# Patent

## Title
NOx adsorber diagnostics and automotive exhaust control system utilizing the same

## Abstract

A process for controlling an exhaust system can comprise flowing exhaust gas from the engine past a first oxygen sensor, through a NOx adsorber, past a second oxygen sensor, through a catalyst and past a third oxygen sensor, wherein the first oxygen sensor, the second oxygen sensor, and the third oxygen sensor, are in operable communication with an electronic control module, and using a switching delay between the first oxygen sensor and the second oxygen sensor to determine a NOx value, wherein the NOx value is selected from the group consisting of a NOx regeneration time, a stored NOx amount, a NOx storage efficiency, and combinations comprising at least one of the foregoing NOx values. A desulfurization process can be initiated when the NOx value is less than or equal to a first selected value. During the desulfurization process, when the third oxygen sensor signals a condition rich of stoichiometry, oxygen can be provided to the catalyst.

## Background
BACKGROUND
Automotive exhaust gas treatment devices have been used as original equipment by automotive manufacturers for many years as a way to reduce the hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxide (NOx) emissions from automotive internal combustion engines.
Some catalytic converters utilize a monolithic structure containing noble metals (e.g., platinum (Pt), palladium (Pd), rhodium (Rh), and/or the like) to provide catalytic afterburning of the engine emissions. More advanced systems utilize a three-way catalytic converter that is capable of simultaneously reducing the emissions of HC, CO. and NOx. To maximize the efficiency of these three-way converters, the engines are typically run at stoichiometry; that is, they are run at an air/fuel ratio in which the amount of air (oxygen) inducted into the cylinder is equivalent to the amount needed to burn all of the injected fuel. The stoichiometric air/fuel ratio is approximately 14.56. One problem with this mode of engine operation is that it is not always possible or desirable to operate the engine at stoichiometry. Rather, for purposes of maximizing fuel economy, it is often desirable to operate the engine in a lean combustion condition in which the amount of intake air is greater than is needed to burn the injected fuel.
Under lean-burn conditions, the air-to-fuel ratio is adjusted to be somewhat greater than the stoichiometric ratio (about 14.7 or greater), generally between about 19 and about 35, in order to realize a fuel economy benefit. However, when operating under lean-burn conditions, typical three-way catalyst systems are efficient in oxidizing unburned HC and CO, but are inefficient in reducing NOx emission. Conversely, during engine warm up and during periods of acceleration when torque is required, it is desirable for driveability to operate the engine in a rich combustion condition in which the amount of fuel injected is greater than the amount of fuel that the inducted air can burn. A rich combustion condition is one in which the air/fuel ratio is less than 14.56.
More recently, NOx adsorbers have been developed which store NOx during periods of lean engine combustion (i.e., excess air) and then periodically release the NOx during periods of rich combustion (i.e., excess fuel) so that the NOx can be catalytically reduced due to the presence of excess HC, CO, and H2.
The amount of NOx that can be stored in a NOx adsorber during any one lean cycle is dependent upon the state, volume, and temperature of the NOx adsorber. A problem with NOx adsorbers is that, over time, the adsorbers can deteriorate due to, for example, poisoning from sulfur oxides (SOx).
When the NOx adsorber has deteriorated to some extent, it needs to be regenerated by running the engine rich until the stored sulfur oxides are released. A common problem that remains unsolved, however, is that during the rich combustion conditions necessary for desulfurization of the NOx adsorber, the amount of HC and CO breakthrough (i.e., released from the system to the environment) increases.
Therefore, a need exists for a more effective system for desulfurization of the NOx adsorber; that is, for an exhaust system that enables improved desulfurization while decreasing HC and CO breakthrough. Additionally, there exists a need for a NOx adsorber diagnostic system that provides an accurate measure of the stored NOx.
There also exists a need for an engine control system, which provides control of the amount of NOx supplied to the NOx adsorber between regenerations.
SUMMARY
Disclosed herein are exhaust control systems, processes for controlling an exhaust system, and processes for controlling emissions of hydrogen sulfide in an exhaust stream. In one embodiment, the process for controlling an exhaust system can comprise flowing exhaust gas from the engine past a first oxygen sensor, through a NOx adsorber, past a second oxygen sensor, through a catalyst and past a third oxygen sensor, wherein the first oxygen sensor, the second oxygen sensor, and the third oxygen sensor, are in operable communication with an electronic control module, and using a switching delay between the first oxygen sensor and the second oxygen sensor to determine a NOx value, wherein the NOx value is selected from the group consisting of a NOx regeneration time, a stored NOx amount, a NOx storage efficiency, and combinations comprising at least one of the foregoing NOx values. A desulfurization process can be initiated when the NOx value is less than or equal to a first selected value. During the desulfurization process, when the third oxygen sensor signals a condition rich of stoichiometry, oxygen can be provided to the catalyst.
In one embodiment, the exhaust system can comprise: a NOx adsorber, a first oxygen sensor located upstream of and in fluid communication with the NOx adsorber, a second oxygen sensor located downstream of and in fluid communication with the NOx adsorber, a catalyst located downstream of and in fluid communication with the second oxygen sensor, a third oxygen sensor located downstream of and in fluid communication with the catalyst, and a control module operably connected to the first oxygen sensor, the second oxygen sensor, and the third oxygen sensor. The control module can be capable of initiating a desulfurization process when information from the first oxygen sensor and/or the second oxygen sensor signals a NOx regeneration time that is less than a selected value, and can be capable of switching an exhaust entering the catalyst during a desulfurization process to a stoichiometric or a lean combustion condition when the third oxygen sensor signals a rich stoichiometry.
The above-described and other features are exemplified by the following figures and detailed description.



DRAWINGS
Referring now to the figures, which are exemplary embodiments, and wherein the like elements are numbered alike:
FIG. 1 is a partial schematic view of an embodiment of an automotive exhaust control system;
FIG. 2 is a partial diagrammatic view of another embodiment of an automotive exhaust control system, showing the exhaust control system integrated into a vehicle electronic control module that is used to control operation of the vehicle engine;
FIG. 3 is a graph showing the delay between switching of the upstream and downstream O2 sensors at the beginning of the rich regeneration period for various amounts of stored NOx resulting from different agings of the NOx adsorber;
FIG. 4 is a graph showing the O2 sensor switching delay due to the release of NOx and O2 at the beginning of the rich regeneration period, and the O2 sensor switching delay due to the storage of O2 at the beginning of the succeeding lean period;
FIG. 5 is a graph showing the effect of release and storage of O2 in the NOx adsorber on the delay between the upstream and downstream O2 sensors;
FIG. 6 is a graph showing the correlation between the calculated NOx release time and the actual grams of NOx stored for a typical NOx adsorber at differing temperatures;
FIG. 7 is a process diagram depicting the operation of the exhaust control system of FIG. 2;
FIG. 8 is an exemplary NOx storage limit lookup table for use in the exhaust control system of FIG. 1 or FIG. 2; and
FIGS. 9 and 10 are flow charts that together depict the software process used in the exhaust control system of FIG. 2.



DETAILED DESCRIPTION
Disclosed herein are an exhaust control system and process for diagnosing the state of a NOx adsorber and for operating an internal combustion engine in a manner so as to minimize the emission of NOx from the NOx adsorber and preferably to provide effective control of H2S emission, and HC and CO breakthroughs during the NOx adsorber desulfurization process. The engine may be diesel, gas, or other fuel. It is noted that the terms “first,” “second,” and the like, herein do not denote any amount, order, or importance, but rather are used to distinguish one element from another, and the terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. Additionally, all ranges disclosed herein are inclusive and combinable (e.g., the ranges of “up to 25 wt %, with 5 wt % to 20 wt % desired,” are inclusive of the endpoints and all intermediate values of the ranges of “5 wt % to 25 wt %,” etc.). Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs. The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context, (e.g., includes the degree of error associated with measurement of the particular quantity). The notation “±10%” means that the indicated measurement may be from an amount that is minus 10% to an amount that is plus 10% of the stated value.
In one embodiment, the engine is operated using a lean/rich cycle in which NOx stored by the NOx adsorber during the lean portion of the cycle is released and catalytically reduced during the rich regeneration portion of the cycle. Once the stored NOx has been released, the engine is switched back to lean for the start of another cycle. The system utilizes a first oxygen sensor (e.g., a switching oxygen sensor, wide-range air/fuel sensor, or the like) located upstream of the NOx adsorber and a second oxygen sensor located downstream of the NOx adsorber, preferably between the NOx adsorber and a down stream catalyst (e.g., a three-way catalyst, an oxidation catalyst, selective catalytic reduction catalyst, or the like), the NOx adsorber being in fluid communication with both the first and the second oxygen sensors.
The determination of the amount of NOx stored by the adsorber is based upon a realization that the delay in switching between the upstream and downstream oxygen sensors during the rich-to-lean transition is due to the storage of oxygen by the NOx adsorber at the beginning of the succeeding lean period, and that this delay can be used to estimate the amount of time that was required to release the stored oxygen during the lean-to-rich transition. Thus, the delay in switching between the upstream and downstream oxygen sensors at the end of the rich regeneration period (the O2 storage time) is used as an indication of the amount of switching delay due to oxygen release during the lean-to-rich transition, and this O2 storage time delay is subtracted from the total delay between switching of the sensors during the lean-to-rich transition (the combined NOx/O2 release time) to thereby obtain an accurate estimate of the amount of sensor switching delay due to the release of the NOx alone (the NOx release time). That is, the NOx release time (NOx regeneration time) is determined in part by the algorithm:

NOx release time=the combined NOx/O2 release time−O2 release time, wherein the O2 release time=the measured O2 storage time.

Once the NOx release time is determined, the amount of NOx released by the adsorber during the rich regeneration can be determined and this amount can be taken as a good estimate of the amount of NOx that was stored during the previous lean period. In this way, the delay in switching of the sensors due to stored oxygen can be determined and eliminated from the NOx calculation without requiring separate lean/rich operating cycles.
Accordingly, an accurate estimate of the amount of NOx stored and released during a particular lean period can be determined using the following steps. First, the engine is run at a lean air/fuel ratio for a period of time and then is switched to a rich air/fuel ratio. The combined NOx/O2 release time is then determined based upon the amount of time between detection by the upstream oxygen sensor of a rich combustion condition and detection by the downstream oxygen sensor of the rich combustion condition. Next, the engine is switched back to operation at a lean air/fuel ratio and the oxygen storage time can be determined based upon the amount of time between detection by the upstream oxygen sensor of a lean combustion condition and detection by the downstream oxygen sensor of the lean combustion condition. Then, the NOx release time can be determined using the combined NOx/O2 release time and the oxygen storage time, e.g., by subtracting the oxygen storage time from the combined release time. Preferably, the NOx release time is used along with the exhaust flow rate and the magnitude of the air/fuel ratio during regeneration to determine the amount of NOx released (and therefore the amount stored during the previous lean period). Thereafter, operation of the engine at the lean air/fuel ratio is continued for a length of time that is dependent upon the calculated amount of NOx released.
This technique for determining the amount of NOx stored during the previous lean period (i.e., stored NOx amount) can be used as a part of an exhaust control system in which the stored NOx amount is used along with the exhaust gas temperature and other factors to determine the point at which the next rich regeneration will take place. This can be accomplished by using the stored NOx amount to determine a NOx storage limit that represents the amount of engine-out NOx that the adsorber is expected to be capable of handling at a particular efficiency. During the next lean period, the amount of engine-out NOx is then monitored and another rich regeneration is performed when the engine-out NOx reaches this NOx storage limit.
Also disclosed is a system for determining the storage efficiency of the NOx adsorber and controlling operation of the engine based upon the determined efficiency. The storage efficiency is determined using the amount of NOx stored during the previous lean period and the amount of engine-out NOx produced during that same period. The amount of stored NOx can be determined in the manner described above. The engine-out NOx can be determined in various manners using such factors as the air flow rate, engine load, engine speed, exhaust gas recirculation setting, spark advance, and the magnitude of the air/fuel ratio during the lean period. The NOx adsorber storage efficiency can then be used to determine the NOx storage limit that is utilized to determine the point at which the next rich regeneration should begin.
The NOx storage limit can be selected from values stored in memory and can be adjusted up or down depending upon whether the determined storage efficiency of the NOx adsorber is greater than or less than a desired efficiency. Then, when the amount of NOx stored falls below a selected threshold, a sulfur purge can be performed (thereby increasing the actual storage capacity) and, upon detecting that the storage efficiency has increased, the system can automatically respond by increasing the determined NOx storage limit that is used to determine how long the engine will be run lean each cycle. This provides closed loop control of the NOx emissions, allowing the system to utilize existing storage capacity in the NOx adsorber at any one time.
An abnormally short NOx regeneration time is indicative of a low NOx storage capacity in the adsorber. If this capacity drops below a certain level, it indicates that the adsorber may be severely sulfur-poisoned. Desulfurization can comprise:

    
    
        1. When the post NOx adsorber, second oxygen sensor (and associated control module) signals a NOx adsorber regeneration time shorter than a preset threshold value, a desulfurization routine may be triggered.
        2. Once a desired desulfurization temperature has been obtained (e.g., greater than or equal to about 650° C. at the NOx adsorber inlet), the engine can be switched to rich operation (A/F less than 14.56). Under these conditions, sulfur is released from the NOx adsorber in the form of H2S and SO2. The rich operation can be terminated when the third oxygen sensor (downstream from the catalyst), signals a condition rich of stoichiometry. This process can take a significant period of time because of the high oxygen storage capacity of the catalyst (the higher the oxygen storage capacity, the longer the period of rich operation). During this long rich pulse, sulfur will continuously release from the NOx adsorber. Meanwhile, the stored oxygen will react with any excess HC and CO minimizing breakthrough of HC and CO at the tailpipe. The stored oxygen will also oxidize any H2S released from the adsorber to SO2 thereby avoiding the undesirable release of H2S at the tailpipe. Hence, the third sensor facilitates diagnosis of the desulfurization process, and can help minimize HC, CO, and H2S slip from the tailpipe.
        3. Because the complete desulfurization of the poisoned adsorber uses a prolonged period of rich operation, following the detection of the rich condition at the third oxygen sensor, the engine can be briefly switched to a stoichiometric or slightly lean operating condition to re-charge the storage capacity of the catalyst before engine operation is switched back to a rich condition allowing the desulfurization process to continue as before. Thereby inhibiting undesirable release of HC, CO, and/or H2S.
        4. By repeating steps 2 and 3 for a selected number of times, desulfurization of the NOx adsorber is ensured and, upon returning to a normal NOx adsorber operating temperature and typical conditions of lean/rich modulation, an acceptable NOx adsorber regeneration time will be signaled by the second oxygen sensor, confirming the restoration of an acceptable NOx storage capacity.
    
    


In addition to using the third oxygen sensor, oxygen (e.g., air) from an external source can be supplied to the catalyst. The external source of oxygen, which may be supplied by a pump, can create a lean condition downstream of the NOx adsorber. This external source and optionally the pump can be the source and/or pump optionally employed to supply oxygen upstream of the start-up catalyst during cold start. The pump may be activated by the second oxygen sensor when the air/fuel ratio is rich or the stoichiometric point or is richer than a selected value. Optionally, the pump can be used in conjunction with a directional valve to create a lean condition (by dilution with air) downstream of the NOx adsorber and/or sulfur trap (with or without a bypass). Therefore, the air pump can be triggered by the second oxygen sensor anytime the air/fuel ratio is indicated to be rich of the stoichiometric point, or richer than a certain selected value. A benefit of this mode of operation is that, anytime a desulfurization process is occurring, air could be added to the exhaust upstream of the trailing catalyst, thereby facilitating oxidation of H2S, CO, and HC, and eliminating unwanted breakthrough of any of these components.
The catalyst, which preferably has a high oxygen storage capability, can be saturated with O2 during the lean operation, such that the stored O2 can be consumed during desulfurization. When all stored O2 from the catalyst has been depleted, the HC and CO breakthrough will occur and H2S will likely be emitted. Therefore, signals from the third O2 sensor will be used to trigger a lean operation to replenish the O2 stored at the three-way catalyst before desulfurization is resumed. This will effectively reduce HC/CO and H2S breakthrough. The system will enable the engine control module to diagnose the effectiveness of the emission system, with an optional signal malfunction light in operable communication therewith to indicate if the NOx adsorber and/or the three-way catalyst has catastrophic failure.
The control module may initiate a desulfurization process when the second oxygen sensor signals a NOx regeneration time that is less than or equal to a selected value. The control module may also initiate the provision of oxygen to the catalyst from an external source, or switching to a lean operating condition to control HC and CO breakthrough. The NOx regeneration time is approximately equal to the NOx release time and is determined in part by an algorithm comprising: NOx release time=the combined O2 and NOx release time−the O2 release time.
The control module initiates alternating lean and rich operating conditions. H2S, HC, and CO, released into the system, are oxidized by oxygen stored in the catalyst. A third oxygen sensor can be positioned downstream of the catalyst. The third oxygen sensor can be used to determine an amount of oxygen in the catalyst that has been depleted. Following the determination, the operation of the engine is switched to a stoichiometric or a lean combustion condition when the amount of oxygen that has been depleted is greater than or equal to a selected value.
Referring now to the drawings, and in particular to FIG. 1, there is shown an exemplary exhaust emission control system, generally shown as 11, including a disclosed NOx adsorber converter system. FIG. 1 depicts an embodiment of a vehicle exhaust control system 11 comprising, in sequence, an internal combustion engine 14; a first oxygen sensor 58; a start-up catalyst (e.g., start-up catalyst and/or sulfur trap) 13; an exhaust emission control device 56 comprising a NOx adsorber 15, a second oxygen sensor 59, and a catalyst 17 (e.g., a three-way catalyst, oxidation catalyst, or the like), a third oxygen sensor 60 downstream of the catalyst 17, and optionally a temperature sensor 62 disposed upstream of the NOx adsorber and downstream of the light-off converter 54. Optionally additional exhaust emission control devices can be employed, such as a particulate filter and/or sulfur trap (e.g., disposed upstream of the NOx adsorber 15 and downstream of the start-up catalyst 13 (not shown)).
Referring now to FIG. 2, there is shown another embodiment of an exemplary exhaust control system designated generally as 10, that is integrated in with an automotive engine electronic control module (ECM) 12. Exhaust control system 10 is used in connection with an internal combustion engine 14 (e.g., gasoline, diesel, or the like) having an air inlet section and an exhaust system. In general, exhaust control system 10 monitors engine performance and exhaust output and controls engine operation in a manner that seeks to maximize engine performance and fuel economy, while minimizing emission of HC, CO, NOx, and other contaminants.
The air inlet section includes an air intake 20 that is connected to an intake manifold (not shown) on engine 14 via a mass air flow sensor 22, throttle 24, and an exhaust gas recirculation (EGR) injection port 26. Air flow sensor 22 is used to provide electronic control module 12 with a signal indicative of the rate of air introduced into engine 14. The engine load is detected by a throttle position sensor 28 that is connected to throttle 24. The measured flow rate and engine load can be used along with other variables by the electronic control module 12 to determine the amount of NOx produced by the engine during each lean cycle, as will be discussed further below.
Electronic control module 12 can have any hardware design capable of performing the stated function of controlling the exhaust system, including a microprocessor (CPU), data, control, and address buses, digital to analog converters (D/A's), analog to digital converters (A/D's), a ROM, RAM, a battery-back up, otherwise non-volatile memory (NVM), a processor(s), computer(s), memory, storage, register(s), timing, interrupt(s), communication interface(s), and input/output signal interfaces, and the like, as well as combinations comprising at least one of the foregoing.
The exhaust system includes an exhaust manifold 50, EGR valve 52, light-off converter 54, exhaust emission control device 56, upstream O2 sensor 58, downstream O2 sensor 60, temperature sensor 62, and switching O2 or wide-range air/fuel (WRAF) sensor 64 at the inlet of exhaust emission control device 56. Light-off converter 54 is located close to exhaust manifold 50 (e.g., close coupled) and is used to promote fast light-off so as to reduce emissions when the engine 14 is first started. Exhaust emission control device 56 is an integrated unit that includes both a NOx adsorber function and downstream function. However, separate units are also possible with the O2 sensor 59 being disposed between the NOx adsorber and the catalytic converter. In the illustrated embodiment, the NOx adsorber can be incorporated into converter 56 as a separate catalyst brick (located upstream of the catalyst brick). O2 sensor 58 will typically be a wide-range air/fuel sensor that may additionally be used for other emissions purposes, such as engine control. However, in addition to or in lieu of sensor 58, switching O2 sensor 64 can be used. The downstream O2 sensor 60 and O2 sensor 59, can, individually, be switching O2 sensors or WRAF sensors. The sensors (temperature and oxygen), are in operable (preferably electrical) communication with the electronic control module 12.
Various catalysts have been developed, including three-way catalysts, oxidation catalysts, selective catalytic reduction catalysts, and the like. Such catalysts typically employ one or more noble metals, such as platinum (Pt), palladium (Pd), and/or rhodium (Rh), as well as other metals, oxides, and the like, disposed on support such as cordierite, ceramics (e.g., alumina), metals (e.g., stainless steel), and the like. Other metals and metal oxides may also be included. Additional promoters such as rare earths, as well as alkaline-earth metals (such as barium (Ba) and the like) have been suggested to improve catalyst performance.
Referring now to FIG. 3, there is shown a graph depicting the delay between switching of an upstream, or inlet, sensor and a downstream, or outlet, sensor for different stored amounts of NOx resulting from different agings of the NOx adsorber. The data used to generate this graph was measured using a 1.4 liter NOx adsorber operating at a temperature of 350° C. with a flow rate of 10 grams/sec and regeneration air/fuel ratio of 12:1. As this graph indicates, the delay between the inlet sensor (shown as a solid line) and the outlet sensor (shown as a broken line) depends on the amount of NOx stored in the NOx adsorber.
The delay between the upstream and downstream O2 sensors at the beginning of the rich regeneration cycle includes a component that is due to the release of stored NOx and a component that is due to the release of stored O2, and as shown in FIG. 4, this delay is therefore referred to herein as the combined NOx/O2 release time. To accurately determine the amount of NOx stored in the NOx adsorber, it is necessary to determine from this combined release time the amount of delay that is due to the NOx release alone. This can be accomplished by determining the amount of the combined release time that is due to oxygen release alone and then subtracting that time from the combined release time, as indicated by the following equation:

NOx release time=the combined NOx/O2 release time−O2 release time   (1)

This O2 release time can be estimated using the delay time between the upstream 64 and downstream 60 sensors during the rich-to-lean transition. More specifically and as shown in FIG. 4, the delay at the beginning of the succeeding lean period is due to the storage in the NOx adsorber of the excess oxygen coming from the engine. Upon switching to lean operation, the excess oxygen immediately causes the upstream O2 sensor to indicate a lean combustion condition. However, this excess oxygen is stored in the NOx adsorber and is not detected by the downstream O2 sensor until a short time later, after the O2 storage capacity of the NOx adsorber has been exceeded. Assuming that the time required to store oxygen in the NOx adsorber is approximately equal to the time required to release the stored oxygen, this measurable delay at the beginning of the lean period provides a good estimate of the amount of the combined NOx/O2 release time that is due to release of the O2 alone. Thus, the measured O2 storage time can be substituted into equation (1) above for the O2 release time to yield the following equation:

NOx release time=the combined NOx/O2 release time−O2 storage time   (2)

The graph of FIG. 4 was generated using data measured with a 1.4 liter NOx adsorber that had been aged ten hours at 400° C. and that was running at a 480° C. bed temperature with a flow rate of 10 grams per second (g/s) and air/fuel (A/F) ratio of 12:1 during the rich regeneration. This graph illustrates the O2 storage time and the O2 release time.
Once the NOx release time has been determined, the amount of NOx released can be determined, this number can be used as an estimate of the total amount of NOx stored during the previous lean period. Preferably, the measured O2 storage time is subtracted from the combined release time measured during the same regeneration cycle. However, as an alternative, the O2 storage time from one cycle can be subtracted from the combined release time measured during the next rich regeneration cycle. Moreover, for a given temperature, flow rate, and rich air/fuel ratio, if the O2 storage time does not vary significantly from one cycle to the next, then it can be measured only periodically for different temperatures and used to update tables or equations that represent the O2 storage time as a function of temperature, flow rate, and rich air/fuel magnitude. These tables or equations could then be used along with the current temperature, flow rate, and commanded air/fuel ratios to obtain an O2 storage time for use in determining the NOx release time according to equation (2). Whether using wide-range or switching sensors to determine the various delay times, it is necessary to determine the thresholds at which the sensor output will be considered indicative of the lean and rich combustion conditions. For example, in the graph shown in FIG. 4, the sensor outputs vary between zero and approximately one volt, with a lean combustion condition giving rise to a lower voltage and a rich condition giving rise to a higher voltage. If desired, a single intermediate voltage (such as 0.5 volts) could be used as the threshold for determining lean versus rich combustion, in which case any voltage less than 0.5 volts would be indicative of a lean combustion condition and any voltage above 0.5 volts indicative of a rich condition. Preferably, however, as indicated by the arrows in FIG. 4, values much closer to the limits of the sensor voltage are used as minimum thresholds for recognizing the engine operation as either being lean or rich. In particular, a rich combustion condition is only recognized when the sensor voltage equals or exceeds 0.8 volts and a lean condition is only recognized when the sensor voltage is less than or equal to 0.2 volts. Alternatively, one or both of these thresholds can be set at a certain percentage (e.g., 95%) of the full sensor voltage swing.
The use of equation (2) assumes that the O2 storage time provides a good estimation of the O2 release time during the preceding and succeeding rich regeneration periods. As indicated in the graph of FIG. 5, the validity of this assumption has been empirically demonstrated. The data used for this graph was measured using a 1.7 liter NOx adsorber that had been aged ten hours at 400° C. and that was running at a 480° C. bed temperature with a flow rate of 10 grams/sec and air/fuel ratio of 12:1 during rich regeneration. The experiment was run such that very little NOx (0.18 grams) was stored by the NOx adsorber so that the effect of O2 storage and release on the delay between the upstream and downstream sensors could be compared. As indicated in FIG. 5, the O2 storage time is substantially the same as the time required to release the stored O2 at the beginning of the rich regeneration period.
Referring now to FIG. 6, it has also been empirically determined that there is good correlation between the NOx release time calculated according to equation (2) and the actual amount of NOx stored, and that this correlation is substantially independent of NOx adsorber aging, adsorber volume, and bed temperature during the regeneration. The data shown in the figure was collected at different temperatures for a particular NOx adsorber technology with the lean cycle and the rich regeneration being maintained at the same temperature. The data shown is for different volumes of the adsorber (1.4 L and 2.8 L) and after various aging conditions. The data shown resulted from tests performed on a fresh adsorber and after aging at 400° C. for 10, 30, and 50 hours. The data also shows the results of tests run on samples after aging at 1,000° C. for 10, 30, and 50 hours. While the amount of NOx stored is a strong function of the adsorber volume, the aging condition, and the temperature during the lean cycle, the relationship between the NOx release time and the amount of NOx stored is basically independent of these parameters. The experimental data shows that, over a wide range of temperatures, there is a fairly linear relationship between the amount of NOx stored in the NOx adsorber and the NOx release time calculated according to equation (2). Thus, while the temperature and state of the NOx adsorber can have a substantial impact on its storage capacity, the temperature and state of the NOx adsorber do not significantly affect the relationship between the amount of stored NOx and the delay between the upstream and downstream O2 sensors. Similarly, it has been found that the relationship between the amount of stored NOx and this delay time is also substantially independent of NOx adsorber volume.
Referring next to FIG. 7, there is shown a process diagram that is used by engine electronic control module 12 of FIG. 2 to provide closed loop control of the amount of engine-out NOx produced during each lean/rich cycle of engine operation. This closed loop control allows the system to provide very high conversion levels. In general, the process involves determining the amount of NOx produced by the engine during a previous period of lean combustion, determining the amount of NOx adsorbed by the NOx adsorber during that lean period, determining the storage efficiency of the NOx adsorber, determining a NOx storage limit which represents the NOx storage capacity of the NOx adsorber at a particular level of storage efficiency, monitoring the amount of NOx produced by the engine during the next lean period, and initiating a rich regeneration when the amount of NOx produced by the engine reaches the NOx storage limit. The NOx storage limit is determined using temperature-dependent stored NOx values that are adjusted upwards if the measured storage efficiency is greater than a selected desired efficiency, adjusted downwards if the measured storage efficiency is less than the desired efficiency, and maintained if the measured efficiency is equal to the desired efficiency.
Beginning at block 70, upon completion of a rich regeneration, a new lean period is initiated and the NOx release time can be calculated using equation (2) along with the most recently measured combined NOx/O2 release time and O2 storage time. This is indicated at block 72. Then, as shown by block 74, using the magnitude of the regeneration air/fuel ratio and the measured mass air flow during regeneration, the amount of NOx released (and therefore stored) by the NOx adsorber can be determined. This determination can be accomplished either using a look-up table or an equation that relates NOx release time to the amount of NOx released. At the same time, the system begins determining the cumulative engine-out NOx produced by the engine since the start of the new lean period. The determination of engine-out NOx can be accomplished using such parameters as the engine load, engine speed, EGR valve setting, spark advance, and the current lean air/fuel ratio. The first two of these are measurements use the throttle position sensor 28 and engine speed sensor 48, respectively (see FIG. 2). The last three of these are determined by engine electronic control module 12 as a part of separate engine operation processes, which are known to those skilled in the art. Using these parameters, the concentration of NOx in the engine emissions can be determined using equations or a table lookup, as indicated by block 76. Then, the determined NOx concentration can be combined with the measured mass air flow rate at block 78 to generate a NOx flow rate which, when integrated over time at block 80, provides an estimate of the total engine-out NOx. Other similar techniques can be used to determine the amount of engine-out NOx. See, for example, U.S. Pat. No. 5,437,153 to Takeshima, et al.
Moving now to block 84, the cumulative engine-out NOx stored during the last lean period is saved each cycle, as indicated at block 82, and is used along with the stored NOx amount determined at block 74 to calculate the storage efficiency of the NOx adsorber during that last lean period. This can be done using the following equation:




  
    
      
        
          
            NO
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          adsorber
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          ⁢
          storage
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          ⁢
          efficiency
        
        =
        
          
            stored
            ⁢
            
              
            
            ⁢
            
              NO
              x
            
            ⁢
            
              
            
            ⁢
            amount
          
          
            engine
            ⁢
            
              -
            
            ⁢
            out
            ⁢
            
              
            
            ⁢
            
              NO
              x
            
          
        
      
    
    
      
        (
        3
        )
      
    
  




Then, using the determined storage efficiency along with the measured temperature during the current lean period, the NOx storage limit for the current temperature is determined, as indicated at block 86. As will be understood from the description further below, this NOx storage limit is the maximum amount that the adsorber can store at a particular desired efficiency (e.g., at 90%). That is, although the NOx adsorber may be able to store more NOx than is represented by the determined NOx storage limit, it can only do so at a lower efficiency than is desirable. That would result in an undesirably large amount of NOx passing through the NOx adsorber and being emitted into the environment. Thus, the NOx storage limit represents the amount of NOx to be adsorbed during the current lean period. Once the NOx storage limit is determined, it is compared at block 88 to the cumulative engine-out NOx that is, of course, ever-increasing as the lean period progresses. Once the engine-out NOx reaches the NOx storage limit, engine operation is switched to rich to regenerate the NOx adsorber, as indicated back at block 70. The cycle then repeats.

The determination of the NOx storage limit can be accomplished by an equation or table lookup that provides a NOx value (in grams) representing the amount of engine-out NOx that the NOx adsorber is expected to be able to handle at the desired efficiency. This NOx value will be temperature dependent and, therefore, the temperature of the current lean period is used at this point so that the system can provide a NOx value that is appropriate for the current bed temperature. An exemplary lookup table is shown in FIG. 8. The spectrum of temperatures over which significant NOx adsorption is possible has been divided into a number of ranges. For each range, there is stored in non-volatile memory a NOx value that represents the grams of engine-out NOx that the NOx adsorber can handle at a particular storage efficiency. Determining the NOx storage limit then simply requires reading from memory the NOx value associated with the temperature range that spans the current temperature.
To provide negative feedback, the actual storage efficiency determined at block 84 is compared to the predetermined desired efficiency and, if the actual storage efficiency is greater, the NOx value produced by the equation or table lookup can be proportionally increased (e.g., by 5%), or, if the actual efficiency is less, the NOx value can be proportionally decreased (e.g., by 10%). That is, if the actual storage efficiency is found to be greater than the desired efficiency, then the NOx storage limit obtained using the equation or table lookup is in actuality too low (since it is based on an assumed lower efficiency) and needs to be increased. Conversely, if the storage efficiency is less than the desired efficiency, then the NOx storage limit is too high and should be decreased. If the efficiency equals the desired efficiency, then the NOx storage limits are maintained at the current levels. This will have the effect of either increasing, decreasing, or maintaining the length of the current lean period since the engine is operated lean until the amount of engine-out NOx equals that NOx limit.
Alternatively, stabilized closed loop control can be accomplished, not by simply adjusting the NOx value produced by the equation or table lookup, but by adjusting the equation parameters or the table values themselves. This adjustment can either be a percentage of the stored values (e.g., 5% or 10% as discussed above), or can be in the form of proportional error correction; that is, proportional to the difference between the determined storage efficiency and the desired storage efficiency. Moreover, the adjustment of the equation parameters or table values can be done according to temperature, either such that the NOx values at all temperatures are similarly adjusted, or so that the adjustment is more significant for certain temperature ranges than for others. For example, if the storage efficiency during the last lean period is below the desired level, a percentage decrease of 15% could be applied to the NOx storage amount in the temperatures of about 250° C. to about 275° C., while a percentage decrease of 12% could be applied to the NOx storage amount at about 275° C. to about 300° C. Also, rather than comparing the actual storage efficiency to a single predetermined desired efficiency, a window can be used, with the stored values of the NOx storage limit being used without adjustment up or down unless the actual efficiency is found to be outside this window. As will be apparent to those skilled in the art, by adjusting the NOx storage limit that is used to determine the length of the lean period, the system automatically adjusts to the current state of the NOx adsorber. This not only allows the system to reduce the lean period as the state of the NOx adsorber degenerates over time, but also allows the system to increase the lean period when the state of the NOx adsorber improves, such as after a sulfur purge.
Turning now to FIGS. 9 and 10, there is shown a flow chart of the program used by electronic control module 12 to carry out the process of FIG. 7. This program can be stored in ROM and executed by a microprocessor either as a separate process or as part of an overall engine control algorithm. The process begins following start block 90 where the engine can be operated lean (block 92) during which time the engine-out NOx can be determined (block 94) and, as indicated at block 96, can then be compared with the NOx storage limit obtained using either an equation or table lookup. The first time through this loop, there will have been no calculated NOx storage efficiency from a previous iteration, so that the NOx value obtained from the equation or table lookup will not be adjusted up or down. If the cumulative amount of engine-out NOx for the current lean period is less than the NOx storage limit, then the NOx adsorber is still capable of NOx storage at or above the desired efficiency and the process returns to block 92 where the lean engine operation is continued. This loop repeats until the engine-out NOx equals or exceeds the NOx storage limit, at which point the process flow moves to block 98 where the rich regeneration is initiated. During the regeneration, the O2 sensors are monitored and, at block 100, the combined NOx/O2 release time is determined once the downstream O2 sensor switches fully to indicate that it sees a rich combustion condition. Then, at block 102, a check is made to determine if the regeneration is complete.
This check can be carried out by, for example, determining if the downstream O2 sensor has reached a certain percentage (e.g., 95%) of the engine-out sensor's full-scale swing. If not, the process loops back on itself while regeneration continues. Once it is determined that the regeneration is complete, the process moves to block 104, where the engine operation is switched back to lean. The O2 sensors are again monitored and, at block 106, the process determines the O2 storage time, which, as discussed above in connection with FIG. 4, is the delay between switching of the sensors to the lean combustion condition.
Now that the combined NOx/O2 release time and the O2 storage time have been determined, the NOx release time can be determined using equation (2), as indicated at block 108. The amount of NOx released (and, thus, the stored NOx amount) can then be determined at block 110 using the regeneration air/fuel ratio and air flow rate data discussed above in connection with FIG. 7. This determination can be made, for example, using a look-up table derived from FIG. 6 that relates the NOx release time, flow rate, and regeneration air/fuel ratio to the grams of NOx released. Next, the NOx adsorber storage efficiency is determined using equation (3), as indicated at block 112. Once the storage efficiency is determined, the process is ready to determine the next value of the NOx storage limit, which will be used to determine the amount of engine-out NOx permitted during the current lean period before regeneration is begun. Although this next value of the NOx storage limit can be found using equations or table lookups, in the process described below a table lookup will be assumed, with the table comprising NOx values at the desired efficiency for each of several different bed temperatures.
To determine the next value of the NOx storage limit, a check is first made at block 114 to determine if the NOx adsorber is within the range of temperatures suitable for NOx adsorption. If not, then a pre-selected NOx storage limit is used, as indicated at block 116, and current loop ends at block 118 with the process then returning to start block 90 for another iteration using the pre-selected NOx storage limit obtained at block 116. If, at block 114, the bed temperature is within range, the process moves to block 120 where a check is made to determine if the storage efficiency of the NOx adsorber is greater than or equal to the desired efficiency. If so, a check is made at block 122 to determine if the storage efficiency is actually greater than the desired efficiency. If it is, then the NOx values stored in the lookup table are increased, as indicated by block 124. Thereafter, the process moves to block 126 where the (now adjusted) NOx storage limit is obtained from the table using the current bed temperature. If at block 122, the storage efficiency had equaled the desired efficiency, then no adjustment of the NOx table values is needed and the process would move directly to block 126 to obtain the new NOx storage limit from the table. The process then moves to block 118 for another iteration.
If, back at block 120, the storage efficiency was determined to be less than the desired efficiency, then the process moves to block 128 where a check can be made to determine if the NOx release time calculated back at block 108 is less than a pre-selected desired minimum value. If so, this indicates that the state of the NOx adsorber has degenerated to a point at which a sulfur purge is needed, as will be discussed below. However, if the NOx release time is still above the pre-selected minimum acceptable value, then the process moves to block 130 where the NOx values stored in the lookup table are decreased, following which the process moves to block 126 and then to block 118 to perform another iteration. If, at block 128 it is determined that a sulfur purge is necessary, then the process moves to block 132 where a check is made to determine whether a sulfur purge has recently been performed. If so, this indicates that another sulfur purge will not adequately improve the state of the NOx adsorber and the process moves to block 134 where the engine is taken out of the lean/rich cycling and is run simply at stoichiometry. If desired, multiple sulfur purges can be performed prior to making a decision that a malfunction condition exists. Then, at block 136, the malfunction indicator light is illuminated to warn the driver of the abnormal engine operating condition. If, at block 132 no sulfur purge has recently been performed, the process moves to block 138 where a sulfur purge is carried out before moving to block 126 to obtain the next value of the NOx storage limit before beginning another iteration.
As will be appreciated, the storage efficiency will normally increase following the sulfur purge and this increase will be detected by the system, resulting in the stored NOx storage limit values being increased to take advantage of the greater NOx storage capacity resulting from the sulfur purge. An engine-out NOx amount representing the amount of NOx produced by the engine during a period of time may be determined; and the engine may be operated in a lean combustion condition for a duration of time that is dependent upon the stored NOx amount and the engine-out NOx amount. Alternatively, a NOx adsorber storage efficiency may be determined using the stored NOx amount and the engine-out NOx amount; and the engine may be operated in a lean combustion condition for a duration of time that is dependent upon the NOx adsorber storage efficiency.
Another alternative comprises determining a NOx storage limit for the NOx adsorber; determining an engine-out NOx amount while operating the engine at the lean combustion condition during the duration of time; and switching operation of the engine from the lean combustion condition to the rich combustion condition when the engine-out NOx equals or exceeds the NOx storage limit. The NOx storage limit represents the amount of NOx that can be stored by the NOx adsorber at one or more particular storage efficiencies.
The step of determining a NOx storage limit may further comprise: obtaining a value representing the NOx storage limit; increasing the value if the NOx adsorber storage efficiency is greater than a first selected efficiency; decreasing the value if the NOx adsorber storage efficiency is less than a second selected efficiency; and thereafter using the value as the NOx storage limit. According to one embodiment, the first selected efficiency and the second selected efficiency are each equal to the same or different pre-selected efficiency.
Yet another alternative comprises determining a NOx storage limit using the stored NOx amount; determining an engine-out NOx amount while operating the engine at the lean combustion condition during the period of time; and switching operation of the engine from the lean combustion condition to the rich combustion condition when the engine-out NOx equals or exceeds the NOx storage limit. During operation of the engine in the rich combustion condition, the engine is operated at an air/fuel ratio with the exhaust gases being exhausted from the engine at a measurable flow rate; and the step of determining a stored NOx amounts further comprises determining the stored NOx amount using values indicative of the NOx release time, the air/fuel ratio, and the flow rate. An embodiment of the process may further comprise the step of measuring the flow rate of air entering the engine and using the flow rate of the air to determine the measurable flow rate. The disclosed exhaust control system or process provides many advantages in addition to those pointed out above. For example, the system or process has advantages over a system wherein high levels of H2S scavengers are incorporated into a trailing catalyst. Because during rich desulfurization of the NOx adsorber, H2S concentrations are very high, efficient scavenging is not possible. The disclosed method can also be useful in bypass systems where the NOx adsorber is being protected from high temperature using a diverter valve. The disclosed method can also be employed for the desulfurization of a sulfur trap rather than a NOx adsorber.
One advantage of this new method is that desulfurization is accomplished by a sequence of alternating high temperature lean and rich operations instead of a single long rich operation. This alternation can take several minutes, a longer overall period than that of other strategies. Although the rich operation is terminated before adsorber desulfurization is completed, and is therefore repeated multiple times, this sequential desulfurization is reported to intrinsically generate less H2S. Additionally, the use of a high OSC catalyst downstream of a NOx adsorber allows for a more effective desulfurization of the NOx adsorber by prolonging the rich desulfurization time without HC and CO breakthrough. The high OSC catalyst serves as a rechargeable oxygen reservoir for oxidizing the HC and CO. During a repetitive lean/rich desulfurization schedule, the achievement of a longer rich regeneration period results in less total time than is required in using a system wherein there is no downstream high OSC catalyst. When desulfurization yields HC and CO breakthroughs, the process must be restricted to minimum time and repeated more often. Furthermore, if H2S is released from the NOx adsorber, it will be transformed to SO2 over the post high OSC catalyst. Also, the third oxygen sensor downstream of the catalyst will effectively utilize diagnostics strategies designed for detecting the completion of NOx regeneration and loss of NOx storage attributable to sulfur poisoning. Signals from the third oxygen sensor may be used in one embodiment to prevent HC and CO breakthroughs during the desulfurization. The trailing high OSC catalyst reduces the amount of HC, CO, and NOx breakthrough during rich pulses utilized for normal regeneration of the NOx adsorber; provides better system control at stoichiometry, and reduces NOx emissions at low temperature. Because the disclosed system, employing an air pump to assist in maintaining the high OSC catalyst, allows desulfurization to occur using a single prolonged rich excursion, the time required for the after-treatment system to be maintained at an elevated temperature is minimized. This in turn minimizes thermal damage of the catalytic components, while simultaneously minimizing the fuel economy penalty which is expected to be incurred by operating the engine in a mode which generates a high temperature in the sulfur-poisoned component, the high temperature being necessary for effective desulfurization.
While the invention has been described with reference to an exemplary embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

