JP6653661B2 - 低温性能が改善されたscr触媒及びその作製ならびに使用方法 - Google Patents
低温性能が改善されたscr触媒及びその作製ならびに使用方法 Download PDFInfo
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- JP6653661B2 JP6653661B2 JP2016554479A JP2016554479A JP6653661B2 JP 6653661 B2 JP6653661 B2 JP 6653661B2 JP 2016554479 A JP2016554479 A JP 2016554479A JP 2016554479 A JP2016554479 A JP 2016554479A JP 6653661 B2 JP6653661 B2 JP 6653661B2
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- iron
- molecular sieve
- containing molecular
- heat treatment
- hydrothermal treatment
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 329
- 239000002808 molecular sieve Substances 0.000 claims description 164
- 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 163
- 229910052742 iron Inorganic materials 0.000 claims description 151
- 238000010335 hydrothermal treatment Methods 0.000 claims description 112
- 239000012298 atmosphere Substances 0.000 claims description 100
- 238000010438 heat treatment Methods 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 64
- 230000001590 oxidative effect Effects 0.000 claims description 50
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 38
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 20
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 19
- 150000002505 iron Chemical class 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001669 Mossbauer spectrum Methods 0.000 claims description 3
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- 239000010457 zeolite Substances 0.000 description 75
- 229910021536 Zeolite Inorganic materials 0.000 description 63
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 61
- 238000006243 chemical reaction Methods 0.000 description 49
- 239000007789 gas Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000007669 thermal treatment Methods 0.000 description 7
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 6
- 229910052676 chabazite Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000004813 Moessbauer spectroscopy Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- WPADTLKJFUUWIK-UHFFFAOYSA-N azane iron oxalic acid Chemical compound N.N.N.[Fe].OC(=O)C(O)=O.OC(=O)C(O)=O.OC(=O)C(O)=O WPADTLKJFUUWIK-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 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
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000005453 pelletization Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000727 reflectance ultraviolet--visible spectrophotometry Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 zeolites and SAPO Chemical compound 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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PCT/GB2015/050569 WO2015128663A1 (en) | 2014-02-28 | 2015-02-27 | Scr catalysts having improved low temperature performance, and methods of making and using the same |
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KR20160129030A (ko) * | 2014-02-28 | 2016-11-08 | 존슨 맛쎄이 퍼블릭 리미티드 컴파니 | 개선된 저온 성능을 가진 scr 촉매, 및 그것의 제조 및 사용 방법 |
CN106061901A (zh) * | 2014-03-26 | 2016-10-26 | 三菱树脂株式会社 | 含过渡金属沸石的制造方法、和通过该方法得到的过渡金属沸石以及使用该沸石的废气净化处理用催化剂 |
WO2016138418A1 (en) * | 2015-02-27 | 2016-09-01 | Basf Corporation | Exhaust gas treatment system |
GB2551871A (en) * | 2016-04-22 | 2018-01-03 | Johnson Matthey Plc | STA-18, A new member of the SFW family of molecular sieve zeotypes, methods of preparation and use |
MY200526A (en) * | 2016-08-05 | 2023-12-30 | Basf Mobile Emissions Catalysts Llc | Selective catalytic reduction articles and systems |
KR101879695B1 (ko) * | 2016-12-02 | 2018-07-18 | 희성촉매 주식회사 | 2가 구리 이온들을 특정비율로 담지한 제올라이트, 이의 제조방법 및 이를 포함하는 촉매조성물 |
GB201705241D0 (en) * | 2017-03-31 | 2017-05-17 | Johnson Matthey Catalysts (Germany) Gmbh | Catalyst composition |
EP3965929A4 (en) * | 2019-05-09 | 2022-12-28 | BASF Corporation | SELECTIVE CATALYTIC REDUCTION CATALYST COMPRISING COPPER CARBONATE |
KR102465459B1 (ko) | 2020-12-08 | 2022-11-10 | 한국생산기술연구원 | 바나듐 기반의 결정성 scr 촉매의 제조방법 및 이를 이용한 결정성 scr 촉매 |
CN114345402B (zh) * | 2021-08-30 | 2024-09-17 | 武汉科技大学 | 一种铁基分子筛催化剂的制备方法 |
CN114950576B (zh) * | 2022-06-20 | 2023-08-22 | 济南大学 | 一种提高金属基小孔分子筛水热稳定性的方法及所得产品和应用 |
WO2024237142A1 (ja) * | 2023-05-12 | 2024-11-21 | 東ソー株式会社 | 鉄含有fer型ゼオライト及びその製造方法 |
DE102024000427A1 (de) * | 2024-02-09 | 2025-08-14 | C&Cs Catalysts And Chemical Specialties Gmbh | Katalysator mit niedriger Aktivierungstemperatur zur Einstellung des temperaturabhängigen Gleichgewichtes von ortho-para Wasserstoffgemischen |
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US4255349A (en) | 1978-12-18 | 1981-03-10 | Mobil Oil Corporation | Conversion of synthesis gas with iron-containing catalyst |
US4961917A (en) * | 1989-04-20 | 1990-10-09 | Engelhard Corporation | Method for reduction of nitrogen oxides with ammonia using promoted zeolite catalysts |
US5520895A (en) * | 1994-07-07 | 1996-05-28 | Mobil Oil Corporation | Method for the reduction of nitrogen oxides using iron impregnated zeolites |
US5552129A (en) * | 1994-07-07 | 1996-09-03 | Mobil Oil Corporation | Catalytic system for the reduction of nitrogen oxides |
FR2773144B1 (fr) | 1997-12-31 | 2000-02-04 | Grande Paroisse Sa | Catalyseur a base de ferrierite/fer pour la reduction catalytique de la teneur de gaz en protoxyde d'azote. son procede d'obtention. application au traitement de gaz industriels |
DE102005022650A1 (de) | 2005-05-11 | 2006-11-16 | Uhde Gmbh | Verfahren zur Verringerung des Gehaltes an Stickoxiden in Gasen |
KR101394774B1 (ko) | 2005-12-14 | 2014-05-15 | 바스프 카탈리스트 엘엘씨 | SCR에서의 NOx 환원이 개선된 제올라이트 촉매 |
JP4803487B2 (ja) * | 2006-02-22 | 2011-10-26 | 株式会社豊田中央研究所 | 窒素酸化物選択還元触媒及びその製造方法 |
EP2517790A3 (en) | 2007-03-26 | 2013-08-21 | PQ Corporation | Novel microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same |
DE102009015592A1 (de) * | 2009-03-30 | 2010-10-07 | Süd-Chemie AG | Alterungsstabiler Katalysator zur Oxidation von NO zu NO2 in Abgasströmen |
CN105749747A (zh) * | 2009-04-17 | 2016-07-13 | 约翰逊马西有限公司 | 小孔分子筛负载铜催化剂 |
DE102009040352A1 (de) * | 2009-09-05 | 2011-03-17 | Johnson Matthey Catalysts (Germany) Gmbh | Verfahren zur Herstellung eines SCR aktiven Zeolith-Katalysators sowie SCR aktiver Zeolith-Katalysator |
JP2011125845A (ja) * | 2009-11-19 | 2011-06-30 | Ibiden Co Ltd | ハニカム構造体の製造方法 |
BR112015019073A2 (pt) * | 2013-02-18 | 2017-07-18 | Johnson Matthey Plc | métodos para produzir uma composição de captação de nox e para tratamento de um gás de escapamento de um motor de combustão interna, composição de captação de nox, captação de nox, sistema de escapamento para motores de combustão interna, e, catalisador de partida a frio |
KR20160129030A (ko) * | 2014-02-28 | 2016-11-08 | 존슨 맛쎄이 퍼블릭 리미티드 컴파니 | 개선된 저온 성능을 가진 scr 촉매, 및 그것의 제조 및 사용 방법 |
JP6126141B2 (ja) * | 2014-05-30 | 2017-05-10 | トヨタ自動車株式会社 | 排ガス浄化用触媒の製造方法 |
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CN106029228A (zh) | 2016-10-12 |
US11000836B2 (en) | 2021-05-11 |
EP3110550B1 (en) | 2024-07-03 |
EP3110550A1 (en) | 2017-01-04 |
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GB2543165B (en) | 2020-09-02 |
DE112015001052T5 (de) | 2016-12-08 |
BR112016019834A2 (en, 2012) | 2017-08-15 |
CN116037220A (zh) | 2023-05-02 |
US20190247836A1 (en) | 2019-08-15 |
KR20160129030A (ko) | 2016-11-08 |
US20150246346A1 (en) | 2015-09-03 |
WO2015128663A1 (en) | 2015-09-03 |
JP2017510437A (ja) | 2017-04-13 |
US10272419B2 (en) | 2019-04-30 |
BR112016019834B1 (pt) | 2021-09-28 |
RU2016138284A (ru) | 2018-04-02 |
GB201616290D0 (en) | 2016-11-09 |
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