PASSIVE AMMONIA-SELECTIVE CATALYTIC REDUCTION FOR NOx CONTROL IN INTERNAL COMBUSTION ENGINES

TECHNICAL FIELD

[0001] This disclosure is related to control of aftertreatment of NOx emissions in internal combustion engines.

BACKGROUND

[0002] The statements in this section merely provide background information related to the present disclosure and may not constitute prior art. [0003] Manufacturers of internal combustion engines are continually developing new engine control strategies to satisfy customer demands and meet various regulations. One such engine control strategy comprises operating an engine at an air/fuel ratio that is lean of stoichiometry to improve fuel economy and reduce emissions. Such engines include both compression- ignition and lean-burn spark-ignition engines.

[0004] Lean engine operation may produce oxides of nitrogen (NOx), a known by-product of combustion, when nitrogen and oxygen molecules present in engine intake air disassociate in the high temperatures of combustion. Rates of NOx production follow known relationships to the combustion process, for example, with higher rates of NOx production being associated with higher combustion temperatures and longer exposure of air molecules to the higher temperatures.

[0005] NOx molecules, once produced in the combustion chamber, can be reduced to nitrogen and oxygen molecules in aftertreatment devices. Efficacy of known aftertreatment devices are largely dependent upon operating conditions, such as device operating temperature driven by exhaust gas flow temperatures and engine air/fuel ratio. Additionally, aftertreatment devices include materials prone to damage or degradation in-use due to exposure to high temperatures and contaminants in the exhaust gas feedstream. [0006] Known engine operating strategies to manage combustion to increase fuel efficiency include operating at a lean air/fuel ratio, using localized or stratified charge combustion within the combustion chamber, while operating in an unthrottled condition. While temperatures in the combustion chamber can get high enough in pockets of combustion to create significant quantities of NOx, the overall energy output of the combustion chamber, in particular, the heat energy expelled from the engine through the exhaust gas flow can be greatly reduced from normal values. Such conditions can be challenging to exhaust aftertreatment strategies, as the aftertreatment devices frequently require elevated operating temperatures, driven by the exhaust gas flow temperature, to operate adequately to treat NOx emissions. [0007] Aftertreatment systems include catalytic devices to generate chemical reactions to treat exhaust gas constituents. Three-way catalytic devices (TWC) are utilized particularly in gasoline applications to treat exhaust gas constituents. Lean NOx adsorbers (NOx trap) utilize catalysts capable of storing some amount of NOx, and engine control technologies have been developed to combine these NOx adsorbers with fuel efficient engine

control strategies to improve fuel efficiency and still achieve acceptable levels of NOx emissions. One known strategy includes using a lean NOx adsorber to store NOx emissions during lean operations and then purge and reduce the stored NOx during rich engine operating conditions with a TWC to nitrogen and water. Diesel particulate filters (DPF) trap soot and particulate matter in diesel applications, and the trapped material is periodically purged during high temperature regeneration events.

[0008] One known aftertreatment device comprises a selective catalytic reduction device (SCR). The SCR device includes catalytic material that promotes the reaction of NOx with a reductant, such as ammonia or urea, to produce nitrogen and water. The reductants may be injected into an exhaust gas feedstream upstream of the SCR device, requiring injection systems, tanks and control schemes. The tanks may require periodic refilling and can freeze in cold climates requiring additional heaters and insulation. [0009] Catalytic materials used in SCR devices have included vanadium (V) and tungsten (W) on titanium (Ti) and base metals including iron (Fe) or copper (Cu) with a zeolite washcoat. Catalytic materials including copper may perform effectively at lower temperatures but have been shown to have poor thermal durability at higher temperatures. Catalytic materials including iron may perform well at higher temperatures but with decreasing reductant storage efficiency at lower temperatures.

[0010] For mobile applications, SCR devices generally have an operating temperature range of 150 ⁰ C to 600 ⁰ C. The temperature range may vary depending on the catalyst. This operating temperature range can decrease

during or after higher load operations. Temperatures greater than 600 ⁰ C may cause reductants to breakthrough and degrade the SCR catalysts, while the effectiveness of NOx processing decreases at temperatures lower than 150 ⁰ C.

SUMMARY

[0011] A method and aftertreatment system for reducing NOx emissions in an exhaust gas feedstream of an internal combustion engine includes a catalytic device fluidly connected upstream of a first ammonia-selective catalytic reduction device fluidly connected upstream of a second ammonia- selective catalytic reduction device. The first ammonia-selective catalytic reduction device includes a respective catalytic material including a first base metal, and the second ammonia-selective catalytic reduction device includes a respective catalytic material comprising a second base metal. Engine operation is modulated to generate an engine-out exhaust gas feedstream including nitric oxide, carbon monoxide, and hydrogen convertible to ammonia on the catalytic device. The ammonia is stored on the first and second ammonia-selective catalytic reduction devices. NOx emissions are reduced in the first and second ammonia-selective catalytic reduction devices using the stored ammonia.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] One or more embodiments will now be described, by way of example, with reference to the accompanying drawings which:

[0013] FIG. 1 is a schematic drawing of an exemplary engine system and aftertreatment system in accordance with the present disclosure;

[0014] FIG. 2 is a control scheme for managing an exhaust gas feedstream from the engine in accordance with the present disclosure;

[0015] FIG. 3 graphically illustrates exemplary test data from an exemplary NOx sensor and an ammonia sensor as a function of engine AFR in accordance with the present disclosure;

[0016] FIG. 4 schematically illustrates a control scheme for managing an exhaust gas feedstream from the engine in accordance with the present disclosure;

[0017] FIG. 5 graphically depicts exemplary test data describing a relationship between ammonia production and vehicle speed in accordance with the present disclosure;

[0018] FIGS. 6A and 6B graphically depict exemplary test data describing a relationship between cumulative NOx emissions and vehicle speed in accordance with the present disclosure;

[0019] FIGS. 7 and 8 schematically illustrate aftertreatment configurations of the exhaust aftertreatment system in accordance with the present disclosure;

[0020] FIG. 9 graphically depicts exemplary test data describing a relationship between ammonia generation and air/fuel ratio in accordance with the present disclosure;

[0021] FIG. 10 schematically illustrates a control scheme for managing an exhaust gas feedstream from the engine in accordance with the present disclosure; and

[0022] FIGS. 11-13 graphically depict exemplary test data in accordance with the present disclosure.

DETAILED DESCRIPTION

[0023] Referring now to the drawings, wherein the depictions are for the purpose of illustrating certain exemplary embodiments only and not for the purpose of limiting the same, FIG. 1 schematically shows an internal combustion engine 10, aftertreatment system 70, and an accompanying control module 5 that have been constructed in accordance with an embodiment of the disclosure. The engine 10 is selectively operative at a rich air/fuel ratio (AFR), a stoichiometric AFR, and at a lean AFR. The disclosure can be applied to various internal combustion engine systems and combustion cycles. [0024] In one embodiment the aftertreatment system 70 can be connected to the engine 10 that is coupled to an electro-mechanical hybrid powertrain system (not shown). The electro-mechanical hybrid powertrain system can include torque machines configured to transfer tractive power to a driveline of a vehicle (not shown).

[0025] The exemplary engine 10 comprises a multi-cylinder direct- injection four-stroke internal combustion engine having reciprocating pistons 14 slidably movable in cylinders 15 which define variable volume combustion chambers 16. The pistons 14 are connected to a rotating crankshaft 12 by which linear reciprocating motion is translated to rotational motion. An air intake system provides intake air to an intake manifold 29 which directs and distributes air into intake runners of the combustion chambers 16. The air

intake system comprises airflow ductwork and devices for monitoring and controlling the airflow. The air intake devices preferably include a mass airflow sensor 32 for monitoring mass airflow and intake air temperature. A throttle valve 34 preferably comprises an electronically controlled device that is used to control airflow to the engine 10 in response to a control signal (ETC) from the control module 5. A pressure sensor 36 in the intake manifold 29 is configured to monitor manifold absolute pressure and barometric pressure. An external flow passage recirculates exhaust gases from engine exhaust to the intake manifold 29, having a flow control valve referred to as an exhaust gas recirculation (EGR) valve 38. The control module 5 is operative to control mass flow of exhaust gas to the intake manifold 29 by controlling opening of the EGR valve 38.

[0026] Airflow from the intake manifold 29 into the combustion chamber 16 is controlled by one or more intake valve(s) 20. Exhaust flow out of the combustion chamber 16 is controlled by one or more exhaust valve(s) 18 to an exhaust manifold 39. The engine 10 is equipped with systems to control and adjust openings and closings of the intake and exhaust valves 20 and 18. In one embodiment, the openings and closings of the intake and exhaust valves

20 and 18 can be controlled and adjusted by controlling intake and exhaust variable cam phasing/variable lift control (VCP/VLC) devices 22 and 24 respectively. The intake and exhaust VCP/VLC devices 22 and 24 are configured to control and operate an intake camshaft 21 and an exhaust camshaft 23, respectively. The rotations of the intake and exhaust camshafts

21 and 23 are linked to and indexed to rotation of the crankshaft 12, thus

linking openings and closings of the intake and exhaust valves 20 and 18 to positions of the crankshaft 12 and the pistons 14.

[0027] The intake VCP/VLC device 22 preferably includes a mechanism configured to switch and control valve lift of the intake valve(s) 20 and variably adjust and control phasing of the intake camshaft 21 for each cylinder 15 in response to a control signal (INTAKE) from the control module 5. The exhaust VCP/VLC device 24 preferably comprises a controllable mechanism operative to variably switch and control valve lift of the exhaust valve(s) 18 and variably adjust and control phasing of the exhaust camshaft 23 for each cylinder 15 in response to a control signal (EXHAUST) from the control module 5.

[0028] The intake and exhaust VCP/VLC devices 22 and 24 each preferably includes a controllable two-step variable lift control (VLC) mechanism configured to control magnitude of valve lift, or opening, of the intake and exhaust valve(s) 20 and 18, respectively, to one of two discrete steps. The two discrete steps preferably include a low-lift valve open position (about 4-6 mm in one embodiment) preferably for load speed, low load operation, and a high- lift valve open position (about 8-13 mm in one embodiment) preferably for high speed and high load operation. The intake and exhaust VCP/VLC devices 22 and 24 each preferably includes a variable cam phasing (VCP) mechanism to control and adjust phasing (i.e., relative timing) of opening and closing of the intake valve(s) 20 and the exhaust valve(s) 18 respectively. Adjusting the phasing refers to shifting opening times of the intake and exhaust valve(s) 20 and 18 relative to positions of the

crankshaft 12 and the piston 14 in the respective cylinder 15. The VCP mechanisms of the intake and exhaust VCP/VLC devices 22 and 24 each preferably has a range of phasing authority of about 60°-90° of crank rotation, thus permitting the control module 5 to advance or retard opening and closing of one of intake and exhaust valve(s) 20 and 18 relative to position of the piston 14 for each cylinder 15. The range of phasing authority is defined and limited by the intake and exhaust VCP/VLC devices 22 and 24. The intake and exhaust VCP/VLC devices 22 and 24 include camshaft position sensors (not shown) to determine rotational positions of the intake and the exhaust camshafts 21 and 23. The VCP/VLC devices 22 and 24 are actuated using one of electro-hydraulic, hydraulic, and electric control force, controlled by the control module 5.

[0029] The engine 10 includes a fuel injection system, comprising a plurality of high-pressure fuel injectors 28 each configured to directly inject a mass of fuel into one of the combustion chambers 16 in response to a signal from the control module 5. The fuel injectors 28 are supplied pressurized fuel from a fuel distribution system (not shown).

[0030] The engine 10 includes a spark-ignition system (not shown) by which spark energy can be provided to a spark plug 26 for igniting or assisting in igniting cylinder charges in each of the combustion chambers 16 in response to a signal (IGN) from the control module 5. [0031] The engine 10 is equipped with various sensing devices for monitoring engine operation, including a crank sensor 42 having output RPM and operative to monitor crankshaft rotational position, i.e., crank angle and

speed, in one embodiment a combustion sensor 30 configured to monitor combustion, and an exhaust gas sensor 40 configured to monitor exhaust gases, comprising an air/fuel ratio sensor in one embodiment. The combustion sensor 30 comprises a sensor device operative to monitor a state of a combustion parameter and is depicted as a cylinder pressure sensor operative to monitor in-cylinder combustion pressure. The output of the combustion sensor 30 and the crank sensor 42 are monitored by the control module 5 which determines combustion phasing, i.e., timing of combustion pressure relative to the crank angle of the crankshaft 12 for each cylinder 15 for each combustion cycle. The combustion sensor 30 can also be monitored by the control module 5 to determine a mean-effective-pressure (IMEP) for each cylinder 15 for each combustion cycle. Preferably, the engine 10 and control module 5 are mechanized to monitor and determine states of IMEP for each of the engine cylinders 15 during each cylinder firing event. Alternatively, other sensing systems can be used to monitor states of other combustion parameters within the scope of the disclosure, e.g., ion-sense ignition systems, and non- intrusive cylinder pressure sensors.

[0032] The control module 5 executes algorithmic code stored therein to control actuators to control engine operation, including throttle position, spark timing, fuel injection mass and timing, intake and/or exhaust valve timing and phasing, and exhaust gas recirculation valve position to control flow of recirculated exhaust gases. Valve timing and phasing may include negative valve overlap (NVO) and lift of exhaust valve reopening (in an exhaust re- breathing strategy). The control module 5 is configured to receive input

signals from an operator (e.g., a throttle pedal position and a brake pedal position) to determine an operator torque request and input from the sensors indicating the engine speed and intake air temperature, and coolant temperature and other ambient conditions.

[0033] The control module 5 is preferably a general-purpose digital computer generally comprising a microprocessor or central processing unit, storage mediums comprising non-volatile memory including read only memory and electrically programmable read only memory, random access memory, a high speed clock, analog to digital and digital to analog circuitry, and input/output circuitry and devices and appropriate signal conditioning and buffer circuitry. The control module 5 has a set of control algorithms, comprising resident program instructions and calibrations stored in the nonvolatile memory and executed to provide the desired functions. The algorithms are preferably executed during preset loop cycles. Algorithms are executed by the central processing unit and are operable to monitor inputs from the aforementioned sensing devices and execute control and diagnostic routines to control operation of the actuators, using preset calibrations. Loop cycles may be executed at regular intervals, for example each 3.125, 6.25, 12.5, 25 and 100 milliseconds during ongoing engine and vehicle operation. Alternatively, algorithms may be executed in response to occurrence of an event.

[0034] In operation, the control module 5 monitors inputs from the aforementioned sensors to determine states of engine operating parameters. The control module 5 is configured to receive input signals from an operator

(e.g., via a throttle pedal and a brake pedal, not shown) to determine an operator torque request. The control module 5 monitors the sensors indicating the engine speed and intake air temperature, and coolant temperature and other ambient conditions.

[0035] The control module 5 executes algorithmic code stored therein to control the aforementioned actuators to form the cylinder charge, including controlling throttle position, spark-ignition timing, fuel injection mass and timing, EGR valve position to control flow of recirculated exhaust gases, and intake and/or exhaust valve timing and phasing on engines so equipped. Valve timing and phasing can include negative valve overlap (NVO) and lift of exhaust valve reopening (in an exhaust re -breathing strategy) in one embodiment. The control module 5 can operate to turn the engine 10 on and off during ongoing vehicle operation, and can operate to selectively deactivate a portion of the combustion chambers 15 or a portion of the intake and exhaust valves 20 and 18 through control of fuel and spark and valve deactivation. The control module 5 can control AFR based upon feedback from the exhaust gas sensor 40. The exhaust gas sensor 40 can comprise a wide-range air/fuel ratio sensor configured to generate a linear signal corresponding to air/fuel ratio over an air/fuel ratio range. Alternatively, in one embodiment the exhaust gas sensor 40 can comprise a switch-type stoichiometric sensor configured to generate an output signal that corresponds to an air/fuel ratio that is one of rich of stoichiometry and lean of stoichiometry. [0036] The exhaust aftertreatment system 70 is fluidly connected to the exhaust manifold 39 and comprises a catalytic device 48, a first ammonia-

selective catalytic reduction (NH3-SCR) device 60, and a second NH3-SCR device 62. The catalytic device 48 is fluidly and serially connected upstream of the first NH3-SCR device 60. The first NH3-SCR device 60 is fluidly and serially connected upstream of the second NH3-SCR device 62. The exhaust aftertreatment system 70 may include other catalytic and/or trap substrates operative to oxidize, adsorb, desorb, reduce, and combust elements of the exhaust gas feedstream as described herein below.

[0037] The exhaust aftertreatment system 70 can be equipped with various sensing devices for monitoring the exhaust gas feedstream from the engine 10, including a first NOx sensor 50 configured to monitor and quantify NOx molecules upstream of the second NH3-SCR 62, a second NOx sensor 52 to detect and quantify NOx molecules downstream of the NH3-SCR 62, a first temperature sensor 51 configured to monitor temperature of the first NH3- SCR device 60, and a second temperature sensor 53 configured to monitor temperature of the second NH3-SCR device 62. Other NOx sensors may be included in the exhaust aftertreatment system 70 to detect and quantify NOx molecules in the exhaust gas feedstream, e.g., a NOx sensor configured to detect NOx molecules entering the aftertreatment system 70 and a NOx sensor configured to monitor NOx molecules exiting the catalytic device 48. [0038] During engine operation, the exemplary engine 10 generates an exhaust gas feedstream containing constituent elements that can be transformed in the aftertreatment system, including hydrocarbons (HC), carbon monoxide (CO), oxides of nitrogen (NOx), and particulate matter (PM), among others. Oxygen (O ₂ ) is present in the exhaust gas feedstream

after operating the engine 10 lean of stoichiometry. Hydrogen (H ₂ ) production can occur in the engine 10 through the combustion process. Combustion in a stoichiometric or rich AFR environment, wherein molecular oxygen is scarce, tends to produce elevated levels of molecular hydrogen. [0039] The catalytic device 48 performs a number of catalytic functions for treating an exhaust gas flow. The catalytic device 48 oxidizes hydrocarbons (HC) and carbon monoxide (CO). The catalytic device 48 is formulated to produce ammonia during stoichiometric and rich engine operation. The formulation may involve using varying catalysts including platinum group metals, e.g., platinum, palladium, and rhodium, with cerium and zirconium oxides for oxygen storage capacity. In one embodiment, the catalytic device 48 is a three-way catalytic converter configured to oxidize hydrocarbons (HC) and carbon monoxide (CO) and reduce NOx during stoichiometric engine operations.

[0040] The first and second NH3-SCR devices 60 and 62 reduce NOx into other molecules, including nitrogen and water as described hereinbelow. An exemplary NH3-SCR device includes a substrate (not shown) coated with a zeolite washcoat and a catalytic material comprising a catalytically active base metal. The first NH3-SCR device 62 is coated with the zeolite washcoat and a first catalytic material comprising a first catalytically active base metal and the second NH3-SCR device 62 is coated with the zeolite washcoat and a second catalytic material comprising a second catalytically active base metal. The first and second catalytically active base metals are preferably different base metals. The substrate comprises a cordierite or metal monolith with a

cell density about 62 to 93 cells per square centimeter (400-600 cells per square inch), and a wall thickness about three to seven mils. The cells of the substrate comprise flow passages through which exhaust gas flows to contact the catalyst to effect storage of ammonia. The substrate is impregnated with the zeolite washcoat. The zeolite washcoat also contains the catalytically active base metals e.g., iron (Fe), copper (Cu), cobalt (Co), nickel (Ni). Alternatively, vanadium-based and/or tungsten (W) on titanium (Ti) compositions may be used as catalysts. Copper catalysts have been shown to perform effectively at lower temperatures, e.g., 100 ⁰ C to 450 ⁰ C, but have poor thermal durability. Iron catalysts may perform well at higher temperatures, e.g., 200 ⁰ C to 650 ⁰ C, but with decreasing reductant storage capacity. [0041] The first and second NH3-SCR devices 60 and 62 store ammonia that reacts with NOx emissions. The stored ammonia selectively reacts with NOx in the presence of the catalytic materials to produce nitrogen and water. The following equations describe the primary reactions with ammonia within the first and second NH3-SCR devices 60 and 62:

4NO + 4NH ₃ + O ₂ → 4N ₂ + 6H ₂ O [1]

3NO ₂ + 4NH ₃ → 3.5N ₂ + 6H ₂ O [2]

2NO + 2NO ₂ + 4NH ₃ → 4N ₂ + 6H ₂ O [3]

[0042] Multiple secondary reactions may concurrently occur and will vary depending on the type of fuel consumed.

[0043] During engine operation, the exhaust gas feedstream transfers thermal energy to the catalytic material on the first and second NH3-SCR devices 60 and 62. The exhaust gas feedstream can cool while flowing through the aftertreatment system 70 creating a temperature gradient from the first NH3-SCR device 60 to the second NH3-SCR device 62 whereby the first NH3-SCR device 60 operates in relatively higher temperature conditions and the second NH3-SCR device 62 operates in relatively lower temperature conditions for a known engine-out exhaust gas temperature. The catalytic material promotes the aforementioned reactions subsequent to achieving a minimum temperature threshold, and is effective until exceeding a maximum temperature threshold. The first NH3-SCR device 60 is associated with a first operating temperature range and the second NH3-SCR device 62 is associated with a second operating temperature range. For example, the first NH3-SCR device 60 reduces NOx when its temperature is within the first operating temperature range and the second NH3-SCR device 62 reduces NOx when its temperature is within the second operating temperature range. FIG. 13 shows NOx conversion efficiency (%) as a function of average catalyst temperature for one embodiment, comprising a zeolite washcoat using copper as the catalytic material (Cu-zeolite) and for a zeolite washcoat using iron as the catalytic material (Fe-zeolite). One method to increase an engine speed- load operating area for lean engine operation comprises increasing the operating temperature ranges for the first and second NH3-SCR devices 60 and 62.

Another method to increase the engine speed-load operating area for lean engine operation comprises configuring the aftertreatment system 70 to maximize conditions whereat the first and second NH3-SCR devices 60 and 62 are within the associated operating temperature ranges during engine operation, including spatial design parameters such as physical distances between the first and second NH3-SCR devices 60 and 62. [0044] In one embodiment, the first NH3-SCR device 60 is preferably positioned near the engine 10 to enable NOx reduction at lower exhaust gas temperatures that can occur during operation at lower speed-load engine operating points and the second NH3-SCR device 62 is preferably positioned downstream of the first NH3-SCR device 60 to enable NOx reduction at higher exhaust gas temperatures that can occur during operation at higher speed-load operating conditions. The position is predetermined and based upon particular engine characteristics and the particular hardware application. In one embodiment, the distance between the first NH3-SCR device 60 and the second NH3-SCR device 62 is configured to cool the exhaust gas flow between the first and second NH3-SCR devices 60 and 62 thereby expanding the speed-load engine operating area for NOx reduction in the first and second NH3-SCR devices 60 and 62. The distance between the first and second NH3- SCR devices 60 and 62 may be determined based upon calibrations according to test results corresponding to a particular hardware application. [0045] In one embodiment, a maximum speed-load engine operating area for NOx reduction during lean engine operation is achieved when the first NH3-SCR device 60 stores ammonia and reduces NOx molecules at relatively

higher temperatures and the second NH3-SCR device 62 stores ammonia and reduces NOx molecules at relatively lower temperatures. Therefore, the first NH3-SCR device 60 preferably comprises a catalytic material configured to store ammonia and reduce NOx molecules at a high catalytically active temperature range, and the second NH3-SCR device 62 preferably comprises catalytic material configured to store ammonia and reduce NOx molecules at a lower catalytically active temperature range. In one embodiment, an iron catalyst is used for the first NH3-SCR device 60 and a copper catalyst is used for the second NH3-SCR device 62. The iron catalyst stores ammonia and reduces NOx molecules at the relatively high catalytically active temperature range for the first NH3-SCR device 60, and the copper catalyst store ammonia and reduce NOx molecules at the relatively lower catalytically active temperature range.

[0046] A method is disclosed herein to selectively and periodically modulate engine operation to generate an engine-out exhaust gas feedstream comprising nitric oxide (NO), carbon monoxide (CO), and hydrogen (H ₂ ) to produce ammonia in a catalytic device, such as the catalytic device 48. [0047] Ammonia may be produced in the catalytic device 48 from a conversion process described by the following equation:

NO + CO + 1.5 H ₂ ^ NH ₃ + CO ₂ [4]

[0048] One having ordinary skill in the art will appreciate that this conversion requires molecular oxygen to be depleted from the catalytic device

48 before NO will react with the molecular hydrogen. In one embodiment, sufficient conversion occurred at temperatures exceeding 250 ⁰ C in the catalytic device 48. Excess oxygen is frequently present when the internal combustion engine is operated in lean operating modes, with a lean AFR or with excess air. Thus, the control module 5 controls the AFR to a stoichiometric AFR or rich AFR to deplete oxygen in the exhaust gas feedstream when ammonia production in the catalytic device 48 is desired. [0049] Further, selection of an AFR within the stoichiometric and rich operating ranges further facilitates ammonia production, for example, by producing nitric oxide (NO) and hydrogen (H ₂ ) in appropriate ratios. Eq. 4 describes an ideal ratio of 1.5:1 of hydrogen to nitric oxide (H ₂ :NO). However, based upon the environment provided by the first and second NH3- SCR devices 60 and 62 and other reactions taking place within the catalytic device 48, a different actual ratio of hydrogen (H ₂ ) to nitric oxide (NO) can produce ammonia. For example, a ratio of between 3:1 and 5:1 hydrogen to nitric oxide (H ₂ :NO) is preferred in one embodiment.

[0050] Modulating engine operation includes operating the engine 10 rich or at stoichiometry while meeting the operator torque request and without changing engine output power. One exemplary method for operating the exemplary engine 10 rich of stoichiometry can include executing multiple fuel injection pulses during a combustion cycle including injecting a first fuel pulse into the combustion chamber 16 during each compression stroke. The mass of fuel injected during the first fuel pulse is determined based upon an amount sufficient to operate the engine 10 to meet the operator torque request and

other load demands. Subsequent fuel pulses can be injected into the combustion chamber 16 during other strokes of the combustion cycle thereby generating an exhaust gas feedstream comprising nitric oxide (NO), carbon monoxide (CO), and hydrogen (H ₂ ) to produce ammonia in the catalytic device 48. In one embodiment, the subsequent fuel pulses are executed late in a power stroke or early in an exhaust stroke of the combustion cycle thereby minimizing likelihood of combustion in the combustion chamber 16. [0051] Selection of a catalytically active material that enables lower ratios of hydrogen (H ₂ ) molecules to nitric oxide (NO) molecules on the catalytic device 48 is preferable, as hydrogen requirements directly relate to an amount of fuel that is consumed by the subsequent fuel pulses to enable ammonia production. Calibration according to test results or modeling according to methods sufficient to accurately estimate engine operation, aftertreatment processes, and conversions can be utilized to select a preferred AFR to control ammonia production. One having ordinary skill in the art will appreciate that carbon monoxide (CO) presence must also be considered to facilitate the reaction described above.

[0052] Ammonia production can be controlled or enabled according to a number of factors affecting ammonia usage within the first and second NH3- SCR devices 60 and 62, including estimated ammonia storage, estimated or detected ammonia breakthrough, estimated or detected NOx breakthrough downstream from the second NH3-SCR device 62, and engine operation conducive to ammonia production. Monitoring of these factors can be accomplished through monitoring a number of inputs, including engine

operation, exhaust gas properties, and NOx conversion efficiency within the first and second NH3-SCR devices 60 and 62. Periods of engine acceleration have been shown to include higher levels of NOx and hydrogen production, and an AFR controlled to stoichiometry. Engine operating conditions that are conducive to ammonia production are preferred to minimize intrusive engine operation. Length of modulating engine operation to produce ammonia will vary depending upon required ammonia production, the particulars of the system employed, and the particular operation of the engine 10. In one embodiment, the first NH3-SCR device 60 is used as a primary NOx reduction device and the second NH3-SCR device 62 is used as a secondary NOx reduction device. The second NH3-SCR device 60 is used primarily to store and reduce breakthrough ammonia molecules from the first NH3-SCR device 60 during engine modulation. The stored ammonia is reduced and desorbed from the second NH3-SCR device 62 by reacting with NOx molecules in the exhaust gas feedstream with the stored ammonia.

[0053] FIG. 2 shows a control scheme 200 for managing an exhaust gas feedstream from the engine 10 during engine operations. The control scheme 200 is depicted as a plurality of discrete elements. Such illustration is for ease of description and it should be recognized that the functions performed by the discrete elements may be combined in one or more devices, e.g., implemented in software, hardware, and/or application-specific integrated circuitry. For example, the control scheme 200 may be executed as one or more algorithms in the control module 5. The control scheme 200 comprises monitoring the exhaust gas feedstream and the aftertreatment system 70 (203). Monitoring

the exhaust gas feedstream comprises detecting NOx breakthrough and ammonia breakthrough downstream of the first and second NH3-SCR devices 60 and 62. Monitoring the aftertreatment system 70 comprises monitoring temperature of the first and second NH3-SCR devices 60 and 62 using the first temperature sensor 51 and the second temperature sensor 53 respectively. [0054] Before initiating lean engine operation or modulating engine operation to produce ammonia, the temperature of at least one of the first and second NH3-SCR devices 60 and 62 must be within the operating temperature range (206). Preferably, the temperatures of the first and second NH3-SCR devices 60 and 62 are monitored continuously using the first and second temperature sensors 51 and 53. During lean engine operation, when the temperatures of both of the first and second NH3-SCR devices 60 and 62 are outside their associated operating temperature ranges, engine operation may be controlled to stoichiometric AFR.

[0055] When the temperature of either one of the first and second NH3- SCR devices 60 and 62 is within its associated operating temperature range, the control scheme 200 modulates engine operation to produce the constituent elements and hydrogen (H ₂ ) for ammonia production (209). Ammonia is produced in the catalytic device 48 using the constituent elements and hydrogen (H ₂ ) as described hereinabove. Ammonia is then transferred downstream to the first and second NH3-SCR devices 60 and 62 where it is stored.

[0056] The control scheme 200 monitors ammonia and discontinues modulating engine operation subsequent to determining the first and second

NH3-SCR devices 60 and 62 are saturated with ammonia (218). Ammonia production can additionally be discontinued after achieving a predetermined threshold of ammonia molecules or when engine operating conditions are not conducive to ammonia production, e.g., during vehicle decelerations, engine idling, or engine stops (219). Saturation may be determined by monitoring the exhaust gas feedstream downstream of the second NH3-SCR device 62 to detect a predetermined ammonia breakthrough threshold. Ammonia breakthrough indicates that the first and second NH3-SCR devices 60 and 62 are saturated with ammonia. Ammonia breakthrough may be detected by monitoring a signal output of an ammonia sensor (not shown) configured to monitor the exhaust gas feedstream downstream of the second NH3-SCR device 62. In one embodiment, saturation and/or ammonia molecule production may be estimated using a model to accurately estimate operation of the combustion cycle, aftertreatment processes, conversions, and monitored operating conditions including intake mass airflow, AFR, engine speed, TWC temperature, TWC aging state, SCR device temperature, and SCR device aging state. The model may be calibrated according to test results corresponding to a particular hardware application.

[0057] FIG. 3 graphically illustrates exemplary test data showing signal outputs from a known NOx sensor and a known ammonia sensor as a function of AFR from the engine 10, illustrative of signal outputs from the first and second NOx sensors 50 and 52 and an ammonia sensor (not shown). Known NOx sensing technologies do not distinguish between NOx molecules and ammonia molecules in the exhaust gas feedstream. During lean engine

operating conditions, when ammonia presence in the exhaust gas feedstream is minimal and NOx molecules are present, signal output from the NOx sensor indicates NOx molecules and increases with increasing AFR. Signal output from the ammonia sensor is minimal. At stoichiometric engine operating conditions, when NOx molecules and ammonia molecules present in the exhaust gas feedstream are minimal, signal output from the NOx sensor and the ammonia sensor are minimal. As the AFR decreases during rich engine operating conditions, the presence of ammonia molecules increase while NOx molecules are minimal in the exhaust gas feedstream. Signal output from the NOx sensor and the ammonia sensor increase during rich engine operation as the AFR decreases. Therefore, during rich engine operation increased signal output from the first and second NOx sensors 50 and 52 can be used to indicate ammonia molecules in the exhaust gas feedstream. Thus, ammonia breakthrough may be detected by monitoring signal output of the first and second NOx sensors 50 and 52 during rich engine operation. In one embodiment, the second NOx sensor 52 is monitored for increased signal output during ammonia production. When signal output from the second NOx sensor 52 increases, the control scheme 200 determines that ammonia breakthrough is occurring.

[0058] After determining the first and second NH3-SCR devices 60 and 62 are saturated with ammonia and/or achieving a predetermined ammonia production threshold, the control scheme 200 discontinues modulating engine operation and ammonia production and transitions engine operation to lean engine operation (221). The combustion process releases NOx emissions into

the exhaust gas flow. The catalytic device 48 reduces a portion of the NOx emissions transferring oxygen and nitrogen downstream to the first and second NH3-SCR devices 60 and 62. Ammonia stored on the first and second NH3- SCR devices 60 and 62 reacts with NOx thereby reducing NOx emissions and producing nitrogen and water. Ammonia storage decreases as ammonia molecules react with NOx molecules. After depleting the ammonia stored in the first and second NH3-SCR devices 60 and 62, NOx emissions pass through the first and second NH3-SCR devices 60 and 62 substantially unreduced resulting in NOx breakthrough.

[0059] The control scheme 200 preferably discontinues lean engine operation and operates the engine 10 at a stoichiometric AFR after determining that NOx breakthrough is occurring downstream from the second NH3-SCR device 62 (224). NOx breakthrough may be detected by monitoring the exhaust gas feedstream or determined by modeling ammonia depletion. Detecting NOx breakthrough comprises monitoring signal output from the first and second NOx sensors 50 and 52. An increase in signal output from the first and second NOx sensors 50 and 52 is correlatable to an increase in NOx emissions out of the first and second NH3-SCR devices 60 and 62 respectively during lean engine operation. NOx breakthrough is detected when the signal output increases from both the first and second NOx sensors 50 and 52.

[0060] Another method for detecting NOx breakthrough comprises modeling ammonia depletion. Ammonia depletion and therefore NOx breakthrough may be estimated using a model according to methods sufficient

to accurately estimate operation of the combustion cycle, aftertreatment processes, conversions, and monitored operating conditions including intake mass airflow, AFR, engine speed, TWC temperature, TWC aging state, SCR device temperature, and SCR device aging state. The model may be calibrated according to test results corresponding to a particular hardware application. [0061] After determining that ammonia is depleted a predetermined amount or, alternatively, detecting NOx breakthrough, the control scheme 200 may confirm NOx breakthrough by operating the engine 10 at a stoichiometric AFR before modulating engine operation to produce ammonia (227). NOx breakthrough is confirmed, after transitioning engine operation to a stoichiometric AFR, based upon signal output from one of the first and second NOx sensors 50 and 52 (230). In one embodiment, a decreasing signal output from the first NOx sensor 50 signal confirms NOx breakthrough during prior lean engine operation thereby permitting the control module 5 to modulate engine operation to produce ammonia (209). Otherwise, the first and second NOx sensors 50 and 52 were measuring ammonia breakthrough indicating presence of ammonia molecules on the catalysts of the first and second SCR devices 60 and 62. In which case, the control module 5 transitions engine operation to the lean AFR (221). After determining that ammonia is depleted or detecting NOx breakthrough, the control scheme 200 may modulate engine operation to produce ammonia (209).

[0062] The abovementioned methods may be used in conjunction with intake air measurements to extend lean engine operation, thereby increasing fuel efficiency. When intake air mass into the engine 10 decreases, less fuel is

burned in the combustion process, and temperature of the exhaust gas feedstream decreases creating conditions for NOx reduction in the aftertreatment system 70.

[0063] FIG. 4 shows a second control scheme 400 that may be used to control engine operation and manage an exhaust gas feedstream subsequent to a high speed-load engine operation. The control scheme 400 is illustrated and described herein as discrete elements. Such illustration is for ease of description and it should be recognized that the functions performed by these elements may be combined in one or more devices, e.g., implemented in software, hardware, and/or application-specific integrated circuitry. For example, the control scheme 400 may be executed as one or more algorithms in the control module 5. The control scheme 400 comprises monitoring intake mass airflow using the mass airflow sensor 32, the exhaust gas feedstream, and the aftertreatment system 70 (403).

[0064] For a minor reduction in intake mass airflow, e.g., greater than 5g/s and less than 10g/s, the control scheme 400 monitors signal output from the second NOx sensor 52 and the temperature of the first and second NH3-SCR devices 60 and 62. When a minor reduction in intake mass airflow occurs (406) after achieving a high speed-load engine operating point, i.e., exceeding a predetermined speed-load threshold, for a predetermined period of time (405), and the temperature of one of the first and second NH3-SCR devices 60 and 62 is less than a predetermined threshold, e.g., 400 ⁰ C (407), the control scheme 400 may modulate engine operation (409) as described hereinabove to produce ammonia on the catalytic device 48. The ammonia is transferred to

the first and second NH3-SCR devices 60 and 62 for storage on the first and second NH3-SCR devices 60 and 62 as described hereinabove. The control scheme 400 determines that the first and second NH3-SCR devices 60 and 62 are saturated by monitoring the second NOx sensor 52 (415). When signal outputs from the second NOx sensor 52 increase, indicating ammonia breakthrough, the control scheme 400 discontinues modulating engine operation and initiates lean engine operation (418). Lean engine operation is discontinued subsequent to detecting NOx breakthrough as described hereinabove (421). In one embodiment, the control scheme 400 may discontinue modulating engine operation and initiate lean engine operation subsequent to producing a predetermined threshold of ammonia molecules. [0065] For substantial reductions in intake mass airflow, e.g., greater than 10g/s, the control scheme 400 monitors signal output from the first and second NOx sensors 50 and 52 and the temperature of the second NH3-SCR device 62. When the intake mass airflow is reduced substantially (456) after achieving a high speed-load operating point, for a predetermined elapsed time (405), and the temperature of the second NH3-SCR device 62 is less than a predetermined threshold, e.g., 400 ⁰ C (458), the control scheme 400 may modulate engine operation (469) as described hereinabove to produce ammonia on the catalytic device 48. The ammonia is transferred to the first and second NH3-SCR devices 60 and 62 for storage on the first and second NH3-SCR devices 60 and 62 as described hereinabove. The control scheme 400 determines that the first and second NH3-SCR devices 60 and 62 are saturated by monitoring signal output from the first NOx sensor 50 (480).

After a predetermined period of time after the signal outputs from the first NOx sensor 50 increase, indicating ammonia breakthrough, the control scheme 400 discontinues modulating engine operation and initiates lean engine operation (488). Lean engine operation is discontinued subsequent to detecting NOx breakthrough as described hereinabove (490). In one embodiment, the control scheme 400 may discontinue modulating engine operation and initiate lean engine operation subsequent to producing a predetermined threshold of ammonia molecules. [0066] FIG. 5 graphically depicts exemplary test data describing a relationship between ammonia production and vehicle speeds. Ammonia concentrations were measured with a Fourier-transform infrared spectrometer during engine operations using the exemplary aftertreatment system 70. As FIG. 5 shows, during engine accelerations, when the exemplary engine 10 operates at stoichiometry or slightly rich of stoichiometry (e.g., AFR between 13.8:1 and 14.2:1), ammonia concentration produced by the catalytic device 48 increases.

[0067] FIG. 6 A graphically depicts exemplary test data depicting a relationship between cumulative NOx emissions out of the exemplary engine 10, catalytic device 48, the first NH3-SCR device 60, and the second NH3- SCR device 62 and vehicle speed, when the engine 10 is controlled to operate lean of stoichiometry. When the exemplary engine 10 is controlled to alternate between lean and rich excursions, significantly less NOx emissions pass out of the aftertreatment system 70 than emitted by the exemplary engine 10 into the exhaust gas feedstream. FIG. 6A also depicts NOx reduction by

the first and second NH3-SCR devices 60 and 62, after NOx reduction in the catalytic device 48.

[0068] FIG. 6B graphically depicts exemplary test data depicting a relationship between cumulative NOx emissions out of the engine 10, catalytic device 48, the first NH3-SCR device 60, and the second NH3-SCR device 62 and vehicle speed, when the engine is controlled to operate at stoichiometry. Significantly less NOx emissions pass out of the catalytic device 48 than that seen with during lean operation. FIG. 6B also depicts NOx reduction by the first and second NH3-SCR devices 60 and 62, after NOx reduction in the catalytic device 48.

[0069] FIG. 7 schematically illustrates another configuration of the exhaust aftertreatment system. The configuration comprises the catalytic device 48 and the first and second NH3-SCR devices 60 and 62. As described hereinabove the first and second NH3-SCR devices 60 and 62 preferably comprise different catalytic materials configured to store ammonia and reduce NOx molecules at different catalytically active temperature ranges. The second NOx sensor 52 is used to determine NOx breakthrough and ammonia presence in the exhaust gas feedstream as described hereinabove. [0070] FIG. 8 schematically illustrates another configuration, comprising an engine 10' and the exhaust aftertreatment system. The configuration comprises the first catalytic device 48 that is preferably close-coupled to the engine 10', and a second catalytic device 48' and the first and second NH3- SCR devices 60 and 62 that are downstream, e.g., in an underfloor location. The engine 10' preferably comprises a port-fuel injection engine that injects

fuel into runners of an intake manifold upstream of each combustion chamber (not shown). The engine 10' is controlled to operate at or about stoichiometry within a narrowly controlled band for +/- δAFR about stoichiometry which can be an air/fuel ratio band of 14.6: 1 +/- 0.05 in one embodiment. As described hereinabove the first and second NH3-SCR devices 60 and 62 preferably comprise different catalytic materials configured to store ammonia and reduce NOx molecules at different catalytically active temperature ranges. [0071] FIG. 10 shows a second control scheme 200' comprising a method for managing an exhaust gas feedstream from the embodiment described with reference to FIG. 8 comprising the port-fuel injection engine 10' and the aftertreatment system comprising the first TWC 48, the second TWC 48' and the first and second NH3-SCR devices 60 and 62 during engine operations, with like elements identified using like numerals. Although not shown in detail, the embodiment described in FIG. 10 includes an engine-out exhaust gas sensor, a first NOx sensor upstream of the first NH3-SCR device 60, a second NOx sensor downstream of the second NH3-SCR device 62, and temperature sensors configured to monitor temperatures of the first and second NH3-SCR devices 60 and 62.

[0072] The control scheme 200' comprises monitoring the exhaust gas feedstream and the aftertreatment system (203). Monitoring the exhaust gas feedstream includes detecting NOx breakthrough and ammonia breakthrough downstream of the second NH3-SCR device 62 using the second NOx sensor. Monitoring the aftertreatment system can include monitoring temperatures of the first and second NH3-SCR devices 60 and 62 using the SCR temperature

sensors. Before modulating engine operation to produce ammonia, the temperature of one of the first and second NH3-SCR devices 60 and 62 is preferably within a predetermined temperature range that corresponds to the specific catalytic material comprising a catalytically active base metal that is used in one of the first and second NH3-SCR devices 60 and 62 (206). In this control scheme 200', engine operation is ongoingly controlled at or near stoichiometry. When the temperatures of both the first and second NH3-SCR devices 60 and 62 are outside the associated predetermined temperature ranges, engine operation is controlled to prevent lean engine operation, including preventing operation in a fuel cutoff mode, e.g., during decelerations, and preventing autonomic engine stops.

[0073] FIG. 9 shows ammonia production (NH3) corresponding to engine- out air/fuel ratio (A/F Ratio) in the exhaust gas feedstream downstream of a close-coupled three-way catalytic converter for an exemplary system at several engine loads (120 kPa, 240 kPa, 320 kPa) at a predetermined engine operating speed (1000 rpm). The results indicate that ammonia production maximizes at an engine -out air/fuel ratio of about 14:1, and within an engine- out air/fuel ratio range between 13.5:1 and 14.5:1, thus indicating a preferred engine-out air/fuel ratio point for maximizing ammonia production. The results further indicate that there is some ammonia production during stoichiometric operation when the engine-out air/fuel ratio oscillates rich and lean of stoichiometry, including when the engine-out air/fuel ratio oscillates rich and lean of stoichiometry with an expanded engine-out air/fuel ratio range of +/- δAFR about stoichiometry, e.g., an air/fuel ratio range of +/- 0.10.

[0074] When the temperature of one of the first and second NH3-SCR devices 60 and 62 is within the predetermined temperature range, the control scheme 200' modulates engine operation to produce the nitric oxide (NO), carbon monoxide (CO), and hydrogen (H ₂ ) for ammonia production (209'). In this embodiment, modulating engine operation may include operating the engine 10' at stoichiometry, operating the engine 10' at stoichiometry with an expanded range for +/- δAFR about stoichiometry, e.g., 14.6:1 +/- 0.2 in one embodiment, and operating the engine 10' at or about an air/fuel ratio of 14:1, depending upon an anticipated need for ammonia. This can include operating the engine within an air/fuel ratio range between 13.5:1 and 14.5:1 to generate the engine-out exhaust gas feedstream in one embodiment. The ammonia produced in the catalytic device 48 as described hereinabove using the nitric oxide (NO), carbon monoxide (CO), and hydrogen (H ₂ ) (212), is transferred downstream to the first and second NH3-SCR devices 60 and 62 for storage (215) while monitoring the first and second NH3-SCR devices 60 and 62 for saturation (217). So long as the first and second NH3-SCR devices 60 and 62 do not saturate, the control scheme 200' may operate within this loop to manage the exhaust gas feedstream.

[0075] When the control scheme 200' determines the first and second NH3-SCR devices 60 and 62 are saturated with ammonia (217), engine operation can be adjusted to discontinue modulating engine operation to produce ammonia (221'). This includes responding to commands for engine operating conditions that are not conducive to ammonia production, including fuel cutoff events, e.g., during deceleration events and engine stopping, and

transitioning engine operation to lean engine operation. The control scheme 200' discontinues modulating engine operation to produce ammonia when the first and second NH3-SCR devices 60 and 62 saturate, and transitions engine operation to lean engine operation resulting in increased NOx emissions into the exhaust gas feedstream. Lean engine operation can include operating at an air/fuel ratio of about 16.0:1. The stored ammonia is depleted as ammonia molecules react with NOx molecules. Although not shown explicitly, the engine 10' may be commanded to operate lean of stoichiometry in response to engine and vehicle operation, including fuel cutoff events, e.g., during deceleration events, engine idling, and engine stopping events, as can occur with engine stop/start systems associated with hybrid powertrain system operation. The control scheme 200' disables or discontinues lean engine operation and returns to operating at stoichiometry after detecting NOx breakthrough downstream from the first and second NH3-SCR devices 60 and 62 (224). After determining that ammonia is depleted or detecting NOx breakthrough, the control scheme 200' again modulates engine operation to produce ammonia (209').

[0076] The abovementioned methods may be employed in multiple exhaust aftertreatment hardware configurations. One configuration can include a particulate filter combined with the catalytic device 48 upstream of the first and second SCR devices 60 and 62. The particulate filter and the catalytic device are configured to oxidize hydrocarbons (HC) and carbon monoxide (CO), and the first and second SCR devices 60 and 62 convert NOx during engine operations. Another configuration can include a three-way

catalytic converter as the catalytic device 48 combined with a particulate filter. This can include coating a particulate filter substrate with a washcoat containing catalytically active platinum-group metals including platinum, palladium, and rhodium. The catalytic device 48 combined with the particulate filter may be configured for ammonia production during stoichiometric or rich engine operation as described hereinabove. A further configuration can include an additional oxidation catalytic device fluidly and serially connected downstream of the second SCR device 62. A further configuration can include a NOx adsorber device fluidly and serially connected downstream of the second SCR device 62 for increased emissions control.

[0077] FIG. 11 graphically shows NOx conversion efficiency (%) corresponding to temperature across an NH3-SCR device using copper as the catalytic material. The results indicate that there is low conversion efficiency when there is no oxygen (O ₂ ) present, but that with low levels of oxygen, e.g., 0.5% concentration in the feedstream, the conversion efficiency increased substantially, including conversion efficiency in excess of 80% at 0.5% oxygen concentration in the feedstream when the temperature was at or above 35O ⁰ C. FIG. 12 graphically shows NOx conversion efficiency (%) corresponding to temperature across an NH3-SCR device using iron as the catalytic material. The results indicate that there is low conversion efficiency when there is no oxygen (O ₂ ) present, but that with low levels of oxygen concentration in the feedstream, e.g., 0.05% or 500 ppm, the conversion efficiency increased substantially, including a conversion efficiency in excess

of 60% at 0.05% oxygen concentration in the feedstream when the temperature was at or above 35O ⁰ C. The results of FIGS. 11 and 12 indicate that there can be substantial NOx conversion at exhaust gas feedstream conditions having low levels of oxygen, e.g., as occurs at stoichiometric engine operation using copper and iron as catalytic materials. [0078] The method described herein contemplates production of ammonia through engine modulation, utilizing components of the exhaust gas feedstream to sustain aftertreatment of NOx in the first and second SCR devices 60 and 62. It will be appreciated that these methods can be used in isolation from urea injection, with the methods described supplying all of the required ammonia. In the alternative, the methods described herein can be used to compliment a urea injection system, extending the range of the system between required filling of a urea storage tank while allowing a full range of engine and powertrain operation without significant monitoring of ammonia production cycles and current storage capacity, due to available urea injection on demand.

[0079] The disclosure has described certain preferred embodiments and modifications thereto. Further modifications and alterations may occur to others upon reading and understanding the specification. Therefore, it is intended that the disclosure not be limited to the particular embodiment(s) disclosed as the best mode contemplated for carrying out this disclosure, but that the disclosure will include all embodiments falling within the scope of the appended claims.