WO2018065354A1 - Article de catalyseur et procédé de réduction d'ammoniac et d'oxydes d'azote - Google Patents
Article de catalyseur et procédé de réduction d'ammoniac et d'oxydes d'azote Download PDFInfo
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- WO2018065354A1 WO2018065354A1 PCT/EP2017/074956 EP2017074956W WO2018065354A1 WO 2018065354 A1 WO2018065354 A1 WO 2018065354A1 EP 2017074956 W EP2017074956 W EP 2017074956W WO 2018065354 A1 WO2018065354 A1 WO 2018065354A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 228
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 119
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 57
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000000149 argon plasma sintering Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims description 19
- 239000010457 zeolite Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims 20
- 239000002356 single layer Substances 0.000 claims 2
- 239000002002 slurry Substances 0.000 description 27
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 19
- 229910001868 water Inorganic materials 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000007654 immersion Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D—SEPARATION
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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
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9436—Ammonia
-
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- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
- B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the invention relates to the removal of nitrogen oxides (NOx) and ammonia from an exhaust gas of a fuel-lean combustion, with a focus on, but not limited to, exhaust gas from compression ignition engines in vehicles.
- NO nitrogen oxides
- NH3 selective catalytic reduction
- NH3 is usually provided by controlled injection of a urea solution in the exhaust gas stream.
- the selective catalytic reduction is usually performed with a slight excess of NH3, since the process then becomes more efficient.
- an NH3 slip is created, which has to be removed from the exhaust gas stream as well by catalytic oxidation of NH3 using the residual oxygen in the exhaust gas stream.
- a standard configuration of a modern exhaust gas aftertreatment system con- sists of an oxidation catalyst for the removal of CO and hydrocarbons, a filter to retain soot particles and an SCR - ammonia slip catalyst (SCR/ASC) system for the abatement of NOx and excess of NH3.
- SCR/ASC SCR - ammonia slip catalyst
- the removal of NOx from the exhaust gas of fuel-lean combustion is based on the se- lective reduction of NOx by ammonia (NH3-SCR): 4 NO + 4 NH 3 + 0 2 ⁇ 4 N 2 + 6 H 2 0.
- the first type of catalysts for this reaction is base metal oxides or a combination of base metal oxides.
- the most commonly used SCR catalysts are based on vanadium oxide, such V2O5/T1O2, V2O5/WO3/T1O2, but other oxides from the metals in groups 3, 4, 5, 6 and 7 may be applied as well.
- the second type of SCR catalysts is based on ion- exchanged zeolites or zeotype materials.
- oxidation catalyst a catalyst active for oxidation of ammonia with oxygen
- any material with activity for ammonia oxidation by oxygen could be used, but by far the most commonly applied catalysts are based on Pt, as these catalysts provide the lowest light-off temperature for ammonia oxidation and are already active at around 200 °C.
- Pt oxidation of ammonia with oxygen produces larger amounts of NO, in particular at temperatures above 250 °C.
- an oxidation cata- lyst is combined with an SCR catalyst, to yield a bifunctional catalyst system which enables the NH3-SCR reaction to occur with the NO produced by oxidation of ammonia with the residual ammonia and oxygen in the gas stream, thus reducing the NH3 slip without compromising the NOx emission.
- NH3 oxidation catalysts and NH3-SCR catalysts can be combined in dif- ferent ways to obtain a bifunctional catalyst system to remove the NH3 from an exhaust gas stream.
- US4188364 discloses a catalyst system comprising two catalyst beds in series in which the first catalyst bed contains an NH3-SCR catalyst and the second catalyst bed contains an oxidation catalyst, thus forming a simple serial arrangement of the two catalysts. Another possible configuration is to mix the oxidation catalyst and the SCR catalyst and apply the mixture on a monolith by a washcoating process.
- JP3436567 discloses a layered arrangement of the oxidation and SCR catalysts in which the top layer contains the active SCR material, and the bottom layer contains the oxidation catalyst.
