Patent Application
20170072364
The invention relates to a NOx trap composition, its use in exhaust systems for internal combustion engines, and a method for treating an exhaust gas from an internal combustion engine.
Internal combustion engines produce exhaust gases containing a variety of pollutants, including hydrocarbons, carbon monoxide, nitrogen oxides (“NOx”), sulfur oxides, and particulate matter. Increasingly stringent national and regional legislation has lowered the amount of pollutants that can be emitted from such diesel or gasoline engines. Many different techniques have been applied to exhaust systems to clean the exhaust gas before it passes to atmosphere.
One such technique utilized to clean exhaust gas is the NOx trap (or “NOx adsorber catalyst”). NOx traps are devices that adsorb NOx under lean exhaust conditions, release the adsorbed NOx under rich conditions, and reduce the released NOx to form N2. A NOx trap typically includes a NOx adsorbent for the storage of NOx and an oxidation/reduction catalyst.
The NOx adsorbent component is typically an alkaline earth metal (such as Ba, Ca, Sr, and Mg), an alkali metal (such as K, Na, Li, and Cs), a rare earth metal (such as La, Y, Pr, and Nd), or combinations thereof. These metals are typically found in the form of oxides. The oxidation/reduction catalyst is typically one or more noble metals, preferably platinum, palladium, and/or rhodium. Typically, platinum is included to perform the oxidation function and rhodium is included to perform the reduction function. The oxidation/reduction catalyst and the NOx adsorbent are typically loaded on a support material such as an inorganic oxide for use in the exhaust system.
The NOx trap performs three functions. First, nitric oxide reacts with oxygen to produce NO2 in the presence of the oxidation catalyst. Second, the NO2 is adsorbed by the NOx adsorbent in the form of an inorganic nitrate (for example, BaO or BaCO3 is converted to Ba(NO3)2 on the NOx adsorbent). Lastly, when the engine runs under rich conditions, the stored inorganic nitrates decompose to form NO or NO2 which are then reduced to form N2 by reaction with carbon monoxide, hydrogen and/or hydrocarbons (or via NHx or NCO intermediates) in the presence of the reduction catalyst. Typically, the nitrogen oxides are converted to nitrogen, carbon dioxide and water in the presence of heat, carbon monoxide and hydrocarbons in the exhaust stream.
NOx traps have been described in the prior art. For instance, U.S. Pat. No. 7,811,536 describes a NOx storage catalyst comprising cobalt, barium and a support. The catalyst may contain platinum or may be platinum-free. The support is alumina, silica, titania, zirconia aluminosilicates, and mixtures thereof, with alumina being preferred.
As with any automotive system and process, it is desirable to attain still further improvements in exhaust gas treatment systems. We have discovered a new NOx trap composition with improved aging characteristics.
The invention is a NOx trap composition that comprises a platinum group metal, barium, cobalt, and a magnesia-alumina support. The invention also includes a NOx trap comprising the NOx trap composition supported on a substrate, and its use in an exhaust system. The NOx trap composition is less prone to storage deactivation and exhibits reduced N2O formation upon aging.
The NOx trap composition of the invention comprises a platinum group metal, barium, cobalt, and a magnesia-alumina support. The platinum group metal (PGM) is preferably platinum, palladium, rhodium, or mixtures thereof; most preferably, the PGM is platinum, palladium, or mixtures thereof.
The magnesia-alumina support is preferably a spinel, a magnesia-alumina mixed metal oxide, a hydrotalcite or hydrotalcite-like material, and combinations of two or more thereof. More preferably, the magnesia-alumina support is a spinel.
Preferably, the magnesia-alumina support comprises 5 to 40 weight percent magnesia, more preferably 10 to 30 weight percent. If the magnesia-alumina support is a hydrotalcite, the support is preferably mixed with an alumina such as boehmite to maintain the overall magnesia content to within 5 to 40 weight percent.
The spinel is preferably a magnesium aluminate spinel, preferably having an atomic ratio of Mg to Al ranging from about 0.17 to about 1, more preferably from about 0.25 to about 0.75, and most preferably from about 0.35 to about 0.65. A most preferred embodiment includes MgAl2O4.
The magnesia-alumina mixed metal oxide comprises Al2O3 and MgO. Portions of the Al2O3 and MgO may be chemically reacted or unreacted. The ratio of Mg/Al in the magnesia-alumina mixed metal oxide may preferably vary from about 0.25 to 10, more preferably from about 0.5 to about 2, and most preferably from about 0.75 to about 1.5.
The magnesia-alumina support may also be a hydrotalcite or hydrotalcite-like (HTL) material. The hydrotalcite or HTL may be collapsed, dehydrated and or dehydroxylated. Non-limiting examples and methods for making various types of hydrotalcites or HTLs are described in U.S. Pat. Nos. 4,866,019, 4,964,581, 4,952,382 6,028,023, 6,479,421, 6,929,736, and 7,112,313; which are incorporated by reference herein in their entirety.
