Patent Application
20230405564
The present invention relates to a process for preparing a catalyst which is suitable for the treatment of an exhaust gas of a diesel combustion engine. Further, the present invention relates to a catalyst which can be prepared according to said process and a use thereof.
Cu-containing zeolitic materials, in particular zeolitic materials having framework structure type CHA, are currently used for automotive light duty diesel-selective catalytic reduction (LDD-SCR) catalysts since they are able to remove NOx emissions from an exhaust stream at very low temperatures. However, such catalysts typically show a comparatively high N2O make at temperatures higher than 300° C. and a poorer NOx conversion at temperatures higher than 500° C. Thus, those Cu-containing zeolites which achieve best results at low temperatures are typically poor in NOx conversion at high temperatures, in particular compared to Fe-Beta zeolites. An approach to solve said deficiency by doping a zeolitic material having framework structure type CHA, in particular chabazites, with Fe, usually leads to a catalyst bearing a strong loss in low temperature conversion although the high temperature conversion can often be improved.
In upcoming legislations, in particular Euro 7 and 8 LDD-legislations, N2O emission limits will be implemented or the strong greenhouse gas N2O will be counted as CO2 equivalent. Accordingly, the need exists to provide a catalyst, in particular a SCR catalyst, showing strongly reduced N2O make while exhibiting an improved high temperature conversion.
WO 2017/134581 A1 relates to a copper and iron exchanged chabazite catalyst. It is disclosed that such a catalyst can be prepared by contacting a chabazite with a copper metal precursor and an iron metal precursor. WO 2020/063360 A1 discloses a method for preparing a molecular sieve SCR catalyst, wherein the molecular sieve can comprise Fe and Cu. CN 104607239 A relates a method for preparing a copper and iron composite SCR catalyst. US 2015/0290632 A1 relates to an iron and copper-containing chabazite zeolite catalyst for use in NOx reduction. WO 2012/075400 A1 discloses a catalyst composition comprising a zeolite material having a CHA framework structure and an extra-framework promoter metal disposed thereon which is selected from copper, iron, and mixtures thereof. WO 2015/084817 A1 relates to a composition comprising a synthetic zeolite having a CHA framework structure which may comprise iron and copper. WO 2020/089275 A1 relates to a selective catalytic reduction catalyst on a filter substrate. US 2019/368399 A1 relates to a particle filter with SCR-active coating. WO 2014/062944 A1 relates to a mixed metal 8-ring small pore molecular sieve catalyst compositions, catalytic articles, systems and methods.
In view of the above, there is a need of a catalyst that exhibits a low temperature NOx conversion as good as a known catalyst optimized for low temperature NOx conversion but which at the same time exhibits a reduced N2O make, in particular at comparatively high temperatures and/or an improved high temperature NOx conversion.
It was therefore an object of the present invention to provide an improved catalyst for the treatment of an exhaust gas of a diesel engine, in particular with respect to its NOx conversion and/or N2O make, more particularly with respect to its NOx conversion at high temperatures and/or N2O make at high temperatures, wherein within the meaning of the present invention high temperatures particularly include temperatures higher than 350° C.
Thus, it was surprisingly found that a catalyst for the treatment of a diesel exhaust gas can solve one or more of the above mentioned problems, in particular with respect to an improved performance with respect to the conversion of NOx and/or the N2O make. Surprisingly, it was found that an improved catalyst can be provided according to the present invention in particular characterized as comprising a specific zeolitic material comprising Fe and Cu. Surprisingly, the catalyst of the present invention permits for an improved catalytic activity. Also, the catalyst of the present invention shows an excellent behavior as concerns N2O make, in particular at comparatively high temperatures, more particularly at temperatures higher than 350° C.
It has been found that by doping a zeolitic material having framework structure type CHA with small amounts of Fe, in particular in the range of from 0.1 to 0.3 weight-%, in addition to a Cu-doping, the low temperature NOx conversion of the zeolitic material is not impacted strongly but the high temperature NOx conversion is strongly improved and/or the N2O make is significantly reduced.
Therefore, the present invention relates to a process for preparing a catalyst for the treatment of an exhaust gas of a diesel engine, the process comprising
It is preferred that the zeolitic material according to (i) of the process has a framework structure type selected from the group consisting of CHA, AEI, RTH, a mixture of two or more thereof and a mixed type of two or more thereof, more preferably selected from the group consisting of CHA and AEI, a mixture thereof and a mixed type thereof, wherein the zeolitic material according to (i) more preferably has a CHA framework structure type.
It is preferred that in the aqueous mixture according to (i) of the process, the weight ratio of Fe comprised in the zeolitic material according to (i), calculated as Fe2O3, relative to Cu comprised in the copper source, calculated as CuO, Fe2O3:CuO, is in the range of from 0.010:1 to 0.095:1, more preferably in the range of from 0.018:1 to 0.085:1, more preferably in the range of from 0.030:1 to 0.075:1, more preferably in the range of from 0.040:1 to 0.067:1.
It is preferred that from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-% of the framework structure of the zeolitic material according to (i) of the process consist of Si, Al, and O, wherein preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.5 to 100 weight-% of the zeolitic material according to (i) consist of Si, Al, O, Fe, and optionally H.
It is preferred that in the framework structure of the zeolitic material according to (i) of the process, the molar ratio of Si to Al, calculated as molar ratio of SiO2:Al2O3, is in the range of from 1 to 50, more preferably in the range of from 8 to 35, more preferably in the range of from 13 to 23, more preferably in the range of from 16 to 20, more preferably in the range of from 17 to 19.
It is preferred that the Cu content, calculated as CuO, of the zeolitic material according to (i) of the process is in the range of from 0 to 0.001 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material according to (i), wherein said zeolitic material more preferably is essentially free of Cu, wherein said zeolitic material more preferably does not comprise Cu.
It is preferred that the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising
It is preferred that the process further comprises preparing the zeolitic material comprising Fe according to (i), said preparation method comprising
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-% of the framework structure of the zeolitic material according to (a) consist of Si, Al, and O, wherein more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.5 to 100 weight-% of the zeolitic material according to (a) consist of Si, Al, O, and H.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that in the framework structure of the zeolitic material according to (a), the molar ratio of Si to Al, calculated as molar ratio of SiO2:Al2O3, is more preferably in the range of from 1 to 50, more preferably in the range of from 8 to 35, more preferably in the range of from 13 to 23, more preferably in the range of from 16 to 20, more preferably in the range of from 17 to 19.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the zeolitic material according to (a) is in its H-form or its NH4+-form.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the zeolitic material according to (a) is a calcined zeolitic material, more preferably a zeolitic material calcined in a gas atmosphere having a temperature in the range of from 400 to 700° C., the gas atmosphere more preferably being one or more of oxygen, nitrogen, and air.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the zeolitic material according to (a) comprises from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, more preferably from 0 to 0.001 weight-%, of one or more of Cu, Li, Na, and K, wherein the zeolitic material according to (a) more preferably is essentially free of, more preferably does not comprise, one or more of Cu, Li, Na, and K.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the zeolitic material according to (a) is in the form of particles characterized by a volume-based particle size distribution exhibiting a Dv90 value in the range of from 1 to 15 micrometer, more preferably in the range of from 3 to 9 micrometer, more preferably in the range of from 4 to 6 micrometer, the Dv90 value more preferably being determined as described in Reference Example 2.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the zeolitic material according to (a) is in the form of particles characterized by a volume-based particle size distribution exhibiting a Dv50 value in the range of from 0.5 to 10 micrometer, more preferably in the range of from 1 to 5 micrometer, more preferably in the range of from 2 to 3 micrometer, the Dv50 value more preferably being determined as described in Reference Example 2.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that in the zeolitic material according to (a) the average crystal size is in the range of from 0.1 to 5 micrometer, more preferably in the range of from 0.2 to 2 micrometer, more preferably in the range of from 0.3 to 1 micrometer.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the volume ratio V(s):V(z) of the volume V(s) of the solution provided in (b) relative to the pore volume V(z) of the zeolitic material provided in (a) is in the range of from 0.5:1 to 1:1, more preferably in the range of from 0.7:1 to 1:1, more preferably in the range of from 0.8:1 to 1:1, wherein the pore volume V(z) is more preferably determined as described in Reference Example 1.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the iron salt according to (b) is an Fe(II) salt, an Fe(III) salt, or a mixture thereof, more preferably an Fe(III) salt, more preferably selected from the group consisting of Fe(III) nitrate, Fe(III) chloride, Fe(IIII) acetate, Fe(II) sulfate, and a mixture of two or more thereof, wherein more preferably, the iron salt comprises, more preferably consists of, Fe(III) nitrate.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-% of the solution according to (b) consist of water and the iron salt.
In the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the process further comprises
In the case where the method comprising (a), (b), and (c) or where the process comprising (a), (b), and (c) further comprises (d), it is preferred that during drying according to (d), the temperature of the gas atmosphere was increased from a temperature in the range of from 50 to 70° C. to a temperature in the range of from 80 to 110° C., wherein the temperature of the gas atmosphere was more preferably increased from the temperature in the range of from 80 to 110° C. to a temperature in the range of from 120 to 140° C.
Further in the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that the process further comprises
Further in the case where the zeolitic material according to (i) of the process is obtainable or obtained by a method comprising (a), (b), and (c), or where the process further comprises preparing the zeolitic material comprising Fe according to (a), (b), and (c), it is preferred that after impregnation according to (c), more preferably after drying according to (d) as defined in embodiment 20 or 21, and prior to (i), the zeolitic material is not subjected to calcination in a gas atmosphere comprising, more preferably being, air, preferably not subjected to calcination in a gas atmosphere comprising, more preferably being, one or more of nitrogen, oxygen, and air, more preferably not subjected to calcination in a gas atmosphere, said gas atmosphere more preferably having a temperature in the range of from 580 to 600° C., more preferably in the range of from 570 to 610° C., more preferably in the range of from 550 to 650° C.
