WO2018065353A1 - Article catalyseur et procédé de réduction d'ammoniac et d'oxydes d'azote - Google Patents
Article catalyseur et procédé de réduction d'ammoniac et d'oxydes d'azote Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 169
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 116
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 55
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 55
- 239000007789 gas Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000000149 argon plasma sintering Methods 0.000 claims abstract description 14
- 239000010457 zeolite Substances 0.000 claims description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 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
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 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
- 230000000694 effects Effects 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009826 distribution Methods 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
- 229920001285 xanthan gum Polymers 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding 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
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003365 glass fiber Substances 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 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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- 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
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- 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
-
- 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
- B01D53/9459—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
- 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
- B01J29/064—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
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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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J37/0201—Impregnation
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- B01J37/0244—Coatings comprising several layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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- 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 catalyst often Pt based, 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 different 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 contains 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 applied 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 signifi- cantly 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, one or more ammonia oxidation catalyst impregnated in the body of the monolith, and and a layer containing one or more SCR catalysts coated on the walls of the monolith, wherein at least one of the SCR cat- alysts 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 with an inlet and an outlet end, in which the one or more oxidation catalysts are impregnated in the body of the monolith walls in a range at the outlet end that extends less than 100% of the monolith length, further con- taining a layer of one or more SCR catalysts, coated at the outlet end extending to the same range as the impregnated oxidation catalyst, 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 third embodiment is a catalyst article with an inlet and an outlet end, in which the one or more oxidation catalysts are impregnated in the body of the monolith walls in a range at the outlet end 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 impregnated oxidation catalyst, 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.
- a fourth embodiment is a catalyst article with an inlet and an outlet end, in which the one or more oxidation catalysts are impregnated in the body of the monolith walls in a range at the outlet end 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.
- 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 substrate, one or more ammonia oxidation catalysts impregnated in the body of the monolith, and a layer containing one or more SCR catalysts coated on the walls of the monolith, 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 with an inlet and an outlet end, in which the one or more oxidation catalysts are impregnated in the body of the monolith walls in a range at the outlet end 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 im- pregnated oxidation catalyst, 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 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 with an inlet and an outlet end, in which the one or more oxidation catalysts are impregnated in the body of the monolith walls in a range at the outlet end 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 impregnated oxidation catalyst, in which at least one SCR catalyst has an average parti- cle 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.
- 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 an inlet and an outlet end, in which the one or more oxidation cata- lysts are impregnated in the body of the monolith walls in a range at the outlet end 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 meas- ured by light scattering, in the range of approximately 4-40 ⁇ .
- 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, in which 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 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, in which 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 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, in which 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.
- an eighth embodiment of the method for the removal of ammonia and nitrogen ox- ides from an engine exhaust gas comprises the step of contacting the exhaust gas with a catalyst article, in which 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.
- the catalyst item of the invention improves the removal of ammonia from a gas stream, without compromising the selectivity to NOx.
- two catalysts both consisting of Pt impregnated on the monolith support and a washcoat based on a Cu-beta zeolite.
- the Cu-beta zeolite had an average agglomerate size, as measured by light scattering, of 3.1 ⁇ .
- the second catalyst the same Cu-beta zeolite was used, but the particles were agglomerated to an average size of 8.4 ⁇ , as measured by light scattering as shown in Figure 1 .
- the monolith substrates used in catalysts A and B were prepared by impregnating a monolith, consisting of glassfiber and T1O2 (ca. 260 cpsi), with Pt by impregnation of an aqueous solution of Pt(NH3)4HCC>3 to a final Pt loading of about 100 mg Pt/I monolith and calcined for 3 h at 550 °C.
- the Cu-zeolite material used in catalyst A 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 zeo- lite 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 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 A as shown in Figure 1.
- This Cu- * BEA zeolite powder was then mixed with water to a dry matter content of 20 wt% and xanthan gum (Keltrol®) was added to a final concentration of 0.12 wt%, to obtain the washcoat slurry.
- a Pt-impregnated monolith (ca. 80 x 50 mm in size) was dipped in the washcoat slurry and dried at room temperature in flowing air for about 1 hour. Then, the monolith was dipped once more in the same slurry, dried for about 1 hr in flowing air and calcined for 3 hours at 550 °C to obtain catalyst A.
- the final load of Cu- * BEA in catalyst A was 141 g Cu- * BEA/I monolith.
- the Cu-zeolite 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 and Levasil 200/30 were added to the solution. The amount of Levasil 200/30 corresponds to 0.05 g dry matter/g zeolite. 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 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 1.
- This Cu- * BEA zeolite powder was then mixed with water to a dry matter content of 30 wt% and Levasil 200/30 (0.02 g dry matter/g powder) and xanthan gum (Keltrol®) was added (0.06 wt%) were added, to obtain the washcoat slurry.
- a Pt-impregnated monolith (ca. 80 x 50 mm in size) was dipped in the washcoat slurry and dried at room temperature in flowing air for about 1 hour.
- catalyst B was calcined for 3 hours at 550 °C to obtain catalyst B.
- the final load of Cu- * BEA in catalyst B was 135 g Cu- * BEA/I monolilth.
- the performance measurements of catalysts A and B were 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 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 .
- 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 1 shows the measured ammonia conversion and total yield of nitrogen for catalysts A and B in temperature range 250-550 °C. These results show that the total yield of nitrogen for catalyst B has increased significantly, in particular in the range 250-400 °C, which is most relevant for diesel exhaust gas cleaning purposes.
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Abstract
L'article de catalyseur comprend un substrat monolithique, un ou plusieurs catalyseurs d'oxydation d'ammoniac imprégnés dans le substrat monolithique, et une couche contenant un ou plusieurs catalyseurs SCR revêtus sur les parois du monolithe, où 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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PCT/EP2017/074956 WO2018065354A1 (fr) | 2016-10-03 | 2017-10-02 | Article de catalyseur et procédé de réduction d'ammoniac et d'oxydes d'azote |
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EP4129475A4 (fr) * | 2020-03-26 | 2024-04-17 | Cataler Corp | Dispositif catalytique de purification de gaz d'échappement |
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CN114072407A (zh) | 2019-04-02 | 2022-02-18 | 阿里戈斯治疗公司 | 靶向prmt5的化合物 |
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 |
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 |
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 |
US8524185B2 (en) | 2008-11-03 | 2013-09-03 | Basf Corporation | Integrated SCR and AMOx catalyst systems |
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 (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 |
US8524185B2 (en) | 2008-11-03 | 2013-09-03 | Basf Corporation | Integrated SCR and AMOx catalyst systems |
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 |
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 |
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 (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4129475A4 (fr) * | 2020-03-26 | 2024-04-17 | Cataler Corp | Dispositif catalytique de purification de gaz d'échappement |
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