Preferably, the magnesia-alumina support is calcined at a temperature greater than 600° C., more preferably greater than 700° C. and most preferably greater than 800° C., prior to its inclusion in the NOx trap composition. The calcination is typically performed in the presence of an oxygen-containing gas (such as air) for greater than 1 hour. The high-temperature calcination leads to the formation of spinel in the magnesia-alumina support.
The NOx trap composition of the present invention may be prepared by any suitable means. Preferably, the platinum group metal, cobalt and barium are loaded onto the magnesia-alumina support by any known means to form the NOx trap composition, the manner of addition is not considered to be particularly critical. For example, a PGM compound (such as platinum nitrate), a cobalt compound (such as cobalt nitrate), and a barium compound (such as barium nitrate) may be supported on the magnesia-alumina support by impregnation, adsorption, ion-exchange, incipient wetness, precipitation, or the like.
The order of addition of the PGM, cobalt and barium compounds to the magnesia-alumina support is not considered critical. For example, the platinum, cobalt, and barium compounds may be added to the magnesia-alumina support simultaneously, or may be added sequentially in any order. Preferably, the cobalt and barium compounds are added to the magnesia-alumina support prior to the addition of the PGM compound(s).
The NOx trap composition preferably comprises 0.1 to 10 weight percent PGM, more preferably 0.5 to 5 weight percent PGM, and most preferably 1 to 3 weight percent PGM. The NOx trap composition preferably comprises 2 to 20 weight percent cobalt, more preferably 5 to 15 weight percent cobalt, and most preferably 7 to 12 weight percent cobalt. The NOx trap composition preferably comprises 1 to 10 weight percent barium, more preferably 2 to 8 weight percent barium, and most preferably 3 to 7 weight percent barium. Preferably, the weight ratio of cobalt:barium is greater than 1, more preferably 2 or higher.
The invention also includes a NOx trap. The NOx trap comprises the NOx trap composition supported on a ceramic substrate or a metallic substrate. The ceramic substrate may be made of any suitable refractory material, e.g., alumina, silica, titania, ceria, zirconia, magnesia, zeolites, silicon nitride, silicon carbide, zirconium silicates, magnesium silicates, aluminosilicates and metallo aluminosilicates (such as cordierite and spodumene), or a mixture or mixed oxide of any two or more thereof. Cordierite, a magnesium aluminosilicate, and silicon carbide are particularly preferred.
The metallic substrate may be made of any suitable metal, and in particular heat-resistant metals and metal alloys such as titanium and stainless steel as well as ferritic alloys containing iron, nickel, chromium, and/or aluminum in addition to other trace metals.
The substrate is preferably a flow-through substrate or a filter substrate. Most preferably, the substrate is a flow-through substrate. In particular, the flow-through substrate is a flow-through monolith preferably having a honeycomb structure with many small, parallel thin-walled channels running axially through the substrate and extending throughout the substrate. The channel cross-section of the substrate may be any shape, but is preferably square, sinusoidal, triangular, rectangular, hexagonal, trapezoidal, circular, or oval.
Preferably, the NOx trap is prepared by depositing the NOx trap composition on the substrate using washcoat procedures. A representative process for preparing the NOx trap using a washcoat procedure is set forth below. It will be understood that the process below can be varied according to different embodiments of the invention.
The washcoating is preferably performed by first slurrying finely divided particles of the NOx trap composition in an appropriate solvent, preferably water, to form a slurry. The slurry preferably contains between 5 to 70 weight percent solids, more preferably between 10 to 50 weight percent. Preferably, the particles are milled or subject to another comminution process in order to ensure that substantially all of the solid particles have a particle size of less than 20 microns in an average diameter, prior to forming the slurry. Additional components, such as stabilizers or promoters may also be incorporated in the slurry as a mixture of water soluble or water-dispersible compounds or complexes.
The substrate may then be coated one or more times with the slurry such that there will be deposited on the substrate the desired loading of the NOx trap composition.
It is also possible to form the NOx trap composition on the substrate in order to produce the NOx trap. In such a procedure, a slurry of the magnesia-alumina support is washcoated onto the substrate as described above. After the magnesia-alumina support has been deposited on the substrate (and optionally calcined), the platinum group metal, cobalt and barium may then be added to the magnesia-alumina washcoat. The PGM, barium and cobalt may be added by any known means, including impregnation, adsorption, or ion-exchange of a PGM compound (such as platinum nitrate), a barium compound (such as barium nitrate), and a cobalt compound (such as cobalt nitrate). The order of this addition is not considered critical such that the platinum group metal compound, the barium compound, and the cobalt compound may be added simultaneously or sequentially in any order.
Preferably, the entire length of the substrate is coated with the NOx trap composition so that a washcoat of the NOx trap composition covers the entire surface of the substrate.
After the NOx trap composition is deposited onto the substrate, the NOx trap is typically dried by heating at an elevated temperature of preferably 80 to 150° C. and then calcined by heating at an elevated temperature. Preferably, the calcination occurs at 400 to 600° C. for approximately 1 to 8 hours.