It is preferred that the source of copper according to (i) of the process is a Cu(I) salt, a Cu(II) salt, or a mixture thereof, wherein the source of copper according to (i) is more preferably selected from the group consisting of copper acetate, copper nitrate, copper sulfate, copper formate, copper oxide, and a mixture of two or more thereof, more preferably selected from the group consisting of copper acetate, copper oxide, and a mixture thereof, wherein more preferably, the source of copper comprises, more preferably consists of, copper oxide, preferably CuO.
It is preferred that the aqueous mixture according to (i) of the process comprises the source of copper at an amount, calculated as CuO, in the range of from 0.025 to 7.5 weight-%, more preferably in the range of from 2 to 6.0 weight-%, more preferably in the range of from 3.5 to 5.5 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i).
It is preferred that the first non-zeolitic oxidic material according to (i) of the process is selected from the group consisting of alumina, silica, titania, zirconia, a mixed oxide comprising one or more of Al, Si, Ti, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, zirconia, a mixed oxide comprising one or more of Al, Si, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, zirconia, a mixed oxide comprising one or more of Al and Zr, and a mixture of two or more thereof, wherein the first non-zeolitic oxidic material according to (i) of the process more preferably comprises, more preferably consists of, zirconia-alumina.
In the case where the first non-zeolitic oxidic material according to (i) of the process is selected from the group consisting of alumina, silica, titania, zirconia, a mixed oxide comprising one or more of Al, Si, Ti, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, zirconia, a mixed oxide comprising one or more of Al, Si, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, zirconia, a mixed oxide comprising one or more of Al and Zr, and a mixture of two or more thereof, wherein the first non-zeolitic oxidic material according to (i) of the process more preferably comprises, more preferably consists of, zirconia-alumina, it is preferred that from 30 to 100 weight-%, more preferably from 60 to 85 weight-%, more preferably from 75 to 82 weight-% of the first non-zeolitic oxidic material according to (i) consist of aluminum, calculated as Al2O3, and preferably from 5 to 35 weight-%, more preferably from 15 to 25 weight-%, more preferably from 18 to 22 weight-% of the first non-zeolitic oxidic material according to (i) consist of zirconium, calculated as ZrO2.
It is preferred that the aqueous mixture according to (i) of the process comprises the first non-zeolitic oxidic material at an amount in the range of from greater than 0 to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i).
It is preferred that the aqueous mixture according to (i) of the process further comprises a source of a second non-zeolitic oxidic material which is different from the first non-zeolitic oxidic material, wherein the second non-zeolitic oxidic material is more preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria, lanthana, praseodymium oxide, manganese oxide, a mixed oxide comprising one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, a mixed oxide comprising one or more of Al, Si, Ti, Zr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of silica, titania, zirconia, a mixed oxide comprising one or more of Si, Ti, and Zr, and a mixture of two or more thereof, wherein the second non-zeolitic oxidic material more preferably comprises, more preferably consists of, zirconia, wherein the aqueous mixture according to (i) more preferably comprises the second non-zeolitic oxidic material at an amount in the range of from greater than 0 to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i).
In the case where the aqueous mixture according to (i) of the process further comprises a source of a second non-zeolitic oxidic material which is different from the first non-zeolitic oxidic material, wherein the second non-zeolitic oxidic material is more preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria, lanthana, praseodymium oxide, manganese oxide, a mixed oxide comprising one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, a mixed oxide comprising one or more of Al, Si, Ti, Zr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of silica, titania, zirconia, a mixed oxide comprising one or more of Si, Ti, and Zr, and a mixture of two or more thereof, wherein the second non-zeolitic oxidic material more preferably comprises, more preferably consists of, zirconia, wherein the aqueous mixture according to (i) more preferably comprises the second non-zeolitic oxidic material at an amount in the range of from greater than 0 to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i), it is preferred that the source of a second non-zeolitic oxidic material is one or more of an aluminum salt, a silicon salt, a zirconium salt, a titanium salt, a cerium salt, a praseodymium salt, a manganese salt, and a lanthanum salt, more preferably one or more of a zirconium salt, and an aluminum salt, more preferably a zirconium salt, more preferably one or more of zirconium acetate, zirconium hydroxide, zirconium chloride, zirconium nitrate, and zirconium sulfate, more preferably zirconium acetate.
Further in the case where the aqueous mixture according to (i) of the process further comprises a source of a second non-zeolitic oxidic material which is different from the first non-zeolitic oxidic material, wherein the the second non-zeolitic oxidic material is more preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria, lanthana, praseodymium oxide, manganese oxide, a mixed oxide comprising one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, a mixed oxide comprising one or more of Al, Si, Ti, Zr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of silica, titania, zirconia, a mixed oxide comprising one or more of Si, Ti, and Zr, and a mixture of two or more thereof, wherein the second non-zeolitic oxidic material more preferably comprises, more preferably consists of, zirconia, wherein the aqueous mixture according to (i) more preferably comprises the second non-zeolitic oxidic material at an amount in the range of from greater than 0 to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i), it is preferred that the second non-zeolitic oxidic material consists of zirconia, and wherein the aqueous mixture according to (i) comprises the source of a second non-zeolitic oxidic material, calculated as ZrO2, at an amount in the range of from 0.5 to 10 weight-%, more preferably in the range of from 2.5 to 5.5 weight-%, more preferably in the range of from 4.8 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i).
It is preferred that (i) of the process comprises
In the case where the process further comprises (i.1), preferably (i.2), optionally (i.3), (i.4), (i.5), preferably (i.6), (i.7), and (i.8), it is preferred the third aqueous mixture obtained in (i.5) has a pH in the range of from 2.0 to 5.0, more preferably in the range of from 2.4 to 4.5, more preferably in the range of from 3.4 to 4.2.
It is preferred that the aqueous mixture obtained in (i) of the process, more preferably in (i.8) according to embodiment 33, has a pH in the range of from 2.0 to 6.0, more preferably in the range of from 3.5 to 5.0, more preferably in the range of from 3.9 to 4.7.
It is preferred that the aqueous mixture obtained in (i) of the process is disposed on the surface of the internal walls of the substrate according to (ii) over 60 to 100%, more preferably over 80 to 100%, more preferably over 95 to 100% of the substrate axial length.
It is preferred that the aqueous mixture obtained in (i) of the process is disposed on the surface of the internal walls of the substrate according to (ii) from the inlet end or from the outlet end of the substrate.
It is preferred that the substrate according to (ii) of the process is a flow-through substrate or a wall flow filter substrate, more preferably a flow-through substrate, wherein the flow-through substrate is more preferably one or more of a cordierite flow-through substrate and a metallic flow-through substrate, more preferably a cordierite flow-through substrate, the substrate preferably having a cylindrical shape, the diameter of the substrate more preferably being in the range of from 25 to 380 millimeters, more preferably in the range of from 45 to 280 millimeters, more preferably in the range of from 55 to 200 millimeters, the substrate more preferably having an axial length in the range of from 40 to 254 millimeters, more preferably in the range of from 50 to 154 millimeters, more preferably in the range of from 75 to 127 millimeters.
It is preferred that the number of passages per square inch (number of passages per 6.4516 cm2) of the substrate according to (ii) of the process is in the range of from 100 to 1200 cpsi, more preferably in the range of from 200 to 900 cpsi, more preferably in the range of from 400 to 600 cpsi.
It is preferred that the gas atmosphere in (iii) of the process has a temperature in the range of from 60 to 150° C., more preferably in the range of from 70 to 140° C., wherein the heat treatment is more preferably conducted for a period in the range of from 0.1 to 2 h, more preferably in the range of from 0.4 to 0.6 h, wherein the gas atmosphere more preferably comprises, more preferably consists of, one or more of oxygen, nitrogen, and air, more preferably air.
It is preferred that the gas atmosphere in (iii) of the process has a temperature in the range of from 500 to 700° C., preferably in the range of from 570 to 610° C., wherein the heat treatment is more preferably conducted for a period in the range of from 0.5 to 5 h, more preferably in the range of from 1.5 to 2.5 h, wherein the gas atmosphere more preferably comprises, more preferably consists of, one or more of oxygen, nitrogen, and air, more preferably air.
It is preferred that the heat treatment in (iii) of the process comprises
Further, the present invention relates to a catalyst for the treatment of an exhaust gas of a diesel combustion engine, obtainable or obtained by a process according to any one of the embodiments disclosed herein.
Yet further, the present invention relates to a catalyst for the treatment of an exhaust gas of a diesel combustion engine, preferably the catalyst obtainable or obtained by a process according to any one of the embodiments disclosed herein, said catalyst comprising
It is preferred that the zeolitic material comprised in the coating according to (B) of the catalyst has a framework structure type selected from the group consisting of CHA, AEI, RTH, a mixture of two or more thereof and a mixed type of two or more thereof, more preferably selected from the group consisting of CHA and AEI, a mixture thereof and a mixed type thereof, wherein the zeolitic material comprised in the coating according to (B) more preferably has a CHA framework structure type,
It is preferred that the coating according to (B) of the catalyst exhibits a weight ratio of Fe, calculated as Fe2O3, relative to Cu, calculated as CuO, Fe2O3:CuO, in the range of from 0.010:1 to 0.095:1, more preferably in the range of from 0.018:1 to 0.085:1, more preferably in the range of from 0.030:1 to 0.075:1, more preferably in the range of from 0.040:1 to 0.067:1.
It is preferred that the coating according to (B) of the catalyst exhibits a weight ratio of Fe, calculated as Fe2O3, relative to Cu, calculated as CuO, Fe2O3:CuO, in the range of from 0.040:1 to 0.098:1, more preferably in the range of from 0.060:1 to 0.097:1, more preferably in the range of from 0.070:1 to 0.096:1.
It is preferred that the copper comprised in the coating according to (B) of the catalyst is comprised in one or more of the zeolitic material comprised in the coating according to (B) and the first non-zeolitic oxidic material comprised in the coating according to (B).
It is preferred that from 75 to 100 weight-%, more preferably from 78 to 100 weight-%, more preferably from 80 to 100 weight-%, of the copper comprised in the coating according to (B) of the catalyst is comprised in the zeolitic material comprised in the coating according to (B).
It is preferred that the substrate according to (A) of the catalyst is a flow-through substrate or a wall flow filter substrate, more preferably a flow-through substrate, wherein the flow-through substrate is more preferably one or more of a cordierite flow-through substrate and a metallic flow-through substrate, more preferably a cordierite flow-through substrate.
It is preferred that the substrate according to (A) of the catalyst has a cylindrical shape, the diameter of the substrate more preferably being in the range of from 25 to 380 millimeters, more preferably in the range of from 45 to 280 millimeters, more preferably in the range of from 55 to 200 millimeters, the substrate more preferably having an axial length in the range of from 40 to 254 millimeters, more preferably in the range of from 50 to 154 millimeters, more preferably in the range of from 75 to 127 millimeters.
It is preferred that the number of passages per square inch (per 6.4516 cm2) of the substrate according to (A) of the catalyst is in the range of from 100 to 1200 cpsi, more preferably in the range of from 200 to 900 cpsi, more preferably in the range of from 400 to 600 cpsi.
It is preferred that from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, of the framework structure of the zeolitic material comprised in the coating according to (B) of the catalyst consist of Si, Al, and O.
It is preferred that the zeolitic material comprised in the coating according to (B) of the catalyst exhibits a molar ratio of silicon oxide to aluminum oxide, calculated as SiO2 to Al2O3, SiO2:Al2O3, in the range of from 1 to 50, more preferably in the range of from 8 to 35, more preferably in the range of from 13 to 23, more preferably in the range of from 16 to 20, more preferably in the range of from 17 to 19.
It is preferred that in the zeolitic material comprised in the coating according to (B) of the catalyst the average crystal size is in the range of from 0.1 to 5.0 micrometers, more preferably in the range of from 0.2 to 2.0 micrometers, more preferably in the range of from 0.3 to 1.0 micrometers.
It is preferred that the zeolitic material comprised in the coating according to (B) of the catalyst comprises Fe in an amount, calculated as Fe2O3, in the range of from 0.05 to 2 weight-%, more preferably in the range of from 0.1 to 1 weight-%, more preferably in the range of from 0.2 to 0.8 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
It is preferred that the first non-zeolitic oxidic material comprised in the coating according to (B) of the catalyst is selected from the group consisting of alumina, silica, titania, zirconia, a mixed oxide comprising one or more of Al, Si, Ti, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, zirconia, a mixed oxide comprising one or more of Al, Si, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, zirconia, a mixed oxide comprising one or more of Al and Zr, and a mixture of two or more thereof, wherein the first non-zeolitic oxidic material comprised in the coating according to (B) more preferably comprises, more preferably consists of, zirconia-alumina.
It is preferred that the first non-zeolitic oxidic material comprised in the coating according to (B) of the catalyst comprises, preferably consists of, zirconia-alumina, wherein from 30 to 100 weight-%, more preferably from 60 to 85 weight-%, more preferably from 75 to 82 weight-%, of the zirconia-alumina consist of alumina.
It is preferred that the first non-zeolitic oxidic material comprised in the coating according to (B) of the catalyst comprises, more preferably consists of, zirconia-alumina, wherein from 5 to 35 weight-%, preferably from 15 to 25 weight-%, more preferably from 18 to 22 weight-%, of the zirconia-alumina consist of zirconia.
It is preferred that the catalyst comprises the first non-zeolitic oxidic material comprised in the coating according to (B) at an amount in the range of from greater than 0 to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
It is preferred that the coating according to (B) of the catalyst further comprises a second non-zeolitic oxidic material, being different to the first non-zeolitic oxidic material, wherein the second non-zeolitic oxidic material is more preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria, lanthana, praseodymium oxide, manganese oxide, a mixed oxide comprising one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, a mixed oxide comprising one or more of Al, Si, Ti, Zr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of silica, titania, zirconia, a mixed oxide comprising one or more of Si, Ti, and Zr, and a mixture of two or more thereof, wherein the second non-zeolitic oxidic material more preferably comprises, more preferably consists of, zirconia, wherein the catalyst more preferably comprises the second non-zeolitic material at an amount in the range of from greater than 0 to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
In the case where the coating according to (B) of the catalyst further comprises a second non-zeolitic oxidic material, being different to the first non-zeolitic oxidic material, it is preferred that the copper comprised in the coating according to (B) is comprised in one or more of the zeolitic material comprised in the coating according to (B), the first non-zeolitic oxidic material comprised in the coating according to (B) and the second non-zeolitc oxidic material comprised in the coating according to (B).
It is preferred that the coating according to (B) of the catalyst comprises one or more of the zeolitic material, the first non-zeolitic oxidic material, and optionally the second non-zeolitic oxidic material as defined in embodiment 60, as particles, wherein said particles are more preferably characterized by a volume-based particle size distribution exhibiting a Dv90 value in the range of from 2 to 20 micrometers, more preferably in the range of from 5 to 15 micrometers, more preferably in the range of from 8 to 12 micrometers, the Dv90 value more preferably being determined as described in Reference Example 2.
It is preferred that the coating according to (B) of the catalyst comprises Cu, calculated as CuO, in an amount in the range of from 3.0 to 7.5 weight-%, more preferably in the range of from 4.5 to 5.8 weight-%, more preferably in the range of from 4.7 to 5.6 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
It is preferred that the coating according to (B) of the catalyst is disposed on the surface of the internal walls of the substrate according to (A) over 60 to 100%, more preferably over 80 to 100%, more preferably over 95 to 100% of the substrate axial length.
It is preferred that the zeolitic material comprised in the coating according to (B) of the catalyst is disposed on the surface of the internal walls of the substrate according to (A) at a loading in the range of from 1.00 to 4.50 g/in3, more preferably in the range of from 1.50 to 3.25 g/in3, more preferably in the range of from 1.65 to 3.10 g/in3.
It is preferred that the first non-zeolitic oxidic material comprised in the coating according to (B) of the catalyst is more preferably disposed on the surface of the internal walls of the substrate according to (A) at a loading in the range of from 0.05 to 0.25 g/in3, more preferably in the range of from 0.08 to 0.20 g/in3, more preferably in the range of from 0.11 to 0.16 g/in3.
Further in the case where the coating according to (B) of the catalyst further comprises a second non-zeolitic oxidic material, being different to the first non-zeolitic oxidic material, it is preferred that the second non-zeolitic oxidic material comprised in the coating according to (B) is disposed on the surface of the internal walls of the substrate according to (A) at a loading in the range of from 0.05 to 0.25 g/in3, more preferably in the range of from 0.08 to 0.20 g/in3, more preferably in the range of from 0.11 to 0.16 g/in3.
It is preferred that the catalyst has a Fe loading, calculated as Fe2O3, in the range of from 0.001 to 0.030 g/in3, more preferably in the range of from 0.003 to 0.015 g/in3, more preferably in the range of from 0.004 to 0.010 g/in3, wherein the Fe is more preferably comprised in the zeolitic material comprised in the coating according to (B).
It is preferred that the catalyst has a Cu loading, calculated as CuO, in the range of from 0.08 to 0.18 g/in3, more preferably in the range of from 0.10 to 0.16 g/in3 more preferably in the range of from 0.11 to 0.15 g/in3, wherein the Cu is more preferably at least partially comprised in the zeolitic material comprised in the coating according to (B).
It is preferred that the catalyst has a loading of the first non-zeolitic oxidic material comprised in the coating according to (B) in the range of from 1 to 10 weight-%, more preferably in the range of from 3 to 7 weight-%, more preferably in the range of from 4 to 6 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
It is preferred that from 95 to 100 weight-%, more preferably from 97 to 100 weight-%, more preferably from 99 to 100 weight-%, of the coating according to (B) of the catalyst consist of the zeolitic material comprised in the coating according to (B), Fe, Cu, O, and the first non-zeolitic oxidic material comprised in the coating according to (B).
It is preferred that the catalyst has a loading of the coating according to (B) in the range of from 1.0 to 5.0 g/in3, more preferably in the range of from 1.75 to 3.75 g/in3, more preferably in the range of from 1.9 to 3.5 g/in3.
It is preferred that from 95 to 100 weight-%, more preferably from 97 to 100 weight-%, more preferably from 99 to 100 weight-%, of the catalyst consist of the substrate according to (A) and the coating according to (B).
Yet further, the present invention relates to a system for the treatment of an exhaust gas of a diesel combustion engine, the system comprising a diesel oxidation catalyst, a catalyzed soot filter, and a catalyst according to any one of embodiments (42) to (73), wherein in said system, the diesel oxidation catalyst is located upstream of the catalyzed soot filter, and wherein the catalyzed soot filter is located upstream of said catalyst according to any one of embodiments (42) to (73).
It is preferred that the system further comprises a reductant injector, more preferably one or more of a hydrocarbon injector, a hydrocarbon in-cylinder post injector, and a urea injector, wherein the reductant injector is more preferably arranged upstream of the catalyzed soot filter, wherein the reductant injector is more preferably arranged downstream of the diesel oxidation catalyst.
Yet further, the present invention relates to a use of a catalyst of any one of the embodiments disclosed herein or a system of any one of the embodiments disclosed herein, for the treatment of an exhaust gas of a diesel combustion engine.
Yet further, the present invention relates to a method for treating an exhaust gas of a diesel combustion engine, said method comprising bringing said exhaust gas in contact with a catalyst according to any one of the embodiments disclosed herein.
Yet further, the present invention relates to a method for treating an exhaust gas of a diesel combustion engine, said method comprising passing said exhaust gas through a system according to any one of the embodiments disclosed herein.
The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as “A further preferred embodiment (4) concretizing any one of embodiments (1) to (3)”, every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to “A further preferred embodiment (4) concretizing any one of embodiments (1), (2) and (3)”. Further, it is explicitly noted that the following set of embodiments is not the set of claims determining the extent of protection, but represents a suitably structured part of the description directed to general and preferred aspects of the present invention.
According to an embodiment (1), the present invention relates to a process for preparing a catalyst for the treatment of an exhaust gas of a diesel engine, comprising
A preferred embodiment (2) concretizing embodiment (1) relates to said, wherein the zeolitic material according to (i) has a framework structure type selected from the group consisting of CHA, AEI, RTH, a mixture of two or more thereof and a mixed type of two or more thereof, more preferably selected from the group consisting of CHA and AEI, a mixture thereof and a mixed type thereof, wherein the zeolitic material according to (i) more preferably has a CHA framework structure type.
A further preferred embodiment (3) concretizing embodiment (1) or (2) relates to said process, wherein in the aqueous mixture according to (i), the weight ratio of Fe comprised in the zeolitic material according to (i), calculated as Fe2O3, relative to Cu comprised in the copper source, calculated as CuO, Fe2O3:CuO, is in the range of from 0.010:1 to 0.095:1, more preferably in the range of from 0.018:1 to 0.085:1, more preferably in the range of from 0.030:1 to 0.075:1, more preferably in the range of from 0.040:1 to 0.067:1.
A further preferred embodiment (4) concretizing any one of embodiments (1) to (3) relates to said process, wherein from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-% of the framework structure of the zeolitic material according to (i) consist of Si, Al, and O, wherein preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.5 to 100 weight-% of the zeolitic material according to (i) consist of Si, Al, O, Fe, and optionally H.
A further preferred embodiment (5) concretizing any one of embodiments (1) to (4) relates to said process, wherein in the framework structure of the zeolitic material according to (i), the molar ratio of Si to Al, calculated as molar ratio of SiO2:Al2O3, is in the range of from 1 to 50, more preferably in the range of from 8 to 35, more preferably in the range of from 13 to 23, more preferably in the range of from 16 to 20, more preferably in the range of from 17 to19.
A further preferred embodiment (6) concretizing any one of embodiments (1) to (5) relates to said process, wherein the Cu content, calculated as CuO, of the zeolitic material according to (i) is in the range of from 0 to 0.001 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material according to (i), wherein said zeolitic material more preferably is essentially free of Cu, wherein said zeolitic material more preferably does not comprise Cu.
A further preferred embodiment (7) concretizing any one of embodiments (1) to (6) relates to said process, wherein the zeolitic material according to (i) is obtainable or obtained by a method comprising
A further preferred embodiment (8) concretizing any one of embodiments (1) to (6) relates to said process, wherein the process further comprises preparing the zeolitic material comprising Fe according to (i), said method comprising
A further preferred embodiment (9) concretizing embodiment (7) or (8) relates to said process, wherein from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-% of the framework structure of the zeolitic material according to (a) consist of Si, Al, and O, wherein more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.5 to 100 weight-% of the zeolitic material according to (a) consist of Si, Al, O, and H.
A further preferred embodiment (10) concretizing any one of embodiments (7) to (9) relates to said process, wherein in the framework structure of the zeolitic material according to (a), the molar ratio of Si to Al, calculated as molar ratio of SiO2:Al2O3, is more preferably in the range of from 1 to 50, more preferably in the range of from 8 to 35, more preferably in the range of from 13 to 23, more preferably in the range of from 16 to 20, more preferably in the range of from 17 to 19.
A further preferred embodiment (11) concretizing any one of embodiments (7) to (10) relates to said process, wherein the zeolitic material according to (a) is in its H-form or its NH4+-form.
A further preferred embodiment (12) concretizing any one of embodiments (7) to (11) relates to said process, wherein the zeolitic material according to (a) is a calcined zeolitic material, more preferably a zeolitic material calcined in a gas atmosphere having a temperature in the range of from 400 to 700° C., the gas atmosphere more preferably being one or more of oxygen, nitrogen, and air.
A further preferred embodiment (13) concretizing any one of embodiments (7) to (12) relates to said process, wherein the zeolitic material according to (a) comprises from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, more preferably from 0 to 0.001 weight-%, of one or more of Cu, Li, Na, and K, wherein the zeolitic material according to (a) more preferably is essentially free of, more preferably does not comprise, one or more of Cu, Li, Na, and K.
A further preferred embodiment (14) concretizing any one of embodiments (7) to (13) relates to said process, wherein the zeolitic material according to (a) is in the form of particles characterized by a volume-based particle size distribution exhibiting a Dv90 value in the range of from 1 to 15 micrometer, more preferably in the range of from 3 to 9 micrometer, more preferably in the range of from 4 to 6 micrometer, the Dv90 value more preferably being determined as described in Reference Example 2.
A further preferred embodiment (15) concretizing any one of embodiments (7) to (14) relates to said process, wherein the zeolitic material according to (a) is in the form of particles characterized by a volume-based particle size distribution exhibiting a Dv50 value in the range of from 0.5 to 10 micrometer, more preferably in the range of from 1 to 5 micrometer, more preferably in the range of from 2 to 3 micrometer, the Dv50 value more preferably being determined as described in Reference Example 2.
A further preferred embodiment (16) concretizing any one of embodiments (7) to (15) relates to said process, wherein in the zeolitic material according to (a) the average crystal size is in the range of from 0.1 to 5 micrometer, more preferably in the range of from 0.2 to 2 micrometer, more preferably in the range of from 0.3 to 1 micrometer.
A further preferred embodiment (17) concretizing any one of embodiments (7) to (16) relates to said process, wherein the volume ratio V(s):V(z) of the volume V(s) of the solution provided in (b) relative to the pore volume V(z) of the zeolitic material provided in (a) is in the range of from 0.5:1 to 1:1, more preferably in the range of from 0.7:1 to 1:1, more preferably in the range of from 0.8:1 to 1:1, wherein the pore volume V(z) is more preferably determined as described in Reference Example 1.
A further preferred embodiment (18) concretizing any one of embodiments (7) to (17) relates to said process, wherein the iron salt according to (b) is an Fe(II) salt, an Fe(III) salt, or a mixture thereof, more preferably an Fe(III) salt, more preferably selected from the group consisting of Fe(III) nitrate, Fe(III) chloride, Fe(IIII) acetate, Fe(II) sulfate, and a mixture of two or more thereof, wherein more preferably, the iron salt comprises, more preferably consists of, Fe(III) nitrate.
A further preferred embodiment (19) concretizing any one of embodiments (7) to (18) relates to said process, wherein from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-% of the solution according to (b) consist of water and the iron salt.
A further preferred embodiment (20) concretizing any one of embodiments (7) to (19) relates to said process, wherein the process further comprises
A further preferred embodiment (21) concretizing embodiment (20) relates to said process, wherein during drying according to (d), the temperature of the gas atmosphere was increased from a temperature in the range of from 50 to 70° C. to a temperature in the range of from 80 to 110° C., wherein the temperature of the gas atmosphere was more preferably increased from the temperature in the range of from 80 to 110° C. to a temperature in the range of from 120 to 140° C.
A further preferred embodiment (22) concretizing any one of embodiments (7) to (21), more preferably (20) or (21), relates to said process, wherein the process further comprises
A further preferred embodiment (23) concretizing any one of embodiments (7) to (21) relates to said process, wherein after impregnation according to (c), more preferably after drying according to (d) as defined in embodiment 20 or 21, and prior to (i), the zeolitic material is not subjected to calcination in a gas atmosphere comprising, more preferably being, air, preferably not subjected to calcination in a gas atmosphere comprising, more preferably being, one or more of nitrogen, oxygen, and air, more preferably not subjected to calcination in a gas atmosphere, said gas atmosphere more preferably having a temperature in the range of from 580 to 600° C., more preferably in the range of from 570 to 610° C., more preferably in the range of from 550 to 650° C.
A further preferred embodiment (24) concretizing any one of embodiments (1) to (23) relates to said process, wherein the source of copper according to (i) is a Cu(I) salt, a Cu(II) salt, or a mixture thereof, wherein the source of copper according to (i) is more preferably selected from the group consisting of copper acetate, copper nitrate, copper sulfate, copper formate, copper oxide, and a mixture of two or more thereof, more preferably selected from the group consisting of copper acetate, copper oxide, and a mixture thereof, wherein more preferably, the source of copper comprises, more preferably consists of, copper oxide, preferably CuO.
A further preferred embodiment (25) concretizing any one of embodiments (1) to (24) relates to said process, wherein the aqueous mixture according to (i) comprises the source of copper at an amount, calculated as CuO, in the range of from 0.025 to 7.5 weight-%, more preferably in the range of from 2 to 6.0 weight-%, more preferably in the range of from 3.5 to 5.5 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i).
A further preferred embodiment (26) concretizing any one of embodiments (1) to (25) relates to said process, wherein the first non-zeolitic oxidic material according to (i) of the process is selected from the group consisting of alumina, silica, titania, zirconia, a mixed oxide comprising one or more of Al, Si, Ti, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, zirconia, a mixed oxide comprising one or more of Al, Si, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, zirconia, a mixed oxide comprising one or more of Al and Zr, and a mixture of two or more thereof, wherein the first non-zeolitic oxidic material according to (i) of the process more preferably comprises, more preferably consists of, zirconia-alumina.
A further preferred embodiment (27) concretizing embodiment (26) relates to said process, wherein from 30 to 100 weight-%, preferably from 60 to 85 weight-%, more preferably from 75 to 82 weight-% of the first non-zeolitic oxidic material according to (i) consist of aluminum, calculated as Al2O3, and preferably from 5 to 35 weight-%, more preferably from 15 to 25 weight-%, more preferably from 18 to 22 weight-% of the first non-zeolitic oxidic material according to (i) consist of zirconium, calculated as ZrO2.
A further preferred embodiment (28) concretizing any one of embodiments (1) to (27) relates to said process, wherein the aqueous mixture according to (i) comprises the first non-zeolitic oxidic material at an amount in the range of from greater than 0 to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i).
A further preferred embodiment (29) concretizing any one of embodiments (1) to (28) relates to said process, wherein the aqueous mixture according to (i) further comprises a source of a second non-zeolitic oxidic material which is different from the first non-zeolitic oxidic material, wherein the the second non-zeolitic oxidic material is more preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria, lanthana, praseodymium oxide, manganese oxide, a mixed oxide comprising one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, a mixed oxide comprising one or more of Al, Si, Ti, Zr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of silica, titania, zirconia, a mixed oxide comprising one or more of Si, Ti, and Zr, and a mixture of two or more thereof, wherein the second non-zeolitic oxidic material more preferably comprises, more preferably consists of, zirconia, wherein the aqueous mixture according to (i) more preferably comprises the second non-zeolitic oxidic material at an amount in the range of from greater than to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i).
A further preferred embodiment (30) concretizing embodiment (29) relates to said process, wherein the source of a second non-zeolitic oxidic material is one or more of an aluminum salt, a silicon salt, a zirconium salt, a titanium salt, a cerium salt, a praseodymium salt, a manganese salt, and a lanthanum salt, more preferably one or more of a zirconium salt, and an aluminum salt, more preferably a zirconium salt, more preferably one or more of zirconium acetate, zirconium hydroxide, zirconium chloride, zirconium nitrate, and zirconium sulfate, more preferably zirconium acetate.
A further preferred embodiment (30) concretizing embodiment (29) or (30) relates to said process, wherein the second non-zeolitic oxidic material consists of zirconia, and wherein the aqueous mixture according to (i) comprises the source of a second non-zeolitic oxidic material, calculated as ZrO2, at an amount in the range of from 0.5 to 10 weight-%, more preferably in the range of from 2.5 to 5.5 weight-%, more preferably in the range of from 4.8 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the aqueous mixture according to (i).
A further preferred embodiment (32) concretizing any one of embodiments (1) to (31) relates to said process, wherein (i) comprises
A further preferred embodiment (33) concretizing embodiment (32) relates to said process, wherein the third aqueous mixture obtained in (i.5) has a pH in the range of from 2.0 to 5.0, more preferably in the range of from 2.4 to 4.5, more preferably in the range of from 3.4 to 4.2.
A further preferred embodiment (34) concretizing any one of embodiments (1) to (33) relates to said process, wherein the aqueous mixture obtained in (i), more preferably in (i.8) according to embodiment 33, has a pH in the range of from 2.0 to 6.0, more preferably in the range of from 3.5 to 5.0, more preferably in the range of from 3.9 to 4.7.
A further preferred embodiment (35) concretizing any one of embodiments (1) to (34) relates to said process, wherein the aqueous mixture obtained in (i) is disposed on the surface of the internal walls of the substrate according to (ii) over 60 to 100%, more preferably over 80 to 100%, more preferably over 95 to 100% of the substrate axial length.
A further preferred embodiment (36) concretizing any one of embodiments (1) to (35) relates to said process, wherein the aqueous mixture obtained in (i) is disposed on the surface of the internal walls of the substrate according to (ii) from the inlet end or from the outlet end of the substrate.
A further preferred embodiment (37) concretizing any one of embodiments (1) to (36) relates to said process, wherein the substrate according to (ii) is a flow-through substrate or a wall flow filter substrate, more preferably a flow-through substrate, wherein the flow-through substrate is more preferably one or more of a cordierite flow-through substrate and a metallic flow-through substrate, more preferably a cordierite flow-through substrate, the substrate preferably having a cylindrical shape, the diameter of the substrate more preferably being in the range of from 25 to 380 millimeters, more preferably in the range of from 45 to 280 millimeters, more preferably in the range of from 55 to 200 millimeters, the substrate more preferably having an axial length in the range of from 40 to 254 millimeters, more preferably in the range of from 50 to 154 millimeters, more preferably in the range of from 75 to 127 millimeters.
A further preferred embodiment (38) concretizing any one of embodiments (1) to (37) relates to said process, wherein the number of passages per square inch (number of passages per 6.4516 cm2) of the substrate according to (ii) is in the range of from 100 to 1200 cpsi, more preferably in the range of from 200 to 900 cpsi, more preferably in the range of from 400 to 600 cpsi.
A further preferred embodiment (39) concretizing any one of embodiments (1) to (38) relates to said process, wherein the gas atmosphere in (iii) has a temperature in the range of from 60 to 150° C., more preferably in the range of from 70 to 140° C., wherein the heat treatment is more preferably conducted for a period in the range of from 0.1 to 2 h, more preferably in the range of from 0.4 to 0.6 h, wherein the gas atmosphere more preferably comprises, more preferably consists of, one or more of oxygen, nitrogen, and air, more preferably air.
A further preferred embodiment (40) concretizing any one of embodiments (1) to (38) relates to said process, wherein the gas atmosphere in (iii) has a temperature in the range of from 500 to 700° C., preferably in the range of from 570 to 610° C., wherein the heat treatment is more preferably conducted for a period in the range of from 0.5 to 5 h, more preferably in the range of from 1.5 to 2.5 h, wherein the gas atmosphere more preferably comprises, more preferably consists of, one or more of oxygen, nitrogen, and air, more preferably air.
A further preferred embodiment (41) concretizing any one of embodiments (1) to (38) relates to said process, wherein the heat treatment in (iii) comprises
An embodiment (42) of the present invention relates to a catalyst for the treatment of an exhaust gas of a diesel combustion engine, obtainable or obtained by a process according to any one of embodiments (1) to (41).
An embodiment (43) of the present invention relates to a catalyst for the treatment of an exhaust gas of a diesel combustion engine, preferably the catalyst of embodiment (42), said catalyst comprising
A preferred embodiment (44) concretizing embodiment (43) relates to said catalyst, wherein the zeolitic material comprised in the coating according to (B) has a framework structure type selected from the group consisting of CHA, AEI, RTH, a mixture of two or more thereof and a mixed type of two or more thereof, more preferably selected from the group consisting of CHA and AEI, a mixture thereof and a mixed type thereof, wherein the zeolitic material comprised in the coating according to (B) more preferably has a CHA framework structure type,
A preferred embodiment (45) concretizing embodiment (43) or (44) relates to said catalyst, wherein the coating according to (B) exhibits a weight ratio of Fe, calculated as Fe2O3, relative to Cu, calculated as CuO, Fe2O3:CuO, in the range of from 0.010:1 to 0.095:1, more preferably in the range of from 0.018:1 to 0.085:1, more preferably in the range of from 0.030:1 to 0.075:1, more preferably in the range of from 0.040:1 to 0.067:1.
A preferred embodiment (46) concretizing embodiment (43) or (44) relates to said catalyst, wherein the coating according to (B) exhibits a weight ratio of Fe, calculated as Fe2O3, relative to Cu, calculated as CuO, Fe2O3:CuO, in the range of from 0.040:1 to 0.098:1, more preferably in the range of from 0.060:1 to 0.097:1, more preferably in the range of from 0.070:1 to 0.096:1.
A further preferred embodiment (47) concretizing any one of embodiments (43) to (46) relates to said catalyst, wherein the copper comprised in the coating according to (B) is comprised in one or more of the zeolitic material comprised in the coating according to (B) and the first non-zeolitic oxidic material comprised in the coating according to (B).
A further preferred embodiment (48) concretizing any one of embodiments (43) to (47) relates to said catalyst, wherein from 75 to 100 weight-%, more preferably from 78 to 100 weight-%, more preferably from 80 to 100 weight-%, of the copper comprised in the coating according to (B) is comprised in the zeolitic material comprised in the coating according to (B).
A further preferred embodiment (49) concretizing any one of embodiments (43) to (45) relates to said catalyst, wherein the substrate according to (A) is a flow-through substrate or a wall flow filter substrate, more preferably a flow-through substrate, wherein the flow-through substrate is more preferably one or more of a cordierite flow-through substrate and a metallic flow-through substrate, more preferably a cordierite flow-through substrate.
A further preferred embodiment (50) concretizing any one of embodiments (43) to (49) relates to said catalyst, wherein the substrate according to (A) has a cylindrical shape, the diameter of the substrate more preferably being in the range of from 25 to 380 millimeters, more preferably in the range of from 45 to 280 millimeters, more preferably in the range of from 55 to 200 millimeters, the substrate more preferably having an axial length in the range of from 40 to 254 millimeters, more preferably in the range of from 50 to 154 millimeters, more preferably in the range of from 75 to 127 millimeters.
A further preferred embodiment (51) concretizing any one of embodiments (43) to (50) relates to said catalyst, wherein the number of passages per square inch (per 6.4516 cm2) of the substrate according to (A) is in the range of from 100 to 1200 cpsi, more preferably in the range of from 200 to 900 cpsi, more preferably in the range of from 400 to 600 cpsi.
A further preferred embodiment (52) concretizing any one of embodiments (43) to (51) relates to said catalyst, wherein from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, of the framework structure of the zeolitic material comprised in the coating according to (B) consist of Si, Al, and O.
A further preferred embodiment (53) concretizing any one of embodiments (43) to (52) relates to said catalyst, wherein the zeolitic material comprised in the coating according to (B) exhibits a molar ratio of silicon oxide to aluminum oxide, calculated as SiO2 to Al2O3, SiO2:Al2O3, in the range of from 1 to 50, more preferably in the range of from 8 to 35, more preferably in the range of from 13 to 23, more preferably in the range of from 16 to 20, more preferably in the range of from 17 to 19.
A further preferred embodiment (54) concretizing any one of embodiments (43) to (53) relates to said catalyst, wherein in the zeolitic material comprised in the coating according to (B) the average crystal size is in the range of from 0.1 to 5.0 micrometers, more preferably in the range of from 0.2 to 2.0 micrometers, more preferably in the range of from 0.3 to 1.0 micrometers.
