートを粘土材料で被覆することで、前記波形シートの各々の内に内部コア層を得る工程、並びに前記ハニカム構造基板を乾燥する工程及び/又は焼成する工程と、
(e)SCR触媒組成物又はその前駆体を含む触媒被覆層で、前記ハニカム構造基板内の前記波形シートの各々の前記内側コア層の各面を被覆する工程と、
(f)工程(e)のハニカム構造基板を焼成することで、前記ハニカムSCR触媒を得る工程と、を含む、方法。 - 工程(b)で得られた各波形シートを、積み重ねる前にライナーで裏打ちする、請求項11に記載の方法。
- 前記ライナーを、粘土材料で被覆する、請求項11に記載の方法。
- 前記不織繊維を、ガラス繊維とする、請求項11又は13のいずれか一項に記載の方法。
- 前記粘土材料が、珪藻土を更に含む、請求項11〜14のいずれか一項に記載の方法。
- 前記触媒被覆層の層厚を、0.05mm〜0.6mmとする、請求項11〜15のいずれか一項に記載の方法。
- 前記内側コア層の層厚を、0.6mm〜1.2mmとする、請求項11〜16のいずれか一項に記載の方法。
- 前記SCR触媒組成物が、チタニア及びバナジウムの酸化物を含む、請求項11〜17のいずれか一項に記載の方法。
- 前記バナジウムの酸化物を、五酸化バナジウムとし、1重量%〜5重量%の量で適用する、請求項18に記載の方法。
- 前記SCR触媒組成物が、タングステンの酸化物を更に含む、請求項18又は19に記載の方法。
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DKPA201500661 | 2015-10-28 | ||
DKPA201500661 | 2015-10-28 | ||
PCT/EP2016/075722 WO2017072137A1 (en) | 2015-10-28 | 2016-10-26 | Honeycomb catalyst for removal of nitrogen oxides in flue and exhaust gasses and method of preparation thereof |
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US (1) | US10737258B2 (ja) |
EP (1) | EP3368216A1 (ja) |
JP (1) | JP2018538122A (ja) |
KR (1) | KR102610338B1 (ja) |
CN (1) | CN108025291B (ja) |
WO (1) | WO2017072137A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP7421571B2 (ja) | 2019-04-26 | 2024-01-24 | トプソー・アクチエゼルスカベット | 複合粒子状物質除去及び窒素酸化物の選択的触媒還元(scr)のための触媒セラミックキャンドルフィルタ |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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- 2016-10-26 WO PCT/EP2016/075722 patent/WO2017072137A1/en active Application Filing
- 2016-10-26 EP EP16785513.9A patent/EP3368216A1/en active Pending
- 2016-10-26 JP JP2018506268A patent/JP2018538122A/ja not_active Ceased
- 2016-10-26 CN CN201680053459.5A patent/CN108025291B/zh active Active
- 2016-10-26 US US15/754,748 patent/US10737258B2/en active Active
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Also Published As
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US20180243733A1 (en) | 2018-08-30 |
CN108025291B (zh) | 2021-07-09 |
KR102610338B1 (ko) | 2023-12-07 |
KR20180077235A (ko) | 2018-07-06 |
EP3368216A1 (en) | 2018-09-05 |
WO2017072137A1 (en) | 2017-05-04 |
US10737258B2 (en) | 2020-08-11 |
CN108025291A (zh) | 2018-05-11 |
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