The invention also encompasses an exhaust system for internal combustion engines that comprises the NOx trap of the invention. Preferably, the exhaust system comprises the NOx trap with an oxidation catalyst and/or a particulate filter. These after-treatment devices are well known in the art. Particulate filters are devices that reduce particulates from the exhaust of internal combustion engines. Particulate filters include catalyzed soot filters (CSF) and bare (non-catalyzed) particulate filters. Catalyzed soot filters (for diesel and gasoline applications) include metal and metal oxide components (such as Pt, Pd, Fe, Mn, Cu, and ceria) to oxidize hydrocarbons and carbon monoxide in addition to destroying soot trapped by the filter.
Particularly preferred exhaust systems include the NOx trap followed by a CSF, both close-coupled; a close-coupled NOx trap with an underfloor CSF; and a close-coupled diesel oxidation catalyst/CSF and an underfloor NOx trap.
The invention also encompasses treating an exhaust gas from an internal combustion engine, in particular for treating exhaust gas from a vehicular lean burn internal combustion engine, such as a diesel engine, a lean-burn gasoline engine, or an engine powered by liquid petroleum gas or natural gas. The method comprises contacting the exhaust gas with the NOx trap of the invention.
The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.
Catalyst 1A (Pt—Pd—Ba—Co/Magnesia-Alumina Support):
Cobalt (II) nitrate (4.92 g) and barium acetate (0.93 g) are dissolved in demineralized water (˜15 mL) using gentle heating. This Co—Ba solution is then added stepwise to magnesia-alumina support (10 g), before being dried at 105° C. for 2-3 hours, followed by calcination at 500° C. for 2 hours to form a Ba—Co/magnesia-alumina. The Ba—Co/magnesia-alumina is contacted with an aqueous solution of platinum and palladium salts (˜7 g solution) to add 1.5 wt. % Pt and 0.5 wt. % Pd onto the final catalyst, before being dried at 105° C. for 2-3 hours, followed by calcination at 500° C. for 2 hours to form Catalyst 1A. Catalyst 1A contains 10 wt. % Co, 5 wt. % Ba, 1.5 wt. % Pt, and 0.5 wt. % Pd.
Comparative Catalyst 1B (Pt—Pd—Ba/Magnesia-Alumina Support):
Comparative Catalyst 1B is prepared according to the procedure of Catalyst 1A with the exception that cobalt nitrate is not utilized. Comparative Catalyst 1B contains 5 wt. % Ba, 1.5 wt. % Pt, and 0.5 wt. % Pd.
Comparative Catalyst 1C (Pt—Pd—Ba—Co/Alumina Support):
Comparative Catalyst 1C is prepared according to the procedure of Comparative Catalyst 1A with the exception that alumina is used in place of the maganesia-alumina support. Comparative Catalyst 1C contains 10 wt. % Co, 5 wt. % Ba, 1.5 wt. % Pt, and 0.5 wt. % Pd.
The catalyst (0.4 g) is stored at 200° C. for 5 minutes in an NO-containing gas, then the temperature is increased to 290° C. at a ramping rate of 20° C./minute to achieve a bed temperature of 275° C., and the catalyst is maintained at a 275° C. bed temperature for 5 minutes. The catalyst is then subjected to a 15 second rich purge in the presence of a rich gas, followed by Temperature Programmed Desorption (TPD) in the presence of a TPD gas until the bed temperature reaches about 500° C. in order to measure the NOx storage and N2O selectivity of the fresh catalysts (“fresh cycle”).
The catalyst is then thermally aged at 800° C. in air for 24 hours, and is subjected to a rich activation for 2 minutes in the presence of the rich gas at a temperature of 500° C.
The procedure is repeated in order to measure the NOx storage and N2O selectivity of the thermally aged catalyst (“aged cycle”).
The NO-containing gas comprises 10.5 vol. % O2, 50 ppm NO, 6 vol. % CO2, 1500 ppm CO, 100 ppm hydrocarbons and 6.3 vol. % H2O.
The rich gas comprises 1.5 vol. % O2, 6 vol. % CO2, 43,200 ppm CO, 1830 ppm hydrocarbons and 6.3 vol. % H2O.
The TPD gas comprises 10.5 vol. % O2, 6 vol. % CO2, 1500 ppm CO, 100 ppm hydrocarbons and 6.3 vol. % H2O.
The NOx storage results are shown in Table 1.
The N2O selectivity results are shown in Table 2.
The results show that the catalyst of the invention (Catalyst 1A) has higher NOx storage and good selectivity to N2O compared to Comparative Catalysts 1B and 1C. Catalyst 1A also retains good NOx storage and N2O selectivity after the high temperature aging at 800° C., as compared with Comparative Catalysts 1B and 1C which show much lower NOx storage and an increase in selectivity to N2O upon aging.
This application is a divisional of U.S. patent application Ser. No. 13/456,374, filed Apr. 26, 2012, the disclosure of which is incorporated herein by reference in its entireties for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13456374 | Apr 2012 | US |
| Child | 15359170 | US |