A further preferred embodiment (55) concretizing any one of embodiments (43) to (54) relates to said catalyst, wherein the zeolitic material comprised in the coating according to (B) comprises Fe in an amount, calculated as Fe2O3, in the range of from 0.05 to 2 weight-%, more preferably in the range of from 0.1 to 1 weight-%, more preferably in the range of from 0.2 to 0.8 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
A further preferred embodiment (56) concretizing any one of embodiments (43) to (55) relates to said catalyst, wherein the first non-zeolitic oxidic material comprised in the coating according to (B) of the catalyst is selected from the group consisting of alumina, silica, titania, zirconia, a mixed oxide comprising one or more of Al, Si, Ti, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, zirconia, a mixed oxide comprising one or more of Al, Si, and Zr, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, zirconia, a mixed oxide comprising one or more of Al and Zr, and a mixture of two or more thereof, wherein the first non-zeolitic oxidic material comprised in the coating according to (B) more preferably comprises, more preferably consists of, zirconia-alumina.
A further preferred embodiment (57) concretizing any one of embodiments (43) to (56) relates to said catalyst, wherein the first non-zeolitic oxidic material comprised in the coating according to (B) comprises, preferably consists of, zirconia-alumina, wherein from 30 to 100 weight-%, more preferably from 60 to 85 weight-%, more preferably from 75 to 82 weight-%, of the zirconia-alumina consist of alumina.
A further preferred embodiment (58) concretizing any one of embodiments (43) to (57) relates to said catalyst, wherein the first non-zeolitic oxidic material comprised in the coating according to (B) comprises, more preferably consists of, zirconia-alumina, wherein from 5 to 35 weight-%, preferably from 15 to 25 weight-%, more preferably from 18 to 22 weight-%, of the zirconia-alumina consist of zirconia.
A further preferred embodiment (59) concretizing any one of embodiments (43) to (58) relates to said catalyst, wherein the catalyst comprises the first non-zeolitic oxidic material comprised in the coating according to (B) at an amount in the range of from greater than 0 to 20 weight-%, more preferably in the range of from 0.5 to 10.5 weight-%, more preferably in the range of from 2.0 to 5.5 weight-%, more preferably in the range of from 3.5 to 5.2 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
A further preferred embodiment (60) concretizing any one of embodiments (43) to (59) relates to said catalyst, wherein the coating according to (B) further comprises a second non-zeolitic oxidic material, being different to the first non-zeolitic oxidic material, wherein the second non-zeolitic oxidic material is more preferably selected from the group consisting of alumina, silica, titania, zirconia, ceria, lanthana, praseodymium oxide, manganese oxide, a mixed oxide comprising one or more of Al, Si, Ti, Zr, La, Mn, Pr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of alumina, silica, titania, zirconia, and ceria, a mixed oxide comprising one or more of Al, Si, Ti, Zr, and Ce, and a mixture of two or more thereof, more preferably selected from the group consisting of silica, titania, zirconia, a mixed oxide comprising one or more of Si, Ti, and Zr, and a mixture of two or more thereof, wherein the second non-zeolitic oxidic material more preferably comprises, more preferably consists of, zirconia,
A further preferred embodiment (61) concretizing embodiment (60) relates to said catalyst, wherein the copper comprised in the coating according to (B) is comprised in one or more of the zeolitic material comprised in the coating according to (B), the first non-zeolitic oxidic material comprised in the coating according to (B) and the second non-zeolitc oxidic material comprised in the coating according to (B).
A further preferred embodiment (62) concretizing any one of embodiments (43) to (61) relates to said catalyst, wherein the coating according to (B) comprises one or more of the zeolitic material, the first non-zeolitic oxidic material, and optionally the second non-zeolitic oxidic material as defined in embodiment 60, as particles, wherein said particles are more preferably characterized by a volume-based particle size distribution exhibiting a Dv90 value in the range of from 2 to 20 micrometers, more preferably in the range of from 5 to 15 micrometers, more preferably in the range of from 8 to 12 micrometers, the Dv90 value more preferably being determined as described in Reference Example 2.
A further preferred embodiment (63) concretizing any one of embodiments (43) to (62) relates to said catalyst, wherein the coating according to (B) comprises Cu in an amount, calculated as CuO, in the range of from 3.0 to 7.5 weight-%, more preferably in the range of from 4.5 to 5.8 weight-%, more preferably in the range of from 4.7 to 5.6 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
A further preferred embodiment (64) concretizing any one of embodiments (43) to (63) relates to said catalyst, wherein the coating according to (B) is disposed on the surface of the internal walls of the substrate according to (A) over 60 to 100%, more preferably over 80 to 100%, more preferably over 95 to 100% of the substrate axial length.
A further preferred embodiment (65) concretizing any one of embodiments (43) to (64) relates to said catalyst, wherein the zeolitic material comprised in the coating according to (B) is disposed on the surface of the internal walls of the substrate according to (A) at a loading in the range of from 1.00 to 4.50 g/in3, more preferably in the range of from 1.50 to 3.25 g/in3, more preferably in the range of from 1.65 to 3.10 g/in3.
A further preferred embodiment (66) concretizing any one of embodiments (43) to (65) relates to said catalyst, wherein the first non-zeolitic oxidic material comprised in the coating according to (B) is more preferably disposed on the surface of the internal walls of the substrate according to (A) at a loading in the range of from 0.05 to 0.25 g/in3, more preferably in the range of from 0.08 to 0.20 g/in3, more preferably in the range of from 0.11 to 0.16 g/in3.
A further preferred embodiment (67) concretizing any one of embodiments (60) to (66) relates to said catalyst, wherein the second non-zeolitic oxidic material comprised in the coating according to (B) is disposed on the surface of the internal walls of the substrate according to (A) at a loading in the range of from 0.05 to 0.25 g/in3, more preferably in the range of from 0.08 to 0.20 g/in3, more preferably in the range of from 0.11 to 0.16 g/in3.
A further preferred embodiment (68) concretizing any one of embodiments (43) to (67) relates to said catalyst, wherein the catalyst has a Fe loading, calculated as Fe2O3, in the range of from 0.001 to 0.030 g/in3, more preferably in the range of from 0.003 to 0.015 g/in3, more preferably in the range of from 0.004 to 0.010 g/in3, wherein the Fe is more preferably comprised in the zeolitic material comprised in the coating according to (B).
A further preferred embodiment (69) concretizing any one of embodiments (43) to (68) relates to said catalyst, wherein the catalyst has a Cu loading, calculated as CuO, in the range of from 0.08 to 0.18 g/in3, more preferably in the range of from 0.10 to 0.16 g/in3 more preferably in the range of from 0.11 to 0.15 g/in3, wherein the Cu is more preferably at least partially comprised in the zeolitic material comprised in the coating according to (B).
A further preferred embodiment (70) concretizing any one of embodiments (43) to (69) relates to said catalyst, wherein the catalyst has a loading of the first non-zeolitic oxidic material comprised in the coating according to (B) in the range of from 1 to 10 weight-%, more preferably in the range of from 3 to 7 weight-%, more preferably in the range of from 4 to 6 weight-%, based on the sum of the weight of Si, calculated as SiO2, and the weight of Al, calculated as Al2O3, comprised in the framework structure of the zeolitic material comprised in the coating according to (B).
A further preferred embodiment (71) concretizing any one of embodiments (43) to (70) relates to said catalyst, wherein from 95 to 100 weight-%, more preferably from 97 to 100 weight-%, more preferably from 99 to 100 weight-%, of the coating according to (B) consist of the zeolitic material comprised in the coating according to (B), Fe, Cu, O, and the first non-zeolitic oxidic material comprised in the coating according to (B).
A further preferred embodiment (72) concretizing any one of embodiments (43) to (71) relates to said catalyst, wherein the catalyst has a loading of the coating according to (B) in the range of from 1.0 to 5.0 g/in3, more preferably in the range of from 1.75 to 3.75 g/in3, more preferably in the range of from 1.9 to 3.5 g/in3.
A further preferred embodiment (73) concretizing any one of embodiments (43) to (72) relates to said catalyst, wherein from 95 to 100 weight-%, more preferably from 97 to 100 weight-%, more preferably from 99 to 100 weight-%, of the catalyst consist of the substrate according to (A) and the coating according to (B).
Yet further, an embodiment (74) of the present invention relates to a system for the treatment of an exhaust gas of a diesel combustion engine, the system comprising a diesel oxidation catalyst, a catalyzed soot filter, and a catalyst according to any one of embodiments (42) to (73), wherein in said system, the diesel oxidation catalyst is located upstream of the catalyzed soot filter, and wherein the catalyzed soot filter is located upstream of said catalyst according to any one of embodiments (42) to (73).
An preferred embodiment (75) concretizing embodiment (74) relates to said system, wherein the system further comprises a reductant injector, more preferably one or more of a hydrocarbon injector, a hydrocarbon in-cylinder post injector, and a urea injector, wherein the reductant injector is more preferably arranged upstream of the catalyzed soot filter, wherein the reductant injector is more preferably arranged downstream of the diesel oxidation catalyst.
Yet further, an embodiment (76) of the present invention relates to a use of a catalyst of any one of embodiments (42) to (73) or a system of embodiment (74) or (75), for the treatment of an exhaust gas of a diesel combustion engine.
Yet further, an embodiment (77) of the present invention relates to a method for treating an exhaust gas of a diesel combustion engine, said method comprising bringing said exhaust gas in contact with a catalyst according to any one of embodiments (42) to (73).
Yet further, an embodiment (78) of the present invention relates to a method for treating an exhaust gas of a diesel combustion engine, said method comprising passing said exhaust gas through a system according to embodiment (74) or (75).
According to the present invention, it is preferred that a pH value is measured according to the international standard ISO 34-8 (International Standard ISO 34-8: Quantities and Units—Part 8: Physical Chemistry and Molecular Physics, Annex C (normative): pH. International Organization for Standardization, 1992). According to the present invention it is yet further preferred that the pH values as defined in the present application are determined in accordance with ISO 80000-9, Annex C, pH.
In the context of the present invention, the second non-zeolitic oxidic material particularly functions as binder.
In the context of the present invention, the term “the surface of the internal walls” is to be understood as the “naked” or “bare” or “blank” surface of the walls, i.e. the surface of the walls in an untreated state which consists—apart from any unavoidable impurities with which the surface may be contaminated—of the material of the walls.
