Composite, zoned oxidation catalys for a compression ignition internal combustion engine
A composite oxidation catalyst for use in an exhaust system for treating an exhaust gas produced by a vehicular compression ignition internal combustion engine is disclosed. The composite oxidation catalyst comprises a honeycomb flow-through substrate monolith and two catalyst washcoat zones arranged axially in series on and along the substrate surface.
1. A composite oxidation catalyst for use in an exhaust system for treating an exhaust gas produced by a vehicular compression ignition internal combustion engine and located upstream of a particulate matter filter in the exhaust system, the composite oxidation catalyst comprising:
a honeycomb flow-through substrate monolith having a total length L and a longitudinal axis and having a substrate surface extending axially between a first substrate end and a second substrate end;
two catalyst washcoat zones arranged axially in series on and along the substrate surface, wherein a first catalyst washcoat zone having a length L 1 , wherein L 1 <L, is defined at one end by the first substrate end and at a second end by a first end of a second catalyst washcoat zone having a length L 2 , wherein L 2 <L, wherein the second catalyst washcoat zone is defined at a second end thereof by the second substrate end, wherein the first catalyst washcoat zone comprises a first refractory metal oxide support material and two or more platinum group metal components supported thereon comprising both platinum and palladium at a weight ratio of platinum to palladium of ≥1; and the second catalyst washcoat zone comprises a second refractory metal oxide support material and one or more platinum group metal components supported thereon; and
a washcoat overlayer extending axially from the first substrate end for protecting at least part of an underlying first catalyst washcoat zone from phosphorus and/or zinc poisoning when in use, which washcoat overlayer comprising a particulate metal oxide loading of >0.8 g/in 3 , wherein the particulate metal oxide has a mean pore diameter of ≥10 nm and/or the washcoat overlayer has a mean interparticle pore diameter of >10 nm,
wherein a total platinum group metal loading in the first catalyst washcoat zone defined in grams of platinum group metal per cubic foot of substrate volume (g/ft 3 ) is greater than a total platinum group metal loading in the second catalyst washcoat zone and wherein the first catalyst washcoat zone comprises a barium or strontium as a first alkaline-earth metal component supported on the first refractory metal oxide support material.
2. The composite oxidation catalyst according to claim 1 , wherein a weight ratio of platinum to palladium in the first catalyst washcoat zone is less than or equal to 10:1 and greater than or equal to 1.5:1.
3. The composite oxidation catalyst according to claim 1 , wherein a total platinum group metal loading in the first catalyst washcoat zone is <100 g/ft 3 calculated as elemental metal.
4. The composite oxidation catalyst according to claim 1 , wherein the one or more platinum group metal component in the second catalyst washcoat zone comprises both platinum and palladium.
5. The composite oxidation catalyst according to claim 4 , wherein a mass ratio of platinum to palladium in the second catalyst washcoat zone is greater than a mass ratio of platinum to palladium in the first catalyst washcoat zone.
6. The composite oxidation catalyst according to claim 1 , wherein L 1 is <50% L.
7. The composite oxidation catalyst according to claim 1 comprising a total platinum group metal loading on the substrate as a whole of 5-60 g/ft 3 calculated as elemental metal.
8. The composite oxidation catalyst according to claim 1 , wherein a total Pt: Pd weight ratio in the composite oxidation catalyst as a whole is 3:2 to 9:1.
9. The composite oxidation catalyst according to claim 1 , wherein a total alkaline-earth metal loading in the first catalyst washcoat zone is 10-100 g/ft 3 calculated as elemental metal.
10. The composite oxidation catalyst according to claim 1 , wherein a weight ratio of total elemental alkaline-earth metal to total elemental platinum group metal in the first catalyst washcoat zone is <1:1.
11. The composite oxidation catalyst according to claim 1 , wherein at least the first refractory metal oxide support material comprises alumina doped with a heteroatom.
12. The composite oxidation catalyst according to claim 11 , wherein at least the first refractory metal oxide support material comprises alumina doped with silica.
13. The composite oxidation catalyst according to claim 1 , wherein the particulate metal oxide in the washcoat overlayer is selected from the group consisting of alumina, silica, titania, zirconia, ceria and a mixed or composite oxide of any two or more thereof or an aluminosilicate zeolite.
14. The composite oxidation catalyst according to claim 1 , wherein the particulate metal oxide in the washcoat overlayer has a specific surface area of >100 m 2 /g.
15. The composite oxidation catalyst according to claim 1 , wherein the particulate metal oxide in the washcoat overlayer supports a platinum group metal, which is platinum or a combination of platinum and palladium at a Pt: Pd weight ratio of ≥1:1.
16. An exhaust system for a vehicular compression ignition engine comprising a composite oxidation catalyst according to claim 1 and a soot filter substrate disposed downstream from the oxidation catalyst, wherein the first substrate end of the composite oxidation catalyst is oriented to an upstream side.
17. A compression ignition internal combustion engine for a heavy-duty diesel vehicle comprising an exhaust system according to claim 16 , wherein the first substrate end of the composite oxidation catalyst is oriented to an upstream side.
18. A heavy-duty diesel vehicle comprising a compression ignition internal combustion engine according to claim 17 .
19. A method of using a composite oxidation catalyst according to claim 1 for heating a soot filter disposed downstream from the composite oxidation catalyst in an exhaust system of a vehicular compression ignition internal combustion engine by generating an exotherm from an increased concentration of hydrocarbon fuel in exhaust gas flowing in the exhaust system relative to normal operating conditions by contacting the oxidation catalyst with exhaust gas comprising the increased concentration of hydrocarbon fuel.
20. A method of making a composite oxidation catalyst for use in an exhaust system for treating an exhaust gas produced by a vehicular compression ignition internal combustion engine, wherein the composite oxidation catalyst comprises:
a honeycomb flow-through substrate monolith having a total length L and a longitudinal axis and having a substrate surface extending axially between a first substrate end and a second substrate end;
two catalyst washcoat zones arranged axially in series on and along the substrate surface, wherein a first catalyst washcoat zone having a length L 1 , wherein L 1 <L, is defined at one end by the first, substrate end and at a second end by a first end of a second catalyst washcoat zone having a length L 2 , wherein L 2 <L, wherein the second catalyst washcoat zone is defined at a second end thereof by the second substrate end, wherein the first catalyst washcoat zone comprises a first refractory metal oxide support material and two or more platinum group metal component supported thereon comprising both platinum and palladium at a weight ratio of platinum to palladium of ≥1; and the second catalyst washcoat zone comprises a second refractory metal oxide support material and one or more platinum group metal component supported thereon, and
a washcoat overlayer extending axially from the first substrate end for protecting at least part of an underlying first catalyst washcoat zone from phosphorus and/or zinc poisoning when in use, which washcoat overlayer comprising a particulate metal oxide loading of >0.8 g/in 3 , wherein the particulate metal oxide has a mean pore diameter of ≥10 nm and/or the washcoat overlayer has a mean interparticle pore diameter of ≥10 nm,
wherein a total platinum group metal loading in the first catalyst washcoat zone defined in grams of platinum group metal per cubic foot of substrate volume (g/ft 3 ) is greater than a total platinum group metal loading in the second catalyst washcoat zone and wherein the first catalyst washcoat zone comprises a barium or strontium as a first alkaline-earth metal component supported on the first refractory metal oxide support material, which method comprising the steps of:
(a) applying a catalyst washcoat layer to the substrate surface for a length extending from one end of the substrate to less than the total length of the substrate, which catalyst washcoat layer comprising a refractory metal oxide support material and one or more platinum group metal components; and
(b) impregnating the catalyst washcoat layer in a zone of length Li defined at one end by the first substrate end with a solution containing one or more platinum group metal,
which method further comprising a step (a′) before step (a) or after step (a) but in either case before step (b) of applying a second catalyst washcoat layer to the substrate for a length extending from the second substrate end to less than the total length of the substrate, such that the first catalyst washcoat layer in part overlaps the second catalyst washcoat layer or the second catalyst washcoat layer in part overlaps the first catalyst washcoat layer, wherein the second catalyst washcoat layer comprises a refractory metal oxide support material and one or more platinum group metal components, wherein the barium or strontium alkaline-earth metal component is present in the catalyst washcoat layer of step (a) and/or an impregnation solution used in step (b).