Abstract:
The method of treating a fuel lean exhaust containing NO X  and SO 2  includes splitting the exhaust into major and minor portions for flow through multiple flow paths each of which contains a particulate trap and an absorber containing a NO X  oxidation catalyst and a nitrate absorbent. The major portion is passed through a flow path in the lean state at a first temperature to convert the NO X  to nitrate and the SO 2  to sulfate. After the first period of operation flows are switched so that one flow path receives a minor exhaust portion for a second period of time during which fuel is injected into that flow path along with diversion of a portion of exhaust from another flow path through a bypass. When during the second period of operation the particulate trap reaches a predetermined temperature, the flow path is opened to an increased exhaust flow to transfer heat from the particulate trap to the NO X  absorber to bring the NO X  absorber to a temperature suitable for sulfation, at which time fuel and a small portion of exhaust gas are again introduced in order to effect the desulfation.

Description:
FIELD OF THE INVENTION 
     This method provides a technique for on-vehicle NO X  adsorber desulfation especially for use in NO X  adsorber catalyst equipped diesel vehicles employing a multi-leg exhaust flow path. 
     THE PRIOR ART 
     New emission reduction standards for lean burn heavy-duty diesel engines are to be implemented starting in model year 2007. The new standards will require catalysts and systems that can suppress the emission of oxides of nitrogen (NO X ) from these engines into the atmosphere. Current NO X  adsorber catalyst formulations typically contain a combination of one or more of the following substances: alkali metals such as potassium (K), sodium (Na), lithium (Li) and cesium (Cs); alkali earth metals such as barium (Ba) and calcium (Ca); rare earth metals such as lanthanum (La) and yttrium (Y); and precious metals such as platinum (Pt) and rhodium (Rh). The precious metals in the catalyst wash coat oxidize NO and NO 2  to nitrate ion (NO 3   − ) and the nitrate ion is subsequently absorbed by the NO X  adsorbent (alkali metals, alkali earth metals and rare earth metals) to form stable nitrates. These nitrate ions are then desorbed in a rich exhaust environment (lambda&lt;&lt;1) at normal engine operating temperatures and reduced over precious metal sites to diatomic nitrogen. 
     It has been found in development testing that the NO X  storage and reduction capacity of the adsorber decreases over time. The main mechanisms responsible for the decrease in adsorber NO X  storage and reduction capacity are thermal degradation of the adsorber wash coat and poisoning due to the presence of sulfur in diesel fuel. The sulfur is first oxidized during combustion, forming SO 2 . The SO 2  is then further oxidized to SO 3  and sulfate ion (SO 4   2− ) via the reaction with O 2   −  or O 2− on the surface of the platinum in the adsorber wash coat. The sulfate ion is then adsorbed by the NO X  adsorbent (alkali metals, alkali earth metals, and rare earth metals) to form stable sulfates (for example BaSO 4 ), reducing the number of sites available for NO X  adsorption. These sulfates have a higher binding affinity for alkali/alkali-earth/rare earth metals than nitrates, thus requiring temperatures that are much higher than those present in typical diesel exhaust to be desorbed. Higher temperatures, in conjunction with a rich exhaust environment (lambda&lt;&lt;1) are required to remove the sulfate ion from the NO X  adsorbent. The process of removal of sulfates from NO X  adsorbers will be referred to herein as desulfation. 
     SUMMARY OF THE INVENTION 
     The present invention provides a method and apparatus for desulfating NO X  adsorber catalysts in a multi exhaust path flow system utilizing in-exhaust fuel injection and exhaust flow bypass. This method minimizes temperature extremes on the surface of the NO X  adsorber, while achieving the precise temperatures required for desulfation. Thus, overall thermal degradation of the adsorber catalyst due to high temperatures is kept to a minimum or ultimately eliminated. This method allows the sulfates to desorb from the adsorber catalyst, as H 2 S and SO 2 , at exhaust lambda values &lt;1. 
     The present invention generates an exotherm on particulates accumulated in a trap upstream of a NO X  adsorber, convectively transfers heat to the NO X  adsorber, and minimizes local temperature extremes on the surface of the NO X  adsorber. This, in turn, reduces the chances for thermal damage, e.g., deactivation of the adsorber NO X  storage and reduction function due to sintering and migration of the wash coat into the catalyst substrate (i.e., migration of alkali, alkali earth, and rare earth metals). The present invention also allows better control over the desulfation and does not affect the drivability of the vehicle, as has been reported in connection with single leg systems. 
     More specifically, the present invention splits an exhaust stream into two or more paths or legs, each leg of the system containing of a NO X  adsorber and a particulate trap, preferably a catalyzed diesel particulate filter (hereinafter “CDPF”), upstream of the NO X  adsorber. While desulfating one of the multiple flow paths, the desulfating path is bypassed so that only a very small fraction of the exhaust flows through the desulfating NO X  adsorber. This flow is due to incomplete sealing of the exhaust brake used to shut flow off to the bypassed leg. The incorporation of the perpendicular exhaust bypass loop allows controlled addition of exhaust from the adsorbing leg to the desulfation leg. This addition of exhaust allows for control over the mass of oxygen in the desulfating leg. Reductant is added via secondary fuel injection directly into the desulfating leg, upstream of the CDPF. The oxygen causes an exothermic oxidation of the reductant across the CDPF. The extent of the exotherm is determined by the lambda value in the desulfating leg, which is a product of the amount of reductant and oxygen present in the leg. Lambda can also be defined as the ratio of actual oxygen concentration to the oxygen concentration required for stoichiometry. The exotherm causes a rise in the CDPF temperature which is monitored. In pilot plant experimentation the CDPF temperature was measured by six thermocouples inserted along the CDPF horizontally. The heat is convectively transferred from the CDPF to the NO X  adsorber catalysts by manipulation of the exhaust bypass flow rate from the adsorbing leg to the desulfating leg. Heat transfer can also occur without using the perpendicular exhaust bypass loop by momentarily opening the desulfating leg to full exhaust flow and then closing off the flow once the heat has transferred. Once the adsorber is heated to the desired temperature, reductant is added to facilitate sulfur release. The perpendicular exhaust bypass loop flow is controlled to maintain an exotherm across the CDPF and to allow heat transfer from the CDPF to the NO X  adsorber to maintain the desired desulfation temperature. 
     Accordingly, the present invention provides a method for treating an exhaust gas stream which is in a lean state, fuel-lean of stoichiometric, and which contains NO X  and SO 2 . The method includes splitting the exhaust gas stream into major and minor exhaust gas portions for flow through at least first and second separate flow paths, each of the flow paths containing a particulate trap and, downstream of the particulate trap, a NO X  adsorber containing a NO X  oxidation catalyst and a nitrate adsorbent. The major portion of the exhaust gas is passed in the lean state, for a first period of operation, along at least one of the flow paths and through, in succession, the particulate trap and the NO X  adsorber to convert NO X  to nitrate, to convert the SO 2  to sulfate and to adsorb the nitrate and the sulfate on the nitrate adsorbent. Temperatures in the particulate trap and the NO X  adsorber are monitored. After the first period of operation, the flows of the exhaust gas portions are switched so that the one flow path receives the minor exhaust gas portion for a second period of time and, during at least a part of the second period of time, fuel is introduced into the one flow path, upstream of the particulate trap, for combustion in the particulate trap to produce a fuel-rich, reducing exhaust flow. During that same second period of operation, a bypass portion of the exhaust gas is diverted from another flow path at a point upstream of the particulate trap and is introduced into the one flow path also upstream of its particulate trap. When the temperature of the particulate trap in the one flow path reaches a first predetermined temperature, heat of fuel thereto is discontinued and exhaust gas flow is increased to transfer heat from the particulate trap to the NO X  adsorber, to raise the temperature of the NO X  adsorber to a second predetermined temperature for desulfation. The major and minor exhaust gas portions are periodically switched between flow paths so that a second period of operation is effected in one flow path while a first period of operation is effected in at least one other flow path. 
     Engine speed and/or engine load may be monitored and the amount of fuel introduced and bypass flow exhaust introduced, during the second period of time, may be set in accordance with the determined engine speed and/or engine load. 
     The method of the present invention may further include sensing the NO X  concentration exiting each NO X  adsorber and, responsive to that sensed concentration exceeding a predetermined value, switching the flows of exhaust gas portions so that a flow path to be subjected to denitration receives the minor exhaust gas portion. Fuel is then introduced into the minor exhaust gas portion to create a reducing atmosphere for reduction of nitrates adsorbed on the nitrate adsorbent, to form molecular nitrogen gas. 
     The present invention is also embodied in an apparatus for treating an exhaust gas stream having the aforementioned characteristics. The apparatus includes plural exhaust flow conduits for respectively receiving portions of exhaust gas from an internal combustion engine. Each exhaust gas conduit includes a particulate trap and, downstream of the particulate trap, a NO X  adsorber containing a NO X  oxidation catalyst. The apparatus further includes temperature sensors for monitoring temperatures of the particulate traps and the NO X  adsorbers. A bypass line connects each exhaust flow conduit with at least one other exhaust flow conduit, at points upstream of the particulate traps. A regulating valve is provided in the bypass line and a fuel injector is provided in each of the exhaust flow conduits, upstream of the particulate trap. A controller controls the regulating valve and the fuel injector for an exhaust flow path for desulfation, responsive to the sensed temperatures and engine speed and/or engine load. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1 is a schematic diagram of a vehicle on-board exhaust treatment system in accordance with a preferred embodiment of the present invention. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     FIG. 1 illustrates one preferred embodiment of the present invention. In terms of apparatus the individual components are conventional, except for the bypass  6 , the bypass control valve  30  and the means  10  for controlling same, and are readily available. The apparatus of the preferred embodiment depicted in FIG. 1 includes that previously described in SAE 2001-01-3619 with addition of a perpendicular exhaust bypass loop  6  that connects both of the exhaust paths “A” and “B” upstream of the CDPFs  18 ,  19 , a bypass control valve  30  and control means therefor. This bypass is a conduit  6  which consists of a one-inch stainless steel tube outfitted with an EGR valve  30  to control bypass flow. Bypass flow was measured through the use of an orifice  14  and pressure transducers  15 . The valving is controlled by a National Instruments, Inc. data acquisition and control system, i.e., controller  10  in FIG.  1 . 
     As further shown in FIG. 1, diesel engine  1  generates an exhaust flow  2  which is spit into flow paths “A” and “B” with flow therethrough governed by open/close control valves  12 ,  13 . Diesel engine  1  is provided with an engine speed sensor  3  and an engine load sensor  4 . The split exhaust flow paths “A”, “B”, each contain a catalytic diesel particulate filter (CDPF)  18 ,  19  and an NO X  adsorber  22 ,  23 . The exhaust gas streams exiting the NO X  adsorbers  22 ,  23  are recombined and passed through a common diesel oxidation catalytic converter (DOC)  34 . In this preferred embodiment as developed by experiment, the system is equipped with seven NGK zirconia oxide (Zro 2 ) oxygen/NO X  sensors. These sensors output signals for both NO X  and lambda (λ). Sensors  35 ,  36 ,  37 ,  38  and  39  are utilized as NO X  sensors and sensors  32  and  33  are utilized as lambda sensors. A flow sensor, in the form of orifice  14  in combination with pressure transducers  15 , is placed in the exhaust flow line  6 . Additionally, NO X  adsorbers  22  and  23  are each provided with a temperature sensor  16 ,  17  and the CDPFs  18 ,  19  are respectively provided with temperature sensors  20 ,  21 . The controller  10  receives signals from all of the aforementioned sensors and, based on the received signals, in the manner described below controls the secondary fuel injectors,  26 ,  27 , the exhaust-flow open/shut control valves  12 ,  13  and the exhaust bypass flow control valve  30 . 
     The method of the present invention, in one departure from the prior art, uses no external heating source to achieve the high adsorber catalyst temperatures needed to initiate sustainable desulfation. Local temperature extremes are minimized on the NO X  adsorber surface by generating the exotherm across the CDPF and then transferring the heat to the adsorber via exhaust flow. If the exotherm were to be generated across the NO X  adsorber, hot spots would locally destroy the catalytic and adsorption functions. The operations constituting the method of the present invention may be summarized as follows: 
     A. At all times at least half of the exhaust system (one or more exhaust paths or “legs”) is operating with a majority of the exhaust flow (“major portion”) in an “adsorption mode”, wherein the exhaust is well fuel-lean of stoichiometric, and NO X  is adsorbed as a metallic nitrate (usually, but not limited to, barium or potassium nitrate) within the NO X  adsorbent material. 
     B. Simultaneously with A, operating at least one of the exhaust paths in a denitration mode by restricting exhaust flow therethrough to small fraction (&lt;5%), and injecting fuel into the exhaust path to make the exhaust fuel rich and thereby reduce the adsorbed nitrates to gaseous (molecular) nitrogen which exits the system. The denitration mode is described in more detail in SAE 2001-01-3619 (coauthored by Charles Schenk, Joseph McDonald and Chris Laroo) the teachings of which are incorporated herein by reference. 
     C. Responsive to detection of NO X  leakage (typically, a concentration exceeding about 10 to 40 ppm) at the exit of a NO 3  absorber in an exhaust path operating in an adsorption mode, switching that exhaust path to the denitration mode. Typically, a given exhaust path will be switched between the NO X  adsorption mode and the denitration mode about every 30 seconds−7 minutes. The fuel injection for denitration is typically effected within 2-3 seconds and denitration continues for 20 seconds to 7 minutes. The remainder of the time an exhaust path is in the denitration mode, if any, it simply sits idle with minimal exhaust gas flow therethrough. The denitration period will vary depending on the nature of the catalyst and adsorbent, the NO X  concentration in the exhaust gas and the engine speed and/or load. 
     D. For desulfation, periodically and simultaneously with NO X  adsorption in at least one other exhaust path, at least one path of the exhaust system has its exhaust flow restricted to only a small fraction (&lt;5%) of the total flow and is operated in a desulfation mode. The desulfation of the NO X  adsorber in each flow path is initiated periodically once per every 50 to 100 hours of operation, automatically, based on a threshold of loss in the NO X  storage capacity. 
     E. While exhaust flow is restricted for desulfation, fuel is sprayed into the desulfating exhaust flow over the CDPF and the perpendicular bypass valve is opened for the first portion of the desulfation to use the CDPF to oxidize the fuel to CO and CO 2  and to generate a heat release over the CDPF due to the exothermic nature of the reaction. The injection of fuel and introduction of bypass exhaust are continued until the CDPF reaches a first predetermined temperature at which time the flow of fuel and bypass exhaust are discontinued. The amounts of fuel flow and bypass exhaust flow are set for in a given type of catalyst and adsorbent in accordance with a detected engine load and/or detected engine speed. The fuel flow might typically be about 2.5 lbs/min and continued (along with bypass exhaust flow) for up to 10 minutes. 
     F. Next, when the CDPF in the exhaust gas path undergoing desulfation reaches the first predetermined temperature, heat is transferred from the CDPF to the NO X  adsorber, bringing the NO X  adsorber catalysts up to the desired desulfating temperature (second predetermined temperature) for that specific catalyst formulation, i.e., to a second predetermined temperature, higher than the NO X  adsorption temperature, and within a range of 500-750° C. This is done by using either the bypass valve to allow a controlled exhaust flow into the desulfating leg or by opening the desulfating leg so that the full engine exhaust flow travels through the desulfating leg. Another predetermined temperature set point is used to shut off the bypass or full flow to the desulfating leg, which temperature is based on the cooling effect of the bypass or full exhaust flow on the CDPF. When the CDPF has cooled to a third predetermined temperature or when the NO X  adsorber temperature has risen to the second predetermined temperature, whichever occurs first, the exhaust flow is closed. If the NO X  adsorber has reached the desired desulfation temperature, the controller proceeds to step G below. If the adsorber had not reached the target desulfation temperature (second predetermined temperature), steps D, E and F are repeated. 
     G. The desulfating leg is closed to exhaust flow when the desired desulfating temperature (“second predetermined temperature”) is reached in the NO X  adsorber. Fuel is then sprayed into a desulfating exhaust flow into the CDPF, the desulfating exhaust flow again being &lt;5% of the total exhaust flow. Fuel injection is controlled to maintain a desired lambda value as monitored by λ/NO X  sensors. Fuel injected at high temperatures causes sulfur to be released from the NO X  adsorbers as H 2 S and SO 2 . Release of these species has been confirmed using a chemical ionization mass spectrometer. If the adsorber catalyst&#39;s temperature decreases below optimal desulfating temperatures during sulfur release, the desulfating leg is again contacted with engine exhaust flow to initiate an exotherm across the CDPF and heat is then again convectively transferred to the adsorber to maintain the adsorber temperature. 
     It is important to note that the injection and bypass timing schedule as outlined above is dependent upon catalyst formulation, engine speed, engine load, and initial exhaust and catalyst temperature. Changes to the duration of each event in the sequence need to be made depending on the system conditions. Regardless of the event length, the overall technique used to perform the desulfation remains the same. 
     TEST PROCEDURES 
     Engine Description 
     The engine used for desulfation testing was a modified 5.9 liter displacement Cummins ISB. The engine modifications are identical to those previously described in SAE 2001-01-3619. The major engine specifications are summarized in Table 1. 
     
       
         
               
             
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 Summary of major engine specifications 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Engine: 
                 1999 Cummins ISB 
               
               
                   
                 Engine 
                 6-cylinder, turbocharged- 
               
               
                   
                 Configuration: 
                 aftercooled, D1 diesel with 4- 
               
               
                   
                   
                 valves/cylinder 
               
               
                   
                 Rated Power: 
                 194 kW (260 bhp) @ 2500 rpm 
               
               
                   
                 Peak Torque: 
                 895 N-m (660 ft-lb) @ 1600 rpm 
               
               
                   
                 Fuel System: 
                 Bosch HPCR 
               
               
                   
                 Engine 
                 Bosch/ETAS 
               
               
                   
                 Management: 
               
               
                   
                 EGR System: 
                 High pressure loop, intake 
               
               
                   
                   
                 venturi w/throttled by-pass 
               
               
                   
                 Bore × Stroke: 
                 102 mm × 120 mm 
               
               
                   
                 Cylinder 
                 5.88 L 
               
               
                   
                 Displacement: 
               
               
                   
                 Compression Ratio: 
                 16.3:1 
               
               
                   
                   
               
             
          
         
       
     
     Exhaust System Description 
     The dual path NO X  adsorber system, specifications of the CDPFs and NO X  adsorbers used with the system, and regeneration/NO X  reduction control strategies used for this testing are similar to those previously described in detail in SAE 2001-01-3619. The entire system was built using readily obtainable components. CDPF and NO X  adsorber volumes were not optimized. All control system components, including exhaust brakes, exhaust fuel injectors, wide-range linear UEGO sensors, and zirconia-NO X  sensors remained the same as in the configuration described in SAE 2001-01-1351 (C. Schenck, J. McDonald and B. Olson), the teachings of which are incorporated herein by reference. 
     Modifications were made to the existing system for the purpose of sulfur removal from the catalyst. Modifications to the previously described system (SAE 2001-01-3619) include addition of an exhaust bypass pathway located downstream of the secondary fuel injectors and upstream of the CDPFs  18 , 19 . These modifications are described in more detail in SAE 2002-01-2871, the teachings of which are incorporated herein by reference. The bypass was constructed of one inch inner diameter stainless steel tubing. The flow through the bypass path was controlled using a Lucas EGR valve,  30 . Bypass flow was measured by determining the pressure difference across a sharp edge orifice  14 . Thermocouples  16 ,  17  were inserted into the NO X  adsorbers  22 ,  23  perpendicular to the flow path, at the mid-bed point of the substrate, for the purpose of monitoring the catalyst bed temperature. The CDPF substrate temperature was also monitored using two triple junction thermocouples  20 ,  21 . These thermocouples  20 ,  21  were inserted along the substrate horizontal at center and 5.25 inches radially from the center point of the flow path. The temperature measurement points of the junctions were located 2, 4, and 9 inches from the back of the CDPF at the center position and 1, 6, and 11 inches from the back of the CDPF at the radial position. 
     Test Cycles 
     All desulfation testing was done at mode  3  of the supplemental emissions test (SET), as described in SAE 2002-01-2871, at 1947 rpm and 328 lb-ft of torque. The engine out exhaust temperature at this mode was 450° C. 
     Test Fuel 
     The fuel used to poison the NO X  adsorbers used for desulfation testing was Phillips Chemical Company Lot OEPULDO 1 . This fuel was specified by the U.S. Department of Energy&#39;s Diesel Emission Control-Sulfur Effects (DECSE) program to have similar properties to today&#39;s on-highway fuel with the exception of very low sulfur content. The fuel properties are shown in Table 2. A very low sulfur fuel was chosen to minimize the impact of sulfur poisoning on NO X  adsorber. 
     The fuel used during desulfation testing was Phillips Chemical Company Lot  1  HPULDO 1 . This fuel was identical to that specified by the U.S. Department of Energy&#39;s Diesel Emission Control-Sulfur Effects (DECSE) program to have similar properties to today&#39;s on-highway fuel with the exception of zero sulfur content. The fuel properties are shown in Table 3. Lab results indicated a fuel sulfur concentration of less than 0.7 ppm by weight, which was below the limit of detection (LOD) for the instrument. Zero sulfur fuel was used in order to ensure that further poisoning of the NO X  adsorbers did not occur during desulfation testing. Although trace amounts of sulfur were present in the fuel, it accounted for less than 28 ppb SO 2  engine out and its contribution to adsorber poisoning, as well as that from engine oil consumption, can be considered negligible. 
     Laboratory 
     The engine was tested at Heavy-Duty Engine (HDE) Site  2  at the U.S. EPA-NVFEL facility in Ann Arbor, Mich. The test site is equipped with a 600 bhp DC dynamometer and a Horiba full-flow CVS and particulate measurement system. Dilute gaseous regulated emissions were measured per 40 CFR § 86 Subpart N. Gaseous analyses were performed using a gas-analysis bench made up of loose analyzers previously described in SAE Tech. Paper Ser. 2001, No. 2001-01-3619. Modal measurement of sulfur released in the form of sulfur dioxide (SO 2 ) and hydrogen sulfide (H 2 S) was performed using a V&amp;F AS-2000 chemical ionization mass spectrometer utilizing internal high speed switching. Sulfur release was measured in between the NO X  adsorbers and downstream of the second adsorber substrate in one leg of the dual path system. High speed sample switching allows measurements to take place in the exhaust at two points with a total cycle time of 1.5 seconds with a T 90  of less than 50 ms. 
     
       
         
               
             
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Summary of low sulfur fuel properties 
               
             
          
           
               
                   
                 Test Method 
                 Results 
               
               
                   
                   
               
               
                   
                 Net Heat of Combustion, ASTM 
                  43.19 
               
               
                   
                 D3338-92 (MJIkg) 
               
               
                   
                 Density @ 15.5° C. (g/cm 3 ) 
                  0.8258 
               
               
                   
                 Cetane Number 
                  43.4 
               
               
                   
                 Cetane Index 
                  53.5 
               
               
                   
                 Olefins, FIA D1319-93 (% Vol.) 
                  3.3 
               
               
                   
                 Aromatics, D1319-93 (% Vol.) 
                  24.2 
               
               
                   
                 Sulfur, ASTM D2622 (ppm 
                  3 
               
               
                   
                 mass) 
               
               
                   
                 Carbon, ASTM D3343-95 (% 
                  0.8638 
               
               
                   
                 mass) 
               
               
                   
                 Distillation Properties, ASTM 
               
               
                   
                 D86 
               
               
                   
                 IBP (° C.): 
                 191 
               
               
                   
                 10% (° C.): 
                 213 
               
               
                   
                 50% (° C.): 
                 258 
               
               
                   
                 90% (° C.): 
                 312 
               
               
                   
                 End Point (° C.): 
                 346 
               
               
                   
                 Residue Diesel (mL): 
                  0 
               
               
                   
                 Recovery: 
                 100% 
               
               
                   
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Summary of zero sulfur fuel properties. 
               
             
          
           
               
                   
                 Test Method 
                 Results 
               
               
                   
                   
               
               
                   
                 Net Heat of Combustion, ASIM 
                  43.06 
               
               
                   
                 D3338-92 (MJIkg) 
               
               
                   
                 Density @ 15.5 ° C. (g/cm 3 ) 
                  0.8348 
               
               
                   
                 Cetane Number 
                  44.8 
               
               
                   
                 Cetane Index 
                  50.6 
               
               
                   
                 Olefins, FIA D1319-93 (% Vol.) 
                  3.2 
               
               
                   
                 Aromatics, D1319-93 (% Vol.) 
                  24.5 
               
               
                   
                 Sulfur, ASTM D2622 (ppm mass) 
                  &lt;0.7 
               
               
                   
                 Carbon, ASTM D3343-95 (% mass) 
                  0.8659 
               
               
                   
                 Distillation Properties, ASTM D86 
               
               
                   
                 IBP (° C.): 
                 181 
               
               
                   
                 10% (° C.): 
                 205 
               
               
                   
                 50% (° C.): 
                 259 
               
               
                   
                 90% (° C.): 
                 318 
               
               
                   
                 End Point (° C.): 
                 351 
               
               
                   
                 Residue Diesel (mL): 
                  0 
               
               
                   
                 Recovery: 
                 100% 
               
               
                   
                   
               
             
          
         
       
     
     Desulfation Strategy 
     Initial Desulfation Testing 
     Initial development performed using the dual path system was done without the use of the exhaust bypass valve. The desulfation routine was automated using a time-based schedule and the general procedure was as follows: 
     1. While the engine operated at mode  3  of the SET fuel was injected into the bypassed leg of the exhaust system creating a very rich environment (λ&lt;0.6). 
     2. The bypass leg was then opened to full exhaust flow for a predetermined time. Oxidation of the hydrocarbon reductant over the CDPF and NO X  adsorbers generated an exotherm causing an elevation in NO X  adsorber temperature. The amount of fuel injected during the first event and the amount of time that the desulfating leg is exposed to full flow determined the temperature rise of the adsorber. If the adsorber reached the desulfation temperature, exhaust flow to the leg was closed off. 
     3. If the rear NO X  adsorber catalyst did not reach the desired desulfation temperature, the process was repeated and the generated exotherm, in conjunction with convective heat transfer, brought both adsorber substrates to the target temperature. 
     4. Fuel was then injected into the leg to maintain the desired lambda value (λ&lt;1) causing sulfur release. The low mass flow through the leg (caused by exhaust brake slip) allowed the adsorbers to stay at the desulfation temperatures for an extended period. 
     Refined Desulfation Testing 
     Further desulfation development performed using the dual path system was done with the use of an exhaust bypass valve to study the impact of exhaust flow. The test controller was automated to allow target lambda and exhaust bypass flows to be met. The desulfation leg lambda and exhaust bypass flow were optimized to allow exotherms to occur on the surface of the CDPF while minimizing exotherms on the NO X  adsorber. The general procedure was as follows: 
     1. Target lambda, bypass flow, NO X  adsorber temperature, and CDPF maximum temperature set points were inputted into the desulfation controller. 
     2. While the engine operated at mode  3  of the SET, fuel was injected into the bypassed leg of the exhaust system to meet the target exhaust lambda value. Bypass exhaust flowed into the desulfating leg at a low flow rate. 
     3. The combination of bypassed exhaust and injected fuel created exotherms from the oxidation of hydrocarbons on the surface of the CDPF causing an elevation in the CDPF temperature. 
     4. When the CDPF reached a predetermined temperature, the desulfation leg was opened to full exhaust flow. Heat was transferred convectively from the CDPF to the NO X  adsorber. When the CDPF reached a preset lower temperature limit, the desulfating leg was switched back to bypass mode. This process was repeated until the NO X  adsorbers reached the desired desulfation temperature. 
     5. When the desulfation temperature was reached, the bypass flow was lowered further and reductant was injected to maintain a desired lambda value causing sulfur release. Low mass flow through the leg allowed the adsorbers to stay at desulfation temperatures for an extended period. 
     Parametric testing was performed to determine the optimum parameters for heating the NO X  adsorbers in preparation for desulfation. The goal was to reach desulfation temperature in the shortest amount of time, while keeping the adsorber temperature rise rate (i.e. exotherm) at a moderate level. 
     RESULTS 
     Initial Technique 
     The original heating/desulfation technique used an event timer table similar to that used in previous FTP tests an example of which appears below as Table X: 
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE X 
               
             
             
               
                   
               
               
                 Heating/Desulfation Timer Table 
               
             
          
           
               
                 Event # 
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
               
               
                   
               
             
          
           
               
                 Time(s) 
                 0 
                 85  
                 115 
                 250  
                 270  
                 850  
               
               
                 Flow path 
                 0 
                 1 
                 0 
                 1 
                 0 
                 0 
               
               
                 in bypass (0 or 1) 
               
               
                 Fuel amount 
                 0.25 
                 0 
                 0.25 
                 0 
                 0 
                 0 
               
               
                 (lbs/min) 
               
               
                   
               
             
          
         
       
     
     This table commanded fueling rates, fueling durations and the flow control valves for the two exhaust legs. For heating and desulfurization, this table was set up to provide very rich (λ&lt;0.6) conditions at low exhaust flows (from exhaust brake slip). Since the CDPF was lightly catalyzed and there was little oxygen present to oxidize all of the injected fuel, accumulation of fuel occurred on the adsorber substrates during the rich, low-flow condition. After about 85 seconds, the heating leg would be exposed to full exhaust flow. The accumulated fuel would then be oxidized producing a very rapid exotherm. The process was then repeated a second time to heat up the second NO X  adsorber substrate (two 9.5″ diameter ×6″ long substrates were used). The  NOX  adsorber and CDPF temperatures can be seen in FIG.  4 . The front adsorber bed temperature increased rapidly after the first exposure to full exhaust flow at 90 seconds. The exhaust flow was reduced again from 115 seconds to 250 seconds while running rich as indicated by Desulfation Lambda. When the leg was opened to full exhaust flow the second time, the second adsorber substrate saw a rapid increase in temperature. The NO X  adsorbers reached their target temperature of 680° C. in about 270 seconds. The target temperature was defined for these tests to be the average of the NO X  adsorber substrate temperatures. 
     Under these hot, rich conditions, sulfur was released in the form of H 2 S. The sulfur release for this adsorber formula started at about 700° C. and progressed until the timer table stopped the fuel injection. The DOC downstream of the adsorbers operates in a lean environment that oxidizes the H 2 S to SO 2 . 
     The drawback to this method of heating/desulfation is that the local surface temperatures seen during this exotherm must be well in excess of the measured temperatures in order to drive such a rapid increase in the adsorber substrate temperatures. Such high temperatures will damage known NO X  adsorber washcoats. Since the local temperatures cannot be measured directly, the temperature change rate (TCR) has been adopted as an indicator of local surface temperatures and the general harshness of an exotherm with respect to the catalyst washcoat. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Measurements made during five desulfation events using the initial 
               
               
                 technique described in the Results section.* 
               
             
          
           
               
                   
                 t R   
                 T R   
                 M R   
                 t M     R     
                 t EoR   
                 T EoR   
                 ΔM/Δt + 
                 ΔM/Δt − 
               
               
                 Event 
                 (s) 
                 (° C.) 
                 (ppm) 
                 (s) 
                 (s) 
                 (° C.) 
                 (ppm/min) 
                 (ppm/min) 
               
               
                   
               
             
          
           
               
                 1 
                 358.3 
                 701.0 
                 416.7 
                 519.5 
                 852.9 
                 645.0 
                 124 
                 −60 
               
               
                 2 
                 349.6 
                 701.6 
                 190.7 
                 543.5 
                 863.4 
                 625.9 
                 47 
                 −29 
               
               
                 3 
                 347.9 
                 701.8 
                 152.2 
                 552.2 
                 858.4 
                 633.8 
                 36 
                 −24 
               
               
                 4 
                 352.5 
                 701.3 
                 109.0 
                 583.2 
                 859.4 
                 631.5 
                 23 
                 −19 
               
               
                 5 
                 348.7 
                 701.6 
                 77.2 
                 594.2 
                 861.0 
                 628.9 
                 15 
                 −14 
               
               
                 σ 
                 1.1 
                 0.04 
                 63 
                 4.8 
                 0.4 
                 1.0 
                 79.9 
                 55.8 
               
               
                 (% of mean) 
               
               
                   
               
               
                 *The columns show, from left to right, attempt number, time to start of release, average NOx adsorber temperature at start of release, magnitude of peak release, time to peak release, time to end of release, and temperature at end of release. The last two columns present an approximation of the rate of release approaching and receding from peak release, respectively. The measured sulfur release was in the form of H 2 S.  
               
             
          
         
       
     
     Using the above technique, measurements of desulfation parameters were taken for five separate, consecutive desulfation events with sufficient equilibration time between events. The measured parameters, shown in Table 4, include time to start of release, t R  average NO X  adsorber temperature at start of release, T R  magnitude of peak release, M R , time to peak release, t MR  time to end of release, t EOR , and temperature at end of release, T EOR . Sulfur release data, from which M R  was taken, was averaged over 10 seconds. The start of release is defined as the point at which release reaches 20% of M R  during positive rate of release while the end of release is defined as the point at which release again reaches 20% of M R  during negative rate of release. Using these definitions, sulfur removal at the start and end of release were determined to be well within the mass spectrometer measurement error of ±1% read value, down to 1 ppm. Approximations of the rate of release approaching (ΔM/Δt + ) and receding from (ΔM/Δt) the peak release were also included as parameters. The approaching and receding rates were approximated by (t MR −t R )/(0.8*M R ) and (t EoR −t MR )/(−0.8*M R ), respectively. All five events were performed over the same CDPF and NO X  adsorbers without re-poisoning the adsorbers between events. Since the amount of sulfur available for removal decreased after each event, this data allows the impact of sulfur load on the desulfation parameters listed in Table 4 to be determined. 
     For these five events, release of H 2 S occurred at an average time of 354 seconds with a deviation of approximately 1%, at a T R  of 702° C. The deviation in T R  is significantly less than the accuracy of the thermocouples used to measure its value. The general characteristics of sulfur removal suggested by ΔM(Δt +  and ΔM/Δt are a rapid increase in the amount of sulfur removed, from the start of release to the peak release, followed by a decrease in sulfur removal over a much longer time-scale. The average duration of release was 508 seconds with a deviation on the order of 1%. For each consecutive desulfation event, M R  decreased by 20-54% while t MR  increased by 2-5%, when compared to the previous event. It should be noted that although the parameters in Table 4 are dependant on NO X  adsorber washcoat formulation, the above data may still be used to determine the qualitative dependence of these parameters on sulfur load for any washcoat with generally similar characteristics to those that have been used here. 
     The relationship between TCR and catalyst durability has not been firmly established and is washcoat and substrate dependent. The TCRs that result from the heating algorithm described above are likely to be damaging to the washcoats, particularly the adsorbers. The CDPF has a simpler washcoat formulation that is designed to be tolerant of the exotherms that occur when accumulated PM rapidly oxidizes. Thus CDPFs are less likely to be damaged by fuel-induced exotherms than NO X  adsorbers. Considering these factors, another heating algorithm was investigated. 
     Refined Heating Technique 
     The next heating algorithm attempted to minimize the adsorber exotherm by oxidizing most of the fuel on a highly catalyzed DPF. The lambda values were also kept at 0.8 or higher to minimize the fuel slippage through the CDPF. 
     In addition to very high TCRs, the previous timer table method suffered from repeatability issues. The exotherm behavior of the catalysts is dependent on their conditioning prior to the start of test. Although substrate temperature repeatability was shown in five consecutive tests, the maximum temperatures and lambdas varied from day to day with the same timer table. To address this, the controller was modified in three ways. The first modification was the addition of a routine that monitored the catalyst temperatures. This routine looked at preset maximum temperatures for the CDPF, shutting off the fuel and opening the desulfating leg to full flow when the CDPF temperature reached the set maximum, allowing for convective heat transfer to the NO X  adsorbers. The adsorber temperatures were also monitored to determine when they had reached the desired temperature. When this happened the controller transitioned from the healing phase to the desulfurization phase. During this phase the exhaust flow was lowered to minimize the exotherm caused by the fuel injected to maintain λ&lt;1. The elevated temperature and the lambda conditions were then held in these desulfation-promoting conditions. 
     The other two modifications were the addition of closed loop lambda control based on feedback from an oxygen sensor and closed loop control of the exhaust bypass flow based on feedback from a sharp edged orifice. The hardware changes are described in the Exhaust System Description. 
     Experimental data indicates that about two-thirds of the sulfur comes off of the front substrate. This would be expected since the front substrate should capture most of the sulfur. The data also dispels the concern that sulfur released from the front substrate gets readsorbed on the rear substrate. This may still be happening to some degree, but the data indicates a net sulfur release from the second substrate. The release shown here is smaller in magnitude than in FIG. 4 due to the frequent desulfurizations that had occurred prior to this data set. 
     This refined method produced maximum TCRs for all of the catalysts which were substantially lower than those of the initial heating technique which indicates that the exotherm has been substantially moved to the CDPF. The exotherm on the CDPF is controlled by higher lambdas during heating and temperature modulation by the controller. The combination of these parameters minimizes fuel slippage to the adsorbers and lowers the CDPF exotherm when exposed to full flow. 
     Desulfation Parametric Study 
     After refining the desulfation heating technique it was decided to run a parametric study to determine which variables affected NO X  adsorber temperature rise. A ( 2   4 ) Two-Level Factorial Design of Experiments was employed to determine which variables had a significant effect on temperature rise over the CDPF and NO X  adsorbers. 
     The variables studied were Exhaust Bypass Flow, Exhaust Lambda, CDPF Hysteresis, and the CDPF Maximum Temperature. Exhaust Bypass Flow was the amount of exhaust flowing into the desulfating leg of the exhaust via the bypass pathway. Exhaust Lambda was measured downstream of the rear NO X  adsorber. CDPF Temperature was used to trigger convective heat transfer from the CDPF to the NO X  adsorber. CDPF Hysteresis is defined as the temperature difference between the Maximum CDPF temperature that initiated convective heat transfer to the NO X  adsorbers and the minimum CDPF temperature that triggers the end of the heat transfer event. There were six response variables that are thought to characterize the heating of the NO X  adsorbers. The responses that were investigated were the TCR of the front NO X , adsorber substrate, TCR Front Adsorber (° C./Sample); the TCR of the rear adsorber substrate, TCR Rear Adsorber (° C./Sample); the average difference in the NO, adsorber substrate temperatures over the test cycle, Average Adsorber Temperature Difference (° C.); TCR of the CDPF to the maximum temperature set point, TCR to CDPF Maximum Temperature (° C./Sample); the time it took the average NO X  adsorber temperature to reach the desired level, Time to Average Adsorber Temperature (s); and the final adsorber temperature difference, Front/Rear Final Adsorber Temperature Difference (° C.). 
     A test matrix of 16 tests was generated and each test was run twice for a total of 32 tests. Table 5 shows the results of the test matrix. The effects of the four main variables were calculated, as well as the first order interactions. To test for significance the effects were compared to the 95% confidence interval of the mean for each response variable. 
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Results of desulfation parametric study. 
               
             
          
           
               
                   
                   
                   
                 Average 
                 TCR to CDPF 
                   
                 Front/Rear 
               
               
                   
                 TCR Front 
                 TCR Rear 
                 Adsorber 
                 Maximum 
                 Time to Average 
                 Adsorber Final 
               
               
                   
                 Adsorber 
                 Adsorber 
                 Temperature 
                 Temperature 
                 Adsorber 
                 Temperature 
               
               
                   
                 (° C./sample) 
                 (° C./sample) 
                 Difference (° C.) 
                 (° C./sample) 
                 Temperature (s) 
                 Difference (° C.) 
               
               
                   
                   
               
             
          
           
               
                 Exhaust 
                 0.4 
                 0.4 
                 30.8 
                 −1.1 
                 −152 
                 −34 
               
               
                 Bypass 
               
               
                 Flow Effects 
               
               
                 Lambda 
                 −0.4 
                 0.3 
                 −22.9 
                 0.1 
                 40 
                 −8 
               
               
                 Effects 
               
               
                 Effect of 
                 0.5 
                 0.1 
                 −11.2 
                 0.3 
                 22 
                 −28 
               
               
                 CDPF 
               
               
                 Hysteresis 
               
               
                 Effect of 
                 −0.7 
                 −0.1 
                 12.6 
                 0.1 
                 −16 
                 39 
               
               
                 CDPF Max 
               
               
                 Effect of 
                 −0.4 
                 0.3 
                 −10.7 
                 0.4 
                 33 
                 8 
               
               
                 X1X2 
               
               
                 Effect of 
                 0.3 
                 0 
                 −0.8 
                 0 
                 30 
                 −4 
               
               
                 X1X3 
               
               
                 Effect of 
                 0.1 
                 −0.1 
                 7.4 
                 −0.1 
                 −24 
                 30 
               
               
                 X1X4 
               
               
                 Effect of 
                 −0.1 
                 0.1 
                 18.8 
                 −0.3 
                 12 
                 −39 
               
               
                 X2X3 
               
               
                 Effect of 
                 0.4 
                 0 
                 −1.5 
                 0.1 
                 −18 
                 33 
               
               
                 X2X4 
               
               
                 Effect of 
                 −0.4 
                 0 
                 4.1 
                 0.2 
                 −16 
                 −3 
               
               
                 X3X4 
               
               
                 95% Conf 
                 0.4 
                 0.2 
                 14.4 
                 0.3 
                 49 
                 26 
               
               
                 Interval 
               
               
                   
               
             
          
         
       
     
     Table 5 shows that the exhaust bypass flow is significant in five of the six response variables. The exhaust Lambda shows a weaker significance in three of the six response variables. The CDPF hysteresis and CDPF maximum temperature variables show a much weaker significance than the bypass flow and lambda. The confounded effects, which show significance, are believed to be artifacts of the multiple tests because they do not show significance when each set of runs is looked at separately. 
     CONCLUSION 
     This sequence of tests has shown that exotherms can be created across the catalysts in a way that minimizes sintering of the washcoats. Temperature change rate (TCR) was used as a measure of sintering potential. The multiple-leg arrangement allows independent control of the exhaust flow and lambda, which are the key parameters controlling the heat released by the oxidation of diesel fuel on the CDPF. The tests have shown that desulfurization temperatures can be repeatably reached using this controlled oxidation. 
     Sulfur was released in these tests as H 2 S. Since the system has a cleanup DOC operating continuously in a lean oxidizing environment, the H 2 S should be oxidized to SO 2 . This remains to be verified. Dual sampling of the H 2 S has revealed a net sulfur release on the front and rear adsorbers rather than a simple transfer of sulfur from the front adsorber to the rear. 
     The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.