Composite, zoned oxidation catalyst for a compression ignition internal combustion engine
A compression ignition internal combustion engine ( 30 ) for a heavy-duty diesel vehicle comprising an exhaust system ( 32 ) comprising a composite oxidation catalyst ( 12, 42 ) and a soot filter substrate ( 44, 50 ) disposed downstream from the composite oxidation catalyst comprising: a substrate ( 5 ), preferably 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 (I) and a second substrate end (O); two catalyst washcoat zones ( 1, 2 ) arranged axially in series on and along the substrate surface, wherein a first catalyst washcoat zone ( 1 ) having a length L 1 and comprising a first catalyst washcoat layer ( 9 ), wherein L 1 <L, is defined at one end by the first substrate end (I) and at a second end by a first end ( 15 ) of a second catalyst washcoat zone ( 2 ) having a length L 2 and comprising a second catalyst washcoat layer ( 11 ), wherein L 2 <L, wherein the second catalyst washcoat zone ( 2 ) is defined at a second end thereof by the second substrate end (O), and wherein the first substrate end (I) of the composite oxidation catalyst ( 12, 42 ) is oriented to an upstream side and wherein the first catalyst washcoat zone ( 1 ) 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 ( 2 ) comprises a second refractory metal oxide support material and one or more platinum group metal components supported thereon; and a washcoat overlayer (G) extending axially from the first substrate end (I) comprising a particulate metal oxide having a loading of >48.8 g/l (>0.8 g/in 3 ), wherein a total platinum group metal loading in the first catalyst washcoat zone ( 1 ) defined in grams of platinum group metal per litre of substrate volume (g/l) is greater than a total platinum group metal loading in the second catalyst washcoat zone ( 2 ) and wherein the first catalyst washcoat zone ( 1 ) comprises one or more first alkaline earth metal components, preferably barium, supported on the first refractory metal oxide support material.
1. A compression ignition internal combustion engine ( 30 ) for a heavy-duty diesel vehicle comprising an exhaust system ( 32 ), which exhaust system comprising a composite oxidation catalyst ( 12 , 42 ) and a soot filter substrate ( 44 , 50 ) disposed downstream from the composite oxidation catalyst, which composite oxidation catalyst ( 12 , 42 ) comprising:
a substrate ( 5 ) having a total length (L) and a longitudinal axis and having a substrate surface extending axially between a first substrate end (I) and a second substrate end (O);
two catalyst washcoat zones ( 1 , 2 ) arranged axially in series on and along the substrate surface, wherein a first catalyst washcoat zone ( 1 ) having a length (L 1 ) and comprising a first catalyst washcoat layer ( 9 ), wherein (L 1 ) is <50% (L), is defined at one end by the first substrate end (I) and at a second end by a first end ( 15 ) of a second catalyst washcoat zone ( 2 ) having a length (L 2 ) and comprising a second catalyst washcoat layer ( 11 ), wherein (L 2 )<(L), wherein the second catalyst washcoat zone ( 2 ) is defined at a second end thereof by the second substrate end (O), and wherein the first substrate end (I) of the composite oxidation catalyst ( 12 , 42 ) is oriented to an upstream side and wherein the first catalyst washcoat zone (1) 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 ( 2 ) comprises a second refractory metal oxide support material and one or more platinum group metal components supported thereon; and
a washcoat overlayer (G) extending axially from the first substrate end (I) for protecting at least part of the underlying first catalyst washcoat zone ( 1 ) from phosphorus and/or zinc poisoning when in use, thereby to retain activity of the first catalyst washcoat zone ( 1 ) to generate an exotherm from an increased concentration of hydrocarbon fuel present in exhaust gas relative to normal operating conditions for heating the downstream filter, which washcoat overlayer (G) comprising a particulate metal oxide having a loading of >48.8 g/l (>0.8g/in 3 ), wherein the washcoat overlayer extends axially for greater than 100% and up to 150% of the axial length of the underlying first catalyst washcoat layer from the first substrate end (I)
wherein a total platinum group metal loading in the first catalyst washcoat zone ( 1 ) defined in grams of platinum group metal per litre of substrate volume (g/l) is greater than a total platinum group metal loading in the second catalyst washcoat zone ( 2 ) and wherein the first catalyst washcoat zone ( 1 ) comprises one or more first alkaline earth metal components supported on the first refractory metal oxide support material.
2. The compression ignition internal combustion engine according to claim 1 , wherein the weight ratio of platinum to palladium in the first catalyst washcoat zone ( 1 ) is less than 1:1 to ≥1:3.
3. The compression ignition internal combustion engine according to claim 1 , wherein the particulate metal oxide in the washcoat overlayer has a mean pore diameter of ≥10 nm and/or the washcoat overlayer has a mean interparticle pore diameter of ≥10 nm.
4. The compression ignition internal combustion engine 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.
5. The compression ignition internal combustion engine according to claim 1 , wherein the particulate metal oxide in the washcoat overlayer has a specific surface area of >100 m 2 /g.
6. The compression ignition internal combustion engine according to claim 1 , wherein the washcoat overlayer extends axially for up to 120%, of the axial length of the underlying first catalyst washcoat layer from the first substrate end.
7. The compression ignition internal combustion engine 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.
8. The compression ignition internal combustion engine according to claim 7 , wherein the platinum group metal loading in the washcoat overlayer is 0.0353-1.2360 g/l (1-35 gft −3 ).
9. The compression ignition internal combustion engine according to claim 1 , wherein a total platinum group metal loading in the first catalyst washcoat zone ( 1 ) is <3.53 g/l (<100 g/ft 3 ) calculated as elemental metal.
10. The compression ignition internal combustion engine according to claim 1 , comprising a total platinum group metal loading on the substrate ( 5 ) as a whole of 0.177-2.119 g/l (5-60 g/ft 3 ) calculated as elemental metal.
11. The compression ignition internal combustion engine according to claim 1 , wherein a total alkaline earth metal loading in the first catalyst washcoat zone ( 1 ) is 0.353-3.531 g/l (10-100 g/ft 3 ) calculated as elemental metal.
12. The compression ignition internal combustion engine 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 ( 1 ) is <1:1.
13. The compression ignition internal combustion engine according to claim 1 , wherein at least the first refractory metal oxide support material comprises alumina doped with a heteroatom, preferably silica.
14. The compression ignition internal combustion engine according to claim 1 , wherein a catalyst washcoat zone defined at a second end thereof by the second substrate end comprises manganese and/or the second catalyst washcoat layer comprises manganese.
15. The compression ignition internal combustion engine according to claim 1 , wherein substrate ( 5 ) comprises a honeycomb flow-through substrate monolith.
16. The compression ignition internal combustion engine according to claim 1 , wherein the first catalyst washcoat zone ( 1 ) comprises barium.