- EP1992409 discloses a different layered structure, in which a first catalyst layer con- tains a mixture of a Pt based oxidation catalyst with a zeolite based material active for SCR, which is coated directly on the wall of the monolith, and a second layer on top of the first layer containing only a zeolite based SCR catalyst.
- the oxidation catalyst or mixture of oxidation catalyst and SCR catalyst can also be impregnated in the walls of the monolith, after which the SCR active layer is ap- plied on the monolith walls by a washcoating process.
- a washcoating process is disclosed in JP3793283B2.
- Layered configurations of SCR and oxidation catalysts are known to result in an efficient removal of ammonia, without excessive NOx slip.
- activity of SCR/ASC catalyst articles can further be improved in terms of oxidation efficiency of NH3 and increase the yield of nitrogen, when including in the catalyst article one or more SCR catalyst(s) in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of 4-40 ⁇ .
- SCR catalyst refers to catalysts with activity for NH3-SCR in the range 150-550 °C and also possess activity for the oxidation of ammonia by oxygen, typically at higher temperatures (> approximately 350 °C).
- ammonia oxidation catalyst refers to catalysts with a significantly higher activity for ammonia oxidation with oxygen below approximately 300 °C.
- this invention provides in a first aspect a catalyst article comprising a monolithic catalyst carrier substrate containing one or more oxidation cat- alysts, and one or more SCR catalysts, wherein at least one of the SCR catalysts has an average particle size or agglomerate size, as measured by light scattering, in the range of 4-40 ⁇ .
- a second embodiment is a catalyst article comprising a monolithic catalyst carrier substrate comprising one coated layer containing a mixture of one or more oxidation cata- lysts and one or more SCR catalysts, wherein at least one of the SCR catalysts has an average particle size or agglomerate size, as measured by light scattering, in the range 4-40 ⁇ .
- a third embodiment is a catalyst article comprising a monolithic catalyst carrier substrate with a first coated layer containing one or more oxidation catalysts, and a second layer containing one or more SCR catalysts, wherein at least one of the SCR catalysts has an average particle size or agglomerate size, as measured by light scattering, in the range 4-40 ⁇ .
- a fourth embodiment is a catalyst article comprising a monolithic catalyst carrier substrate with a first coated layer containing one or more oxidation catalysts and further containing one or more SCR catalysts, and a second layer containing one or more SCR catalysts, wherein at least one of the SCR catalysts has an average particle size or agglomerate size, as measured by light scattering, in the range 4-40 ⁇ .
- a fifth embodiment is a catalyst article with an inlet and an outlet end, in which the first catalyst layer containing one or more oxidation catalysts and optionally one or more SCR catalysts is applied at the outlet end in a range that extends less than 100% of the monolith length, in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of approximately 4-40 ⁇ .
- a sixth embodiment is a catalyst article with an inlet and an outlet end, in which the first catalyst layer containing one or more oxidation catalysts and optionally one or more SCR catalysts is applied at the outlet end in a range that extends less than 100% of the monolith length, further containing a layer of one or more SCR catalysts, coated at the outlet end extending to the same range as the first catalyst layer, in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of approximately 4-40 ⁇ .
- a seventh embodiment is a catalyst article with an inlet and an outlet end, in which the first catalyst layer containing one or more oxidation catalysts and optionally one or more SCR catalysts is applied at the outlet end in a range that extends less than 100% of the monolith length, further containing a layer of one or more SCR catalysts, coated at the outlet end extending to the same range as the first catalyst layer, in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of approximately 4-40 ⁇ further containing a different SCR catalyst at the inlet end.
- An eighth embodiment is a catalyst article with an inlet and an outlet end, in which the first catalyst layer containing one or more oxidation catalysts and optionally one or more SCR catalysts is applied at the outlet end in a range that extends less than 100% of the monolith length, further containing a layer of one or more SCR catalysts, coated at the outlet end extending to a larger range as the impregnated oxidation catalyst and a maximum of 100% of the monolith length, in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of approximately 4-40 ⁇ .
- the one or more ammonia oxidation catalysts in any of the previous embodiments are selected from the group of Pt, Ir, Pd, Rh and mixtures thereof.
- the one or more SCR catalysts in any of the previous embodiments comprise a zeolite or zeotype material containing Cu, Fe or combinations thereof.
- the zeolite or zeotype material is selected from the group having a framework type of AEI, AFX, CHA, KFI, ERI, LTA, IMF, ITH, MEL, MFI, SZR, TUN, * BEA, BEC, FAU, FER, MOR, LEV.
- the one or more SCR catalysts in any of the previous embodi- ments comprises an oxide selected from oxides of Mo, Cr, V, W, Ta, Nb, Ti, Ce and combinations thereof.
- auxiliary agents such as binders
- a second aspect of the invention is a method for the removal of ammonia and nitrogen oxides from an engine exhaust gas, comprising the step of contacting the exhaust gas with a catalyst article comprising a monolithic catalyst carrier substrate, containing one or more oxidation catalysts, and one or more SCR catalysts, wherein at least one of the SCR catalysts has an average particle size or agglomerate size, as measured by light scattering, in the range of 4-40 ⁇ .
- a second embodiment of the method for the removal of ammonia and nitrogen oxides from an engine exhaust gas comprises the step of contacting the exhaust gas with a catalyst article comprising a monolithic catalyst carrier substrate comprising one coated layer containing a mixture of one or more oxidation catalysts and one or more SCR catalysts, wherein at least one of the SCR catalysts has an average particle size or ag- glomerate size, as measured by light scattering, in the range 4-40 ⁇ .
- a third embodiment of the method for the removal of ammonia and nitrogen oxides from an engine exhaust gas comprises the step of contacting the exhaust gas with a catalyst article comprising a monolithic catalyst carrier substrate with a first coated layer containing one or more oxidation catalysts, and a second layer containing one or more SCR catalysts, wherein at least one of the SCR catalysts has an average particle size or agglomerate size, as measured by light scattering, in the range 4-40 ⁇ .
- a fourth embodiment of the method for the removal of ammonia and nitrogen oxides from an engine exhaust gas comprises the step of contacting the exhaust gas with a catalyst article with a first coated layer containing one or more oxidation catalysts, and a second layer containing one or more SCR catalysts, wherein at least one of the SCR catalysts has an average particle size or agglomerate size, as measured by light scattering, in the range 4-40 ⁇ .
- a fifth embodiment of the method for the removal of ammonia and nitrogen oxides from an engine exhaust gas comprises the step of contacting the exhaust gas with a catalyst article with an inlet and an outlet end, in which the first catalyst layer containing one or more oxidation catalysts and optionally one or more SCR catalysts is applied at the outlet end in a range that extends less than 100% of the monolith length, in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of approximately 4-40 ⁇ .
- a sixth embodiment of the method for the removal of ammonia and nitrogen oxides from an engine exhaust gas comprises the step of contacting the exhaust gas with a catalyst article with an inlet and an outlet end, in which the first catalyst layer containing one or more oxidation catalysts and optionally one or more SCR catalysts is applied at the outlet end in a range that extends less than 100% of the monolith length, further containing a layer of one or more SCR catalysts, coated at the outlet end extending to the same range as the first catalyst layer, in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of approximately 4-40 ⁇ .
- a seventh embodiment of the method for the removal of ammonia and nitrogen oxides from an engine exhaust gas comprises the step of contacting the exhaust gas with a catalyst article with an inlet and an outlet end, in which the first catalyst layer containing one or more oxidation catalysts and optionally one or more SCR catalysts is applied at the outlet end in a range that extends less than 100% of the monolith length, further containing a layer of one or more SCR catalysts, coated at the outlet end extending to the same range as the first catalyst layer, in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of approximately 4-40 ⁇ further containing a different SCR catalyst at the inlet end.
- An eighth embodiment of the method for the removal of ammonia and nitrogen oxides from an engine exhaust gas comprises the step of contacting the exhaust gas with a catalyst article with an inlet and an outlet end, in which the first catalyst layer containing one or more oxidation catalysts and optionally one or more SCR catalysts is applied at the outlet end in a range that extends less than 100% of the monolith length, further containing a layer of one or more SCR catalysts, coated at the outlet end extending to a larger range as the impregnated oxidation catalyst and a maximum of 100% of the monolith length, in which at least one SCR catalyst has an average particle size or agglomerate size, as measured by light scattering, in the range of approximately 4-40 ⁇ .
- the one or more ammonia oxidation catalysts in any of the previous embodiments are selected from the group of Pt, Ir, Pd, Rh and mixtures thereof.
- the one or more SCR catalysts in any of the previous embodiments comprise a zeolite or zeotype material containing Cu, Fe or combinations thereof.
- the zeolite or zeotype material is selected from the group having a framework type of AEI, AFX, CHA, KFI, ERI, LTA, IMF, ITH, MEL, MFI, SZR, TUN, * BEA, BEC, FAU, FER, MOR, LEV.
- the one or more SCR catalysts in any of the previous embodiments comprises an oxide selected from oxides of Mo, Cr, V, W, Ta, Nb, Ti, Ce and combinations thereof.
- This example highlights the performance of a catalyst item in which the oxidation catalyst is mixed with an SCR catalyst.
- the catalyst item was prepared by using a Cu-*BEA zeolite material with a particle size distribution, as measured by light scattering, given in Figure 1 .
- the average particle size is 1 1.9 ⁇ .
- a glassfiber monolith coated with T1O2 (50x80 mm, ca. 260 cpsi) was immersed in the washcoat slurry and dried at room temperature. Then, water was added to the washcoat slurry to obtain a slurry with a dry matter content of 17.5% and the monolith was dipped once more in the washcoat slurry. The monolith was then dried at room temperature, and calcined for 3 h at 550 °C in air. Total washcoat loading after calcination was 170 g/l.
- the performance measurement of the catalyst item was done by cutting a sample of 30x50 mm from the monoliths prepared as described above, and placing it in a reactor. Prior to the activity measurement, the catalyst was heated to 550 °C for 2 hours in the reaction feed gas consisting of 200 ppm NH3, 12% O2, and 4% H2O in N2, at a total flow of 15 m 3 /h, corresponding to a SV of 250,000 h "1 . In the activity measurement, the temperature was varied between 170°C and 550 °C, using the same reactor feed gas and flow. The concentrations of ammonia and NOx in the reactor exit gas were continuously monitored by an FTI R spectrometer, and the conversion of ammonia and the total yield of N2 were evaluated. Table 1 shows the measured ammonia conversion and total yield of nitrogen for this catalyst in the temperature range 250-550 °C. Table 1
- the performance of two monolith catalysts with a first washcoat layer of Pt/TiC>2 and a second washcoat layer containing a Cu- * BEA catalyst is shown, in which the agglomerate size of the Cu- * BEA particles is different.
- the agglomerate size, measured with light scattering, of the Cu- * BEA material was 2.9 ⁇ ; in the second catalyst (Catalyst B), the agglomerate size of the Cu- * BEA material was 9.3 ⁇ .
- the particle size distributions are shown in Figure 2.
- the monolith sub- strates used in catalysts A and B consisted of glassfiber coated with T1O2, with a channel density of about 260 cpsi, and were about 80 x 50 mm (height x diameter) in size.
- the slurry for the Pt/TiC>2 washcoat for both Catalysts A and B was prepared as follows.
- 32.8 g of this Pt/Ti0 2 powder was mixed with 174 g of a solution of 0.23 wt% xanthan gum in water, and water was added to a total amount of 800 g slurry.
- the slurry was shaked in a paint shaker for 6 min.
- the dry matter content of the slurry was determined to be 4.1 %.
- the Cu- * BEA material used in Catalyst A was prepared as follows. An aqueous solu- tion of 133 g Cu(N0 3 )2-3H 2 0. in 6500 g water was prepared. 1000 g of an H- * BEA zeolite with a Si/AI ratio of 15 was added to the solution and the mixture was stirred for ca. 1 hr at room temperature to perform the ion-exchange. The mixture was then dried at 120 °C and calcined to 450 °C in a rotary furnace to obtain a dry powder of Cu- * BEA with about 3.5 wt% Cu, with the particle size distribution for catalyst A as shown in Figure 1 .
- Catalyst A was prepared by immersion of a monolith in the Pt slurry for 1 .5 min, followed by drying at room temperature and 250 °C. The uptake of slurry was determined to 1 1.6 g/ 1 monolith. Then, the monolith containing the Pt slurry was immersed three times in Slurry A for 1 .5 min, and dried at room temperature between the immersions. In the first immersion, the dry matter content of the Slurry A was adjusted to 20%; in the second immersion, the dry matter content was adjusted to 15.9% and in the third immersion the dry matter content was adjusted to 12%. After the final immersion, the monolith was calcined at 550 °C for 3 h. The total uptake was 175 g/l.
- the Cu- * BEA material used in Catalyst B was prepared as follows. An aqueous solution of 133 g Cu(N0 3 )2-3H 2 0. in 6500 g water was prepared. 1000 g of an H- * BEA zeolite with a Si/AI ratio of 15 was added to the solution. Furthermore, a solution of 30 % Levasil 200 N, to a total amount of 50 g on a dry matter basis, and a solution of polyvinyl alcohol (PVA), to a total amount of 50 g PVA, were added. The mixture was stirred for about 1 hr at room temperature to perform the ion exchange.
- PVA polyvinyl alcohol
- the mixture was then dried at 120 °C and calcined at 550 °C for 3 h to obtain a dry powder of Cu- * BEA with about 3.5 wt% Cu, with the particle size distribution for catalyst B as shown in Figure 2.
- the Cu- * BEA slurry for catalyst B (Slurry B) was obtained by mixing 180 g of this Cu- * BEA material with 400 g of a 2 wt% solution of methyl cellulose (4000 cP) in water, and 30 g of a 30% solution of Levasil 200 N and a solution of NH4OH (33%) to adjust the pH to 9. Water was added until the dry matter content of the slurry was 18%.
- Catalyst B was prepared by immersion of a monolith in the Pt slurry for 1 .5 min, followed by drying at room temperature and 250 °C. The uptake of slurry was determined to 1 1 .9 g/ 1 monolith. Then, the monolith containing the Pt slurry was immersed three times in the Slurry B for 1 .5 min, and dried at room temperature between the immersions. In the first immersion, the dry matter content of the Cu- * BEA slurry was adjusted to 16%; in the second immersion, the dry matter content was adjusted to 14.5% and in the third immersion the dry matter content was adjusted to 10%. After the final immersion, the monolith was calcined at 550 °C for 3 h. The total uptake was 165 g/l.
- Catalysts A and B were done by cutting a sample of 30 x50 mm from the monoliths prepared as described above, and placing it in a re- actor. Prior to the activity measurement, the catalysts were heated to 550 °C for 2 hours in the reaction feed gas consisting of 200 ppm NH3, 12% O2, and 4% H2O in N2, at a total flow of 15 m 3 /h, corresponding to a SV of 250,000 h "1 . In the activity measurement, the temperature was varied between 170°C and 550 °C, using the same reactor feed gas and flow. The concentrations of ammonia and NOx in the reactor exit gas were continuously monitored by an FTIR spectrometer. The conversion of ammonia and the total yield of N2 were evaluated
- Table 2 shows the measured ammonia conversion and total yield of nitrogen for catalysts A and B in temperature range 250-550 °C. The results show a significantly improved conversion of NH3 and N2 yield in Catalyst B in the range 250-400 °C.
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Abstract
L'article de catalyseur comprend un substrat monolithique, un ou plusieurs catalyseurs d'oxydation,et un ou plusieurs catalyseurs de SCR, au moins l'un des catalyseurs SCR ayant une taille de particule moyenne ou une taille d'agglomérat, telle que mesurée par diffusion de lumière, dans la plage de 4 à 40 µm et un procédé d'élimination d'ammoniac et d'oxydes d'azote à partir d'un gaz d'échappement de moteur en présence de l'article de catalyseur.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4188364A (en) | 1977-05-31 | 1980-02-12 | Caterpillar Tractor Co. | Two-stage catalysis of engine exhaust |
JP3436567B2 (ja) | 1993-06-23 | 2003-08-11 | バブコック日立株式会社 | 排ガス浄化触媒およびその製造方法 |
JP3793283B2 (ja) | 1996-06-20 | 2006-07-05 | バブコック日立株式会社 | 排ガス浄化用触媒およびそれを用いた排ガス浄化装置 |
EP1992409A1 (fr) | 2007-05-09 | 2008-11-19 | N.E. Chemcat Corporation | Catalyseur de type de réduction catalytique sélective, et équipement de purification de gaz d'échappement et procédé de purification de gaz d'échappement l'utilisant |
US20100111796A1 (en) * | 2008-11-03 | 2010-05-06 | Basf Catalysts Llc | Integrated SCR and AMOX Catalyst Systems |
US20130216439A1 (en) * | 2010-11-02 | 2013-08-22 | HARLDOR Topsoe A/S | Method for the preparation of a catalysed particulate filter and catalysed particulate filter |
US20130216441A1 (en) * | 2010-11-02 | 2013-08-22 | Haldor Topsoe A/S | Method for the preparation of a catalysed particulate filter and catalysed particulate filter |
US20150321184A1 (en) * | 2014-05-09 | 2015-11-12 | Johnson Matthey Public Limited Company | Ammonia slip catalyst having platinum impregnated on high porosity substrates |
-
2017
- 2017-10-02 WO PCT/EP2017/074955 patent/WO2018065353A1/fr not_active Application Discontinuation
- 2017-10-02 WO PCT/EP2017/074956 patent/WO2018065354A1/fr not_active Application Discontinuation
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4188364A (en) | 1977-05-31 | 1980-02-12 | Caterpillar Tractor Co. | Two-stage catalysis of engine exhaust |
JP3436567B2 (ja) | 1993-06-23 | 2003-08-11 | バブコック日立株式会社 | 排ガス浄化触媒およびその製造方法 |
JP3793283B2 (ja) | 1996-06-20 | 2006-07-05 | バブコック日立株式会社 | 排ガス浄化用触媒およびそれを用いた排ガス浄化装置 |
EP1992409A1 (fr) | 2007-05-09 | 2008-11-19 | N.E. Chemcat Corporation | Catalyseur de type de réduction catalytique sélective, et équipement de purification de gaz d'échappement et procédé de purification de gaz d'échappement l'utilisant |
US20100111796A1 (en) * | 2008-11-03 | 2010-05-06 | Basf Catalysts Llc | Integrated SCR and AMOX Catalyst Systems |
US8524185B2 (en) | 2008-11-03 | 2013-09-03 | Basf Corporation | Integrated SCR and AMOx catalyst systems |
US20130216439A1 (en) * | 2010-11-02 | 2013-08-22 | HARLDOR Topsoe A/S | Method for the preparation of a catalysed particulate filter and catalysed particulate filter |
US20130216441A1 (en) * | 2010-11-02 | 2013-08-22 | Haldor Topsoe A/S | Method for the preparation of a catalysed particulate filter and catalysed particulate filter |
US20150321184A1 (en) * | 2014-05-09 | 2015-11-12 | Johnson Matthey Public Limited Company | Ammonia slip catalyst having platinum impregnated on high porosity substrates |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020205867A1 (fr) | 2019-04-02 | 2020-10-08 | Aligos Therapeutics, Inc. | Composés ciblant prmt5 |
US11198699B2 (en) | 2019-04-02 | 2021-12-14 | Aligos Therapeutics, Inc. | Compounds targeting PRMT5 |
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