In the context of the present invention, the term “consists of” with regard to the weight-% of one or more components indicates the weight-% amount of said component(s) based on 100 weight-% of the entity in question. For example, the wording “wherein from 0 to 0.001 weight-% of the first coating consists of X” indicates that among the 100 weight-% of the components of which said coating consists of, 0 to 0.001 weight-% is X.
Furthermore, in the context of the present invention, a term “X is one or more of A, B and C”, wherein X is a given feature and each of A, B and C stands for specific realization of said feature, is to be understood as disclosing that X is either A, or B, or C, or A and B, or A and C, or B and C, or A and B and C. In this regard, it is noted that the skilled person is capable of transfer to above abstract term to a concrete example, e.g. where X is a chemical element and A, B and C are concrete elements such as Li, Na, and K, or X is a temperature and A, B and C are concrete temperatures such as 10° C., 20° C., and 30° C. In this regard, it is further noted that the skilled person is capable of extending the above term to less specific realizations of said feature, e.g. “X is one or more of A and B” disclosing that X is either A, or B, or A and B, or to more specific realizations of said feature, e.g. “X is one or more of A, B, C and D”, disclosing that X is either A, or B, or C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D, or A and B and C and D.
In the context of the present invention, a weight/loading of a non-zeolitic oxidic material is calculated as the weight/loading of the respective non-zeolitic oxidic material as oxide or the sum the weights/loadings of the respective non-zeolitic oxidic material as oxides. For example, if a non-zeolitic oxidic material is silica, the weight of said non-zeolitic oxidic material is calculated as SiO2. As a further example, if a non-zeolitic oxidic material consists of a mixed oxide comprising Ti and Al, the weight of said non-zeolitic oxidic material is calculated as sum of TiO2 and Al2O3.
The present invention is further illustrated by the following examples and reference examples.
The pore volume was determined by mercury intrusion using mercury porosimetry according to DIN 66133 and ISO 15901-1.
The volume-based particle size distributions, in particular Dv50 and Dv90 values, were determined by a static light scattering method using Sympatec HELOS (3200) & QUIXEL equipment, wherein the optical concentration of the sample was in the range of from 6 to 10%.
Two different slurries, slurry (1) and slurry (2), were prepared separately from each other.
For slurry (1), a copper oxide powder having a Dv50 of 33 micrometers as a source of copper was added to water. The amount of copper oxide was calculated such that the total amount of copper, calculated as CuO, in the coating after calcination was 5.5 weight-% based on the weight of the zeolitic material having framework structure type CHA. The resulting aqueous mixture was milled using a continuous milling apparatus so that the Dv90 value of the particles was about 5.8 micrometers. The resulting slurry had a solid content of 8 weight-% based on the total weight of said slurry. A zirconium acetate solution as a source of an oxidic component was added to the copper oxide-containing aqueous mixture forming a slurry. The amount of zirconium acetate was calculated such that the amount of zirconia in the coating, calculated as ZrO2, was 5 weight-% based on the weight of the zeolitic material having framework structure type CHA. Water and a zeolitic material having framework structure type CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer) were added to the slurry to form an aqueous mixture having a solid content of about 40 weight-% based on the total weight of said aqueous mixture. The amount of the Cu-containing zeolitic material having framework structure type CHA was calculated such that the loading of the Cu-containing zeolitic material having framework structure type CHA after calcination was 87 weight-% of the loading of the coating in the catalyst after calcination. The resulting slurry was milled using a continuous milling apparatus so that the Dv90 value of the particles was smaller than 10 micrometers.
For slurry (2), an aqueous slurry having a solid content of 41.5 weight-% based on the total weight of said slurry and comprising water and alumina as a non-zeolitic oxidic material (consisting of 80 weight-% Al2O3 and 20 weight-% ZrO2) was prepared. The amount of said zirconia-containing alumina was calculated such that the amount thereof after calcination was 5 weight-% based on the weight of the zeolitic material having framework structure type CHA after calcination.
Subsequently, slurries (1) and (2) were combined to obtain a final slurry. The pH of the final slurry was determined as being 4.6. The solid content of the final slurry was about 40.3 weight-% based on the total weight of the final slurry.
A cylindrical cordierite flow through substrate (having an axial length of 101.6 mm, a diameter of 58 mm) was coated from the inlet end with the final slurry over 100% of the substrate axial length. To this effect, the substrate was dipped in the final slurry diluted to a solid content of 38 weight-% from the inlet end until the slurry reached the top of the substrate. Further, the coated substrate was dried in air at 130° C. for 30 minutes and then calcined in air at 450° C. for 2 hours.
The final coating loading after calcination was about 2 g/in3, including about 1.73 g/in3 of a zeolitic material having framework structure type CHA, 0.09 g/in3 of zirconia-containing alumina, about 0.09 g/in3 of zirconia and 0.095 g/in3 of copper oxide.
A zeolitic material having framework type CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, an average crystal size of 0.4 micrometer) was impregnated with a solution of Fe(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and water. The amount of water was chosen so that the solution fills 90% of the pore volume of the zeolitic material and the amount of Fe(III) nitrate nonahydrate was chosen so that the iron oxide loading on the zeolitic material having framework structure type CHA after calcination was 0.2 weight-%. Subsequently, the impregnated zeolitic material was heated in air to 60° C. and held at this temperature for 2 hours, heated to 90° C. and held at this temperature for 1 hour, heated to 130° C. and held at this temperature for 2 hours, and finally heated to 590° C. and held at this temperature for 2 hours.
For preparing a final slurry and a coated substrate, the recipe according to comparative example 1 was followed but the zeolitic material having framework structure type CHA was replaced by the calcined Fe-impregnated zeolitic material having framework structure type CHA. Further, the copper oxide content on the zeolitic material having framework structure type CHA was 4.8 weight-%. The pH of slurry (1) comprising the zeolitic material impregnated with Fe and comprising copper oxide was determined before milling as being 4.1. The pH of the final slurry was determined as being 4.4. The final washcoat loading after calcination was 2.0 g/in3.
Fe(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and Cu acetate monohydrate (CuAc2·H2O) were dissolved in water whereby additionally 0.3 weight-% of citric acid were added, calculated based on the total weight of the Cu acetate monohydrate. In a next step, the resulting solution was impregnated on a zeolitic material having framework structure type CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer). The amount of Cu acetate monohydrate and Fe(III) nitrate nonahydrate were chosen so that the final copper oxide loading and iron oxide loading after calcination were 4.8 weight-% and 0.2 weight-%, respectively. The amount of water was chosen so that this solution fills 90% of the pores of the zeolitic material. Subsequently, the resulting impregnated zeolitic material was heated in air to 60° C. and held at this temperature for 2 hours, heated to 130° C. and held at this temperature for 1 hour, and finally heated to 590° C. and held at this temperature for 4 hours. For preparing a final slurry and a coated substrate, the recipe according to comparative example 1 was followed without using the copper oxide slurry. The pH of slurry (1) comprising the zeolitic material impregnated with Fe and comprising copper oxide was determined before milling as being 4. The pH of the final slurry was determined as being 4.4. The final washcoat loading after calcination was 2.0 g/in3.
Catalytic testings were performed using cores having a diameter of 25.4 mm which were drilled out from the prepared coated substrates. Further, the cores were shortened to a length of 76.2 mm. The thus obtained samples were tested in a gas stream comprising 150 ppm NO, 225 ppm NH3, 80 ppm C3H6 (C1 basis) 10% O2, 5% CO2 and 5% H2O. The gas hourly space velocity was set to 60000/h for measurements in the temperature range of from 160 to 500° C. and to 120000/h for measurements at a temperature of 600° C. The results of the catalytic testings are shown in
As shown in
Water was impregnated on a zeolitic material having framework structure type CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer) so that the water volume fills 90% of the pores of the zeolitic material having framework structure type CHA. Then, the resulting zeolitic material was calcined in air at 590° C. For preparing a final slurry and a coated substrate, the recipe according to Comparative Example 1 was followed but the zeolitic material having framework structure type CHA was replaced by the calcined zeolitic material having framework structure type CHA. Thus, the copper oxide content on the zeolitic material having framework structure type CHA was 5.5 weight-%. The final washcoat loading after calcination was 2.0 g/in3.
A zeolitic material having framework t structure ype CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer) was impregnated with a solution of Fe(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and water. The amount of water was chosen so that the solution fills 90% of the pore volume of the zeolitic material having framework structure type CHA and the amount of Fe(III) nitrate nonahydrate was chosen so that the iron oxide loading on the zeolitic material after calcination was 0.3 weight-%. For preparing a final slurry and a coated substrate, the recipe according to Comparative Example 1 was followed but the zeolitic material having framework structure type CHA was replaced by the Fe-impregnated zeolitic material having framework structure type CHA and the copper oxide content on the zeolitic material having framework structure type CHA was 4.8 weight-%. The final washcoat loading after calcination was 2.0 g/in3.
A zeolitic material (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer) was impregnated with a solution of Fe(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and water. The amount of water was chosen so that the solution fills 90% of the pore volume of the zeolitic material having framework structure type CHA. The Fe(III) nitrate nonahydrate (Fe(NO3)3·9H2O) was chosen so that the iron oxide loading on the zeolitic material having framework structure type CHA after calcination was as noted in table 1 below for Examples 4-7. For preparing final slurries and coated substrates, the recipe according to Comparative Example 1 was followed but the zeolitic material having framework structure type CHA was replaced by the Fe-impregnated zeolitic material having framework type CHA. The copper oxide content on the zeolitic material having framework structure type CHA was as noted in table 1 below for Examples 4-7. The pH of slurry (1) comprising the zeolitic material impregnated with Fe and comprising copper oxide was determined for each of Examples 4-7, the respective values are listed in table 2. Also, the pH of the final slurry was determined for each of Examples 4-7. The final washcoat loading after calcination was 2.0 g/in3 for Examples 4-7.
The catalysts were tested on a Euro 6 engine. In order to do that, the coated catalysts were canned and aged hydrothermally at 800° C. for 16 h. Then the catalysts were placed downsteam of a combination of a DOC and a CSF and tested, whereby emissions measurements were made at 220° C., 575° C. and 630° C. The NOx inlet emissions comprised 470 ppm, 700 ppm, 680 ppm, respectively, and the volume flows were set to 20 m3/h for all temperatures.
It was surprisingly found that the catalyst of Example 3, thus, prepared without calcining the iron impregnated zeolitic material before further use, showed improved catalytic performance compared to the catalyst of Example 5, which comprised approximately the same contents of iron oxide and copper oxide. Further, it was surprisingly found that a higher copper oxide loading of 5.5 weight-% compared to 4.8 weight-% leads to a higher NOx conversion at low temperatures. The high temperature NOx conversion was improved for the catalysts of Examples 3-7 with the additional Fe impregnation.
Further, the catalytic performance was evaluated with respect to the N2O emissions which were produced over the SCR. The results are shown in
A zeolitic material having framework structure type CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer) was impregnated with a solution of Fe(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and water. The amount of water was chosen so that the solution fills 90% of the pore volume of the zeolitic material having framework structure type CHA and the amount of Fe(III) nitrate nonahydrate was chosen so that the iron oxide loading on the zeolitic material having framework structure type CHA after calcination was as given in table 3 below for Examples 9-12.
For preparing final slurries and coated substrates, the recipe according to Comparative Example 1 was followed but the zeolitic material having framework structure type CHA was replaced by the Fe-impregnated zeolitic material having framework structure type CHA and the copper oxide content on the zeolitic material having framework structure type CHA was as noted in table 4 for the Examples 9-12. The final washcoat loading after calcination was 2.0 g/in3.
Examples 9-12 and Comparative Example 2 were tested on a Euro 6 engine. In order to do that, the coated catalysts were canned and aged hydrothermally at 800° C. for 16 h. Then, the catalysts were tested downstream of a combination of a DOC and CSF at temperatures of 200° C., 220° C., 575° C. and 630° C. The NOx inlet emissions were 450 ppm, 480 ppm, 700 ppm, 700 ppm, respectively, and the volume flows were set to 20 m3/h for all temperatures.
The results of the catalytic testing are shown in
Further, the catalytic performance was evaluated with respect to the N2O emissions which were produced over the SCR. The results are shown in
Further, it can be seen that a comparatively higher copper content of led to higher N2O emissions whereas an increasing iron oxide content led to N2O reduction.
For slurry (1), a copper oxide powder (a CuO powder having a Dv50 of 33 micrometers) was added to water. The amount of copper oxide was calculated such that the total amount of copper, calculated as CuO, in the coating after calcination was 5.5 weight-% based on the weight of the zeolitic material having framework structure type CHA. The resulting aqueous mixture was milled using a continuous milling apparatus so that the Dv90 value of the particles was about 5.8 micrometers. The resulting slurry had a solid content of 30 weight-% based on the total weight of the slurry. A zirconium acetate solution as a source of an oxidic component was added to the copper oxide-containing aqueous mixture forming a slurry. The amount of zirconium acetate was calculated such that the amount of zirconia in the coating, calculated as ZrO2, was 5 weight-% based on the weight of the zeolitic material having framework structure type CHA. Water and a zeolitic material having framework structure type CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer) were added to the slurry to form an aqueous mixture having a solid content of about 42.5 to 45 weight-% based on the total weight of said aqueous mixture. The amount of Cu-containing zeolitic material having framework structure type CHA was calculated such that the loading of the zeolitic material having framework structure type CHA after calcination was 87% of the loading of the coating in the catalyst after calcination. The resulting slurry was milled using a continuous milling apparatus so that the Dv90 value of the particles was smaller than 7 micrometers.
For slurry (2), an aqueous slurry having a solid content of about 42 weight-% based on the total weight of the slurry and comprising water and alumina as a non-zeolitic oxidic material (consisting of 80 weight-% Al2O3 and 20 weight-% ZrO2) was separately prepared. The amount of said zirconia-containing alumina was calculated such that the amount thereof after calcination was 5 weight-% based on the weight of the Cu-containing zeolitic material having framework structure type CHA after calcination.
Subsequently, slurries (1) and (2) were combined, the solid content of the obtained final slurry was about 42 weight-% based on the total weight of the final slurry.
A cylindrical cordierite flow through substrate (having a diameter of 143.8 mm and an axial length of 76.2 mm) was coated from the inlet end with the final slurry over 100% of the substrate axial length. To this effect, the substrate was dipped in the final slurry diluted to a solid content of 38 weight-% from the inlet end until the slurry reached the top of the substrate. Further, the coated substrate was dried in air at 130° C. for 30 minutes and then calcined in air at 590° C. for 2 hours.
The final coating loading after calcination was about 3.37 g/in3, including about 2.92 g/in3 of a zeolitic material having framework structure type CHA, 0.15 g/in3 of zirconia-containing alumina, about 0.15 g/in3 of zirconia and 0.16 g/in3 of copper oxide.
A zeolitic material having framework structure type CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer) was impregnated with a solution of Fe(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and water. The amount of water was chosen so that the solution fills 90% of the pore volume of the zeolitic material having framework structure type CHA and the amount of Fe(III) nitrate nonahydrate was chosen so that the iron oxide loading on the zeolitic material having framework structure type CHA after calcination was 0.2 weight-%. Subsequently, the resulting impregnated zeolitic material having framework structure type CHA was dried, heated in air to a temperature of 590° C. and held for 2 hours at this temperature.
For preparing a final slurry and a coated substrate, the recipe according to Comparative Example 3 was followed but the zeolitic material having framework structure type CHA was replaced by the Fe-impregnated zeolitic material having framework structure type CHA and the copper oxide content on the zeolitic material having framework structure type CHA was 4.8 weight-%. The final washcoat loading after calcination was 2.75 g/in3, including 2.39 g/in3 of zeolitic material having framework structure type CHA, 0.12 g/in3 of zirconia-containing alumina, 0.11 g/in3 of copper oxide, 0.12 g/in3 of zirconia and 0.005 g/in3 of FeOx.
A zeolitic material having framework structure type CHA (a chabazite having a Dv50 of 2.2 micrometers, a Dv90 of 5.2 micrometers, a SiO2:Al2O3 molar ratio of 18, and an average crystal size of 0.4 micrometer) was impregnated with a solution of Fe(III) nitrate nonahydrate (Fe(NO3)3·9H2O) and water. The amount of water was chosen so that the solution fills 90% of the pore volume of the zeolitic material having framework structure type CHA and the amount of Fe(III) nitrate nonahydrate was chosen so that the iron oxide loading on the zeolitic material having framework structure type CHA after calcination was 0.3 weight-%.
For preparing a final slurry and a coated substrate, the recipe according to Comparative Example 3 was followed but the zeolitic material having framework structure type CHA was replaced by the Fe-impregnated zeolitic material having framework structure type CHA and that the copper oxide content on the zeolitic material having framework structure type CHA was 4.8 weight-%. The final washcoat loading after calcination was 3.4 g/in3, including 2.95 g/in3 of zeolitic material having framework structure type CHA, 0.15 g/in3 of zirconia-containing alumina, 0.14 g/in3 of copper oxide, 0.15 g/in3 zirconia and 0.009 g/in3 FeOx.
In a first test set, comparative Example 3 and Examples 14-15 were tested on a reactor with respect to their catalytic performance. Catalytic testings were performed using cores having a diameter of 25.4 mm which were drilled out from the prepared coated substrates. Further, the cores were shortened to a length of 76.2 mm. Then, the cores were hydrothermally aged at 800° C. for 16 h. The thus obtained samples were tested in a gas stream comprising 325 ppm NO, 125 ppm NO2, and 750 ppm NH3. The gas hourly space velocity was set to 100000/h. The results of the catalytic testings are shown in
In a second test set, catalytic testings were performed on full size catalysts as obtained from the respective examples, thus, where a catalyst comprised a cylindrical substrate having a diameter of 143.8 mm and an axial length of 76.2 mm. The catalysts were hydrothermally aged for 16 h at 800° C. and then canned. The catalysts were tested on a Euro 6 engine in a temperature ramp test. The test procedure is detailed in
The results of the testing are shown in
The slurries and a coated substrate were prepared according to Example 15 considering the following. The copper oxide content on the zeolitic material having framework structure type CHA was 4.5 weight-% and the iron oxide loading was 0.3 weight-%. The final washcoat loading after calcination was 3.4 g/in3 including 2.96 g/in3 of zeolitic material having framework structure type CHA, 0.15 g/in3 of zirconia-containing alumina, 0.13 g/in3 of copper oxide, 0.15 g/in3 zirconia and 0.009 g/in3 FeOx.
As samples of the catalysts according to Example 15, 18 and Comparative Example 3 cylindrical cores having a diameter of 143.8 mm (5.66 inch) and an axial length of 76.2 mm (3 inch) were prepared. The samples were hydrothermally aged at 800° C. for 16 h. Then, the samples were tested on an engine bench. At several steady state conditions, urea was dosed: at 210° C. and 260° C. The NOx conversion was measured at 10 ppm NH3 slip whereas at 600° C. the average NOx conversion at constant slip was measured. The volume flow was set to about 80 m3/h and the NH3/NOx molar ratio (normalized stoichiometric ratio (NSR)) at 210° C. and at 260° C. was set to 1.5. Said NH3/NOx molar ratio was calculated based on the assumption that one urea molecule decomposes to two NH3 molecules at temperatures higher than 200° C. At 600° C. the volume flow was set to 20 m3/h and the NH3/NOx molar ratio to 1 (grey bars) or 3 (white bars).
The test results are shown in
As discussed above with respect to the catalytic testing according to Example, the N2O slip was strongly reduced for the catalyst of Example 15 compared to that of Comparative Example 3. The catalyst of Example 18 showed a further improved reduction in N2O Slip.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20204846.8 | Oct 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/080128 | 10/29/2021 | WO |