## Claims

1. A process for controlling an exhaust system for an internal combustion engine, comprising:
flowing exhaust gas from the engine past a first oxygen sensor, through a NOx adsorber, past a second oxygen sensor, through a catalyst and past a third oxygen sensor, wherein the first oxygen sensor, the second oxygen sensor, and the third oxygen sensor, are in operable communication with an electronic control module;
using a switching delay between the first oxygen sensor and the second oxygen sensor to determine a NOx value, wherein the NOx value is selected from the group consisting of a NOx regeneration time, a stored NOx amount, a NOx storage efficiency, and combinations comprising at least one of the foregoing NOx values; and
initiating a desulfurization process when the NOx value is less than or equal to a first selected value, wherein the desulfurization process comprises
increasing a temperature in the exhaust gas to a desulfurization temperature;
switching the engine operation from a normal combustion condition to a rich combustion condition to produce a rich exhaust gas;
monitoring the rich exhaust gas exiting the catalyst; and
providing oxygen to the catalyst when, during the desulfurization process, the third oxygen sensor signals a third condition rich of stoichiometry.

2. The process of claim 1, wherein providing oxygen to the catalyst further comprises switching the engine operation to a stoichiometric or a lean combustion condition.

3. The process of claim 2, wherein the engine is switched to the stoichiometric or the lean combustion condition for a period of time sufficient to increase the amount of oxygen stored in the catalyst to a desired oxygen level.

4. The process of claim 1, wherein providing oxygen to the catalyst further comprises providing the oxygen from an external source to the exhaust gas downstream of the NOx adsorber.

5. The process of claim 1, wherein the switching delays comprise a first time delay between (the first oxygen sensor switching a first sensor first value to a first sensor second value) and (the second oxygen sensor switching from a second sensor first value to a second sensor second value); and
a second time delay between (the first oxygen sensor switching from the first sensor second value to the first sensor first value) and (the second oxygen sensor switching from the second sensor second value to the second sensor first value).

6. The process of claim 1, wherein the desulfurization process further comprises repeating the
switching the engine operation from a normal combustion condition to a rich combustion condition;
monitoring the exhaust gas exiting the catalyst; and
providing oxygen to the catalyst when, during the desulfurization process, the third oxygen sensor signals a third condition rich of stoichiometry;

wherein the repeating continues until the NOx regeneration time is greater than or equal to a second selected value.

7. The process of claim 1, further comprising
operating the engine under lean combustion conditions to produce a lean exhaust gas at the normal operating temperature;
monitoring a first air/fuel ratio of the lean exhaust gas when passing the first oxygen sensor as a first sensor first value;
monitoring a second air/fuel ratio of the lean exhaust gas exiting the NOx adsorber with the second oxygen sensor as a second sensor first value;
operating the engine under rich combustion conditions to produce a rich exhaust gas;
monitoring the first oxygen sensor for a first sensor second value indicating a switch to the rich combustion conditions;
monitoring the second oxygen sensor for a second sensor second value indicating the switch to the rich combustion conditions;
determining a combined NOx/O2 release time that is related to an amount of time delay between (the first oxygen sensor switching from the first sensor first value to the first sensor second value) and (the second oxygen sensor switching from the second sensor first value to a second sensor second value);
switching the engine operation to the lean combustion condition;
determining an O2 storage time that is related to an amount of time delay between (the first oxygen sensor switching a from the first sensor second value back to the first sensor first value) and (the second oxygen sensor switching from the second sensor second value back to the second sensor first value);
determining the NOx regeneration time using the combined NOx/O2 release time and the O2 storage time;
determining a stored NOx amount and using the stored NOx amount to determine a NOx storage time and NOx storage efficiency;
determining whether the stored NOx amount is less than or equal to the first selected value;
when the stored NOx amount is less than or equal to the first selected value, initiating the desulfurization process; and
switching to the lean combustion conditions at the normal operating temperature when the desulfurization process is complete.

8. The process of claim 7, wherein the desulfurization process further comprises
switching to the lean combustion conditions at the desulfurizing temperature when the third oxygen sensor signals a rich stoichiometry;
switching back to the rich combustion conditions at the desulfurizing temperature when the third oxygen sensor signals a lean stoichiometry; and
repeating the switching to the lean combustion conditions at the desulfurizing temperature and the switching back to the rich combustion conditions at the desulfurizing temperature, until the NOx adsorber is desulfurized.

9. The process of claim 7, wherein the NOx regeneration time is determined in part by an algorithm comprising:
NOx regeneration time=the combined and NOx/O2 release time-the O2 release time.

10. The process of claim 7, wherein providing oxygen to the catalyst further comprises providing the oxygen from an external source to the rich exhaust gas downstream of the NOx adsorber.

11. An exhaust system, comprising:
a NOx adsorber;
a first oxygen sensor located upstream of and in fluid communication with the NOx adsorber;
a second oxygen sensor located downstream of and in fluid communication with the NOx adsorber;
a catalyst located downstream of and in fluid communication with the second oxygen sensor;
a third oxygen sensor located downstream of and in fluid communication with the catalyst; and
a control module operably connected to the first oxygen sensor, the second oxygen sensor, and the third oxygen sensor;
wherein the control module is capable of initiating a desulfurization process when information from the first oxygen sensor and/or the second oxygen sensor signals a NOx regeneration time that is less than or equal to a first selected value; and
wherein the control module is capable of switching an exhaust entering the catalyst during a desulfurization process to a stoichiometric or a lean combustion condition when the third oxygen sensor signals a condition rich of stoichiometry.

12. The exhaust system of claim 11, further comprising a temperature sensor disposed upstream of and in fluid communication with the NOx adsorber, and in operable communication with the control module.

13. The exhaust system of claim 11, further comprising a pump capable of providing oxygen to the catalyst from an external source.

14. The exhaust system of claim 13, wherein the pump is capable of providing the oxygen to downstream of the NOx adsorber.

15. The exhaust system of claim 11, further comprising a start-up catalyst disposed upstream of the NOx adsorber.

16. The exhaust system of claim 11, further comprising a particulate filter disposed upstream of the NOx adsorber and downstream of the start-up catalyst.