The present disclosure relates to an emissions reduction system, for example, for diesel engines.
Diesel engines generally operate at a lower temperature and run leaner compared to conventional gasoline engines. While gasoline engines may put out more NOx on a ppm basis due to higher combustion temperatures, the three-way catalyst may reduce the NOx with high efficiency when the A/F ratio is at stoichiometry. Consequently, the NOx emissions from the catalyst-equipped gasoline engine can be lower than the NOx emissions from a diesel engine. Since diesels operate lean, the three-way catalyst may not reduce NOx. The reduction of NOx emissions is therefore a unique challenge for diesel engines. One approach to NOx reduction on diesel engines is the use of selective catalytic reduction (SCR) systems. SCR systems with urea injection may be very effective for reducing NOx under lean conditions once the temperature of the SCR catalyst is above a minimum operating level (e.g., 150° C. or 200° C.). However, before the SCR catalyst has reached this operating temperature, much of the NOx in the exhaust passes through the SCR catalyst without being reduced and is emitted from the vehicle.
In at least one embodiment, an exhaust system for a diesel engine is provided. The system may include a diesel oxidation catalyst (DOC) configured to receive exhaust gases from the engine and oxidize hydrocarbons in the exhaust gases and a passive NOx adsorber (PNA) downstream from the DOC and configured to store NOx from the exhaust gases at temperatures up to 150° C. A selective catalytic reduction (SCR) system may be downstream from the PNA and configured to reduce NOx.
In one embodiment, the PNA is configured to store NOx from the exhaust gases at temperatures up to 180° C. In another embodiment, the PNA is configured to release the stored NOx at temperatures above 200° C. The PNA may be configured to release substantially all stored NOx at a temperature of 350° C. or less. The DOC may have a palladium to platinum content of over 1:1, such as at least 3:1. The PNA may have a palladium to platinum content of at least 3:1. The exhaust system may emit less than 10 ppm of N2O during the first 2,000 seconds after engine start.
In one embodiment, the DOC may be coupled to the PNA by an exhaust conduit. In another embodiment, the DOC and the PNA may be contained in a single housing. The DOC and the PNA may be formed as layers on a single substrate. The PNA may contain substantially no alkali metals or alkaline-earth metals, such as barium. The PNA may contain one or more rare earth elements, such as cerium.
In at least one embodiment, a process of treating exhaust from a diesel engine is provided. The process may include introducing a first exhaust gas (FEG) to a diesel oxidation catalyst (DOC) from the engine to generate a second exhaust gas (SEG) and introducing the SEG to a passive NOx adsorber (PNA) from the DOC to generate a third exhaust gas (TEG). The PNA may store NOx from the SEG at temperatures up to 150° C. The TEG may be introduced to a NOx reduction system from the PNA.
In one embodiment, at temperatures above 200° C. the PNA releases stored NOx into the TEG. At a temperature of 400° C. or less, the PNA may release substantially all stored NOx into the TEG. In one embodiment, during a first 2,000 seconds after starting the diesel engine, an output exhaust gas (OEG) from the NOx reduction system includes less than 10 ppm of N2O. The diesel engine may substantially always run with a lean air to fuel ratio.
In at least one embodiment, an exhaust system for treating exhaust gases from a diesel engine is provided. The system may include a passive NOx adsorber (PNA) layer disposed on a substrate and configured to store NOx from the exhaust gases at temperatures up to 150° C. and a diesel oxidation catalyst (DOC) layer disposed on the PNA layer and configured to oxidize hydrocarbons in the exhaust gases. A selective catalytic reduction (SCR) system may be downstream from the PNA and DOC layers and configured to reduce NOx in the exhaust gases. In one embodiment, the PNA and DOC layers may each have a palladium to platinum content of at least 3:1 and the PNA layer may include substantially no alkali metals or alkaline-earth metals.
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. The figures are not necessarily to scale; some features may be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.
The time period during which the SCR catalyst is not yet up to its minimum operating level may be referred to as the “cold start” time period. The cold start period may last up to several minutes, for example, up to about 200 seconds. The primary pollutants that are emitted from a diesel engine are hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), and particulate matter (e.g., soot). As described in the Background, during the cold start period, the exhaust temperatures are too low for the SCR catalyst to reduce NOx, so the NOx is released into the atmosphere. A Passive NOx Adsorber (PNA) may be added to the exhaust system to adsorb and store at least some of the engine-out NOx during this cold start period. The PNA may contain platinum (Pt) and/or palladium (Pd) and NOx storage materials (e.g., ceria). Unlike the SCR system, the objective for the PNA is to store NOx and then release it at a later time, not to reduce or oxidize the NOx itself. The PNA may store the NOx until after the urea injection system is operational and the downstream SCR catalyst has reached its operating temperature (e.g., at least 150° C. or 200° C.), at which time the NOx is released from the PNA. The PNA therefore stores the NOx that would otherwise have passed through the SCR system unreacted until the SCR catalyst has reached a temperature that allows it to reduce the NOx that is released from the PNA.
The PNA was designed to replace the diesel oxidation catalyst (DOC) that has typically been the first catalyst brick in the diesel aftertreatment system. Therefore, in addition to storing and releasing NOx during the cold start period, the PNA is also configured to provide the DOC functions of oxidizing HC and carbon monoxide (CO). In addition, once the exhaust system is warmed up (e.g., about 200° C.), the Pt in the PNA may oxidize a portion of the engine-out NO to NO2 and thereby provide a mixture of NO and NO2 to the SCR catalyst, which improves its NOx reduction capability at low temperatures.
However, when the PNA is used as the first brick in the exhaust system, it is continually exposed to the full concentration of NOx and HC emitted from the engine. After the cold start period is over (e.g., about 200 seconds) and the exhaust system is up to full operating temperature, it has been discovered that the PNA can generate N2O as a result of a reaction between the hydrocarbons and NOx at temperatures around 200° C. This reaction may be referred to as lean NOx catalysis or hydrocarbon-SCR. This reaction has been found to be more pronounced over platinum than over palladium. The production of N2O is undesirable, since N2O is a very effective greenhouse gas. For example, N2O is hundreds of times more effective at trapping heat than carbon dioxide.
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It has been discovered that the N2O formation by the PNA can be decreased by placing a Pd-rich DOC in front of the PNA. The DOC, once at its operating temperature, may oxidize the hydrocarbons upstream of the PNA to carbon dioxide and water, thereby eliminating or reducing the amount of HC available to react with NOx (e.g., NO) over the PNA to form N2O. With reference to
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In contrast to LNTs, PNAs 16 are configured or adapted to operate at low temperatures, such as up to 150° C., 180° C., or 200° C. In addition, PNAs do not reduce NOx; they simply store the NOx during cold start temperatures and release the NOx at higher temperatures. By storing the NOx at low temperatures, the PNA gives the SCR system 18 (or other downstream system(s)) time to warm up. Once the downstream systems have reached their operating temperature, the PNA releases the stored NOx and allows the downstream systems to reduce, oxidize, or otherwise react the NOx into less harmful substances. The PNA 16 may be passive, in that it does not require any energy input, change in fuel composition, or other active steps to operate. This is in contrast to LNTs, which require alternating between lean and rich operation to regenerate the trap. Also, the PNA 16 may adsorb the NOx as nitrites, instead of nitrates (like LNTs). Nitrites may be less stable, allowing them to be released without a rich fuel cycle. By operating at low temperatures, the PNA may have a significant impact on NOx emissions directly after engine start, such as the first 100, 150, or 200 seconds. While this might seem like a short timeframe, relatively large amounts of harmful emissions may be released into the atmosphere during this time period due to the relative ineffectiveness of other emissions systems during the cold start. Since most of the tailpipe emissions from the vehicle may be emitted during the cold start period, reducing the cold start emissions can be important in meeting strict emission standards.
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DOCs are known in the art and will not be described in detail. The DOC 14 may be any device that is configured to oxidize hydrocarbons (HC) and carbon monoxide (CO) to form carbon dioxide (CO2) and water (H2O). The DOC 14 may be a pass-through device having a substrate and an active layer including one or more catalyst materials. The DOC 14 may not contain materials that store NOx, such as cerium. The substrate may have a plurality of channels or openings through which the exhaust gas passes. The substrate may be a monolith or extruded material, such as cordierite. The active layer may be applied to the substrate using a washcoat. While DOCs typically include platinum and palladium as the primary catalyst materials, in at least one embodiment, the DOC 14 may have more palladium than platinum (e.g., Pd:Pt ratio of >1). For example, the DOC 14 may have a Pd:Pt ratio of at least 2:1, 3:1, 4:1, or greater. In another embodiment, the DOC may include no platinum, or substantially no platinum (e.g., less than 1 wt. % of total catalyst material). As described above, it has been discovered that the use of platinum results in greater N2O production, compared to other catalysts. Accordingly, by reducing the amount of Pt in the DOC 14, the total N2O production may be reduced.
The PNA 16 may be any device that is configured to store NOx at relatively low temperatures, such as up to 150° C., 180° C. or 200° C. and begin to release the NOx at temperatures where other emissions systems start to operate, such as 180° C. or 200° C. For example, the PNA 16 may be configured to store NOx at temperatures from 0° C. or 20° C. to 150° C., 180° C., or 200° C. The PNA 16 may store and release the NOx by adsorption and desorption. In one embodiment, all or substantially all (e.g., at least 95%) of the stored NOx may be released by the PNA 16 at a temperature of up to 450° C., such as up to 400° C., or up to 350° C. The PNA 16 may store the NOx as nitrites or nitrates. The PNA 16 may be a pass-through device having a substrate and an active layer including one or more catalyst materials. The substrate may have a plurality of channels or openings through which the exhaust gas passes. The substrate may be a monolith or extruded material. Non-limiting examples of suitable substrate materials include cordierite, aluminum titanate, and silicon carbide. The active layer may be applied to the substrate using a washcoat.
The PNA 16 may include catalyst materials including platinum, palladium, and rhodium. In at least one embodiment, the PNA 16 may have more palladium than platinum (e.g., Pd:Pt ratio of >1). For example, the PNA 16 may have a Pd:Pt ratio of at least 2:1, 3:1, 4:1, or greater. In another embodiment, the PNA 16 may include no platinum, or substantially no platinum. The washcoat used to apply the active material may include materials such as alumina (e.g., Al2O3) and/or cerium oxide (e.g., CeO2), or other rare earth elements or oxides thereof. In at least one embodiment, the washcoat may have little or no alkali metals or alkaline-earth metals, such as barium. For example, the washcoat may have more alumina and/or cerium oxide than alkali metals or alkaline-earth metals (e.g., barium). In one embodiment, the washcoat includes less than 5 wt. % alkali metals or alkaline-earth metals (e.g., barium), such as less than 1 wt. % or no alkali metals or alkaline-earth metals (e.g., 0 wt. %), such as barium. Alkali metals or alkaline-earth metals may store NOx, but require high temperatures to release it, which may make them unsuitable for use in a PNA. As described above, it has been discovered that the use of platinum results in greater N2O production, compared to other catalysts. Accordingly, by reducing the amount of Pt in the PNA 16, the total N2O production may be reduced.
As described above, SCR systems 18 are well known in the art, and will not be described in detail. In general, SCR systems convert NOx into nitrogen, water, and carbon dioxide, depending on the system, using a catalyst and a reductant. The reductant is typically anhydrous ammonia, aqueous ammonia, or urea and may be added to a stream of flue or exhaust gas. SCR catalysts may include, zeolites or oxides of base metals. For example, zeolites including copper or iron or oxides of vanadium, molybdenum and tungsten may be used. As described above, the system 10 may include an SCR system 18 downstream from the DOC 14 and PNA 16. Additional NOx reduction systems may also be included downstream of the DOC 14 and PNA 16, either upstream or downstream from the SCR system 18. Alternatively, the SCR system 18 may be replaced by one or more other NOx reduction systems, for example, a LNT.
Embodiments of a system 10 for reducing NOx, and particularly N2O, emissions have been disclosed. The systems 10 may include a DOC 14 upstream from a PNA 16, which is upstream from a NOx reduction device, such as an SCR system 18. It has been discovered that PNAs can generate N2O, a powerful greenhouse gas, when the PNA receives both hydrocarbons and NOx from the engine 12. The N2O production may be greater when the PNA is platinum-heavy.
The disclosed systems 10 address this problem by including a DOC 14 upstream from the PNA 16, instead of the PNA replacing the DOC. The DOC 14, once at its operating temperature, oxidizes most or all of the HC before they reach the PNA 16, thereby drastically reducing the amount of one of the reactants in the reaction that forms N2O over the PNA 16. The systems 10 therefore address several challenges facing diesel engine exhaust systems. As just described, the systems 10 greatly reduce the amount of N2O produced and emitted into the atmosphere by providing a combination of a DOC and a PNA, with the DOC reducing the amount of hydrocarbons received by the PNA. The DOC may oxidize HC once it warms to it operating temperature, such as at temperatures of 200° C. and above. This includes the DOC reducing the HC received by the PNA while the PNA is in the temperature range of about 200 to 250° C., where N2O production is the greatest.
In addition, the PNA 16 facilitates greatly reduced NOx emissions from the system 10 during the cold start period (e.g., the first 200 seconds). The PNA 16 adsorbs the NOx at low temperatures, such as up to 150° C., 180° C. or 200° C. This time period is critical, because the downstream systems, such as a SCR system 18, are not effective at reducing the NOx until a minimum operating temperature is reached (e.g., about 200° C.). Therefore, any NOx that is passed to the SCR system 18 during the cold start will not be reduced and will be emitted from the vehicle. The PNA 16 adsorbs and holds the NOx during this cold start period and then releases it once the temperature of the system has reached a level where the downstream components are effective. Accordingly, the disclosed systems 10 provide NOx reduction during both “cold” and “hot” engine operation, while also greatly reducing the production of N2O by the PNA 16. The DOC may also protect the PNA from high temperatures and helps its durability. For example, the PNA may be located in a remote location from the DOC (e.g., connected by a conduit), which may lower the temperatures experienced by the PNA. Very high temperatures, such as over 700° C. or 800° C., may damage or reduce the durability of the precious metal catalysts in the PNA.
While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention.