Experimental and modeling study of the filtration and oxidation characteristics of a diesel oxidation catalyst and a catalyzed particulate filter

A diesel oxidation catalyst (DOC) with a catalyzed diesel particulate filter (CPF) is an effective exhaust aftertreatment device that reduces particulate emissions from diesel engines, and properly designed DOC-CPF systems provide passive regeneration of the filter by the oxidation of PM via thermal and NO2/temperature-assisted means under various vehicle duty cycles. However, controlling the backpressure on engines caused by the addition of the CPF to the exhaust system requires a good understanding of the filtration and oxidation processes taking place inside the filter as the deposition and oxidation of solid particulate matter (PM) change as functions of loading time. In order to understand the solid PM loading characteristics in the CPF, an experimental and modeling study was conducted using emissions data measured from the exhaust of a John Deere 6.8 liter, turbocharged and after-cooled engine with a low-pressure loop EGR system and a DOC-CPF system (or a CCRT® - Catalyzed Continuously Regenerating Trap®, as named by Johnson Matthey) in the exhaust system. A series of experiments were conducted to evaluate the performance of the DOC-only, CPF-only and DOC-CPF configurations at two engine speeds (2200 and 1650 rpm) and various loads on the engine ranging from 5 to 100% of maximum torque at both speeds. Pressure drop across the DOC and CPF, mass deposited in the CPF at the end of loading, upstream and downstream gaseous and particulate emissions, and particle size distributions were measured at different times during the experiments to characterize the pressure drop and filtration efficiency of the DOCCPF system as functions of loading time. Pressure drop characteristics measured experimentally across the DOC-CPF system showed a distinct deep-bed filtration region characterized by a non-linear pressure drop rise, followed by a transition region, and then by a cake-filtration region with steadily increasing pressure drop with loading time at engine load cases with CPF inlet temperatures less than 325 °C. At the engine load cases with CPF inlet temperatures greater than 360 °C, the deep-bed filtration region had a steep rise in pressure drop followed by a decrease in pressure drop (due to wall PM oxidation) in the cake filtration region. Filtration efficiencies observed during PM cake filtration were greater than 90% in all engine load cases. Two computer models, i.e., the MTU 1-D DOC model and the MTU 1-D 2-layer CPF model were developed and/or improved from existing models as part of this research and calibrated using the data obtained from these experiments. The 1-D DOC model employs a three-way catalytic reaction scheme for CO, HC and NO oxidation, and is used to predict CO, HC, NO and NO2 concentrations downstream of the DOC. Calibration results from the 1-D DOC model to experimental data at 2200 and 1650 rpm are presented. The 1-D 2-layer CPF model uses a ‘2-filters in series approach’ for filtration, PM deposition and oxidation in the PM cake and substrate wall via thermal (O2) and NO2/temperature-assisted mechanisms, and production of NO2 as the exhaust gas mixture passes through the CPF catalyst washcoat. Calibration results from the 1-D 2-layer CPF model to experimental data at 2200 rpm are presented. Comparisons of filtration and oxidation behavior of the CPF at sample load-cases in both configurations are also presented. The input parameters and selected results are also compared with a similar research work with an earlier version of the CCRT®, to compare and explain differences in the fundamental behavior of the CCRT® used in these two research studies. An analysis of the results from the calibrated CPF model suggests that pressure drop across the CPF depends mainly on PM loading and oxidation in the substrate wall, and also that the substrate wall initiates PM filtration and helps in forming a PM cake layer on the wall. After formation of the PM cake layer of about 1-2 µm on the wall, the PM cake becomes the primary filter and performs 98-99% of PM filtration. In all load cases, most of PM mass deposited was in the PM cake layer, and PM oxidation in the PM cake layer accounted for 95-99% of total PM mass oxidized during loading. Overall PM oxidation efficiency of the DOC-CPF device increased with increasing CPF inlet temperatures and NO2 flow rates, and was higher in the CCRT® configuration compared to the CPF-only configuration due to higher CPF inlet NO2 concentrations. Filtration efficiencies greater than 90% were observed within 90-100 minutes of loading time (starting with a clean filter) in all load cases, due to the fact that the PM cake on the substrate wall forms a very efficient filter. A good strategy for maintaining high filtration efficiency and low pressure drop of the device while performing active regeneration would be to clean the PM cake filter partially (i.e., by retaining a cake layer of 1-2 µm thickness on the substrate wall) and to completely oxidize the PM deposited in the substrate wall. The data presented support this strategy.

Filtration and oxidation characteristics of a diesel oxidation catalyst and a catalyzed particulate filter : development of a 1-D 2-layer model

The emissions, filtration and oxidation characteristics of a diesel oxidation catalyst (DOC) and a catalyzed particulate filter (CPF) in a Johnson Matthey catalyzed continuously regenerating trap (CCRT ®) were studied by using computational models. Experimental data needed to calibrate the models were obtained by characterization experiments with raw exhaust sampling from a Cummins ISM 2002 engine with variable geometry turbocharging (VGT) and programmed exhaust gas recirculation (EGR). The experiments were performed at 20, 40, 60 and 75% of full load (1120 Nm) at rated speed (2100 rpm), with and without the DOC upstream of the CPF. This was done to study the effect of temperature and CPF-inlet NO2 concentrations on particulate matter oxidation in the CCRT ®. A previously developed computational model was used to determine the kinetic parameters describing the oxidation characteristics of HCs, CO and NO in the DOC and the pressure drop across it. The model was calibrated at five temperatures in the range of 280 – 465° C, and exhaust volumetric flow rates of 0.447 – 0.843 act-m3/sec. The downstream HCs, CO and NO concentrations were predicted by the DOC model to within ±3 ppm. The HCs and CO oxidation kinetics in the temperature range of 280 - 465°C and an exhaust volumetric flow rate of 0.447 - 0.843 act-m3/sec can be represented by one ’apparent’ activation energy and pre-exponential factor. The NO oxidation kinetics in the same temperature and exhaust flow rate range can be represented by ’apparent’ activation energies and pre-exponential factors in two regimes. The DOC pressure drop was always predicted within 0.5 kPa by the model. The MTU 1-D 2-layer CPF model was enhanced in several ways to better model the performance of the CCRT ®. A model to simulate the oxidation of particulate inside the filter wall was developed. A particulate cake layer filtration model which describes particle filtration in terms of more fundamental parameters was developed and coupled to the wall oxidation model. To better model the particulate oxidation kinetics, a model to take into account the NO2 produced in the washcoat of the CPF was developed. The overall 1-D 2-layer model can be used to predict the pressure drop of the exhaust gas across the filter, the evolution of particulate mass inside the filter, the particulate mass oxidized, the filtration efficiency and the particle number distribution downstream of the CPF. The model was used to better understand the internal performance of the CCRT®, by determining the components of the total pressure drop across the filter, by classifying the total particulate matter in layer I, layer II, the filter wall, and by the means of oxidation i.e. by O2, NO2 entering the filter and by NO2 being produced in the filter. The CPF model was calibrated at four temperatures in the range of 280 – 465 °C, and exhaust volumetric flow rates of 0.447 – 0.843 act-m3/sec, in CPF-only and CCRT ® (DOC+CPF) configurations. The clean filter wall permeability was determined to be 2.00E-13 m2, which is in agreement with values in the literature for cordierite filters. The particulate packing density in the filter wall had values between 2.92 kg/m3 - 3.95 kg/m3 for all the loads. The mean pore size of the catalyst loaded filter wall was found to be 11.0 µm. The particulate cake packing densities and permeabilities, ranged from 131 kg/m3 - 134 kg/m3, and 0.42E-14 m2 and 2.00E-14 m2 respectively, and are in agreement with the Peclet number correlations in the literature. Particulate cake layer porosities determined from the particulate cake layer filtration model ranged between 0.841 and 0.814 and decreased with load, which is about 0.1 lower than experimental and more complex discrete particle simulations in the literature. The thickness of layer I was kept constant at 20 µm. The model kinetics in the CPF-only and CCRT ® configurations, showed that no ’catalyst effect’ with O2 was present. The kinetic parameters for the NO2-assisted oxidation of particulate in the CPF were determined from the simulation of transient temperature programmed oxidation data in the literature. It was determined that the thermal and NO2 kinetic parameters do not change with temperature, exhaust flow rate or NO2 concentrations. However, different kinetic parameters are used for particulate oxidation in the wall and on the wall. Model results showed that oxidation of particulate in the pores of the filter wall can cause disproportionate decreases in the filter pressure drop with respect to particulate mass. The wall oxidation model along with the particulate cake filtration model were developed to model the sudden and rapid decreases in pressure drop across the CPF. The particulate cake and wall filtration models result in higher particulate filtration efficiencies than with just the wall filtration model, with overall filtration efficiencies of 98-99% being predicted by the model. The pre-exponential factors for oxidation by NO2 did not change with temperature or NO2 concentrations because of the NO2 wall production model. In both CPF-only and CCRT ® configurations, the model showed NO2 and layer I to be the dominant means and dominant physical location of particulate oxidation respectively. However, at temperatures of 280 °C, NO2 is not a significant oxidizer of particulate matter, which is in agreement with studies in the literature. The model showed that 8.6 and 81.6% of the CPF-inlet particulate matter was oxidized after 5 hours at 20 and 75% load in CCRT® configuration. In CPF-only configuration at the same loads, the model showed that after 5 hours, 4.4 and 64.8% of the inlet particulate matter was oxidized. The increase in NO2 concentrations across the DOC contributes significantly to the oxidation of particulate in the CPF and is supplemented by the oxidation of NO to NO2 by the catalyst in the CPF, which increases the particulate oxidation rates. From the model, it was determined that the catalyst in the CPF modeslty increases the particulate oxidation rates in the range of 4.5 – 8.3% in the CCRT® configuration. Hence, the catalyst loading in the CPF of the CCRT® could possibly be reduced without significantly decreasing particulate oxidation rates leading to catalyst cost savings and better engine performance due to lower exhaust backpressures.

Parameter identification of a copper-zeolite SCR catalyst model using reactor data

The selective catalytic reduction system is a well established technology for NOx emissions control in diesel engines. A one dimensional, single channel selective catalytic reduction (SCR) model was previously developed using Oak Ridge National Laboratory (ORNL) generated reactor data for an iron-zeolite catalyst system. Calibration of this model to fit the experimental reactor data collected at ORNL for a copper-zeolite SCR catalyst is presented. Initially a test protocol was developed in order to investigate the different phenomena responsible for the SCR system response. A SCR model with two distinct types of storage sites was used. The calibration process was started with storage capacity calculations for the catalyst sample. Then the chemical kinetics occurring at each segment of the protocol was investigated. The reactions included in this model were adsorption, desorption, standard SCR, fast SCR, slow SCR, NH3 Oxidation, NO oxidation and N2O formation. The reaction rates were identified for each temperature using a time domain optimization approach. Assuming an Arrhenius form of the reaction rates, activation energies and pre-exponential parameters were fit to the reaction rates. The results indicate that the Arrhenius form is appropriate and the reaction scheme used allows the model to fit to the experimental data and also for use in real world engine studies.

A SCR Model based on Reactor and Engine Experimental Studies for a Cu-zeolite Catalyst

A NOx reduction efficiency higher than 95% with NH3 slip less than 30 ppm is desirable for heavy-duty diesel (HDD) engines using selective catalytic reduction (SCR) systems to meet the US EPA 2010 NOx standard and the 2014-2018 fuel consumption regulation. The SCR performance needs to be improved through experimental and modeling studies. In this research, a high fidelity global kinetic 1-dimensional 2-site SCR model with mass transfer, heat transfer and global reaction mechanisms was developed for a Cu-zeolite catalyst. The model simulates the SCR performance for the engine exhaust conditions with NH3 maldistribution and aging effects, and the details are presented. SCR experimental data were collected for the model development, calibration and validation from a reactor at Oak Ridge National Laboratory (ORNL) and an engine experimental setup at Michigan Technological University (MTU) with a Cummins 2010 ISB engine. The model was calibrated separately to the reactor and engine data. The experimental setup, test procedures including a surrogate HD-FTP cycle developed for transient studies and the model calibration process are described. Differences in the model parameters were determined between the calibrations developed from the reactor and the engine data. It was determined that the SCR inlet NH3 maldistribution is one of the reasons causing the differences. The model calibrated to the engine data served as a basis for developing a reduced order SCR estimator model. The effect of the SCR inlet NO2/NOx ratio on the SCR performance was studied through simulations using the surrogate HD-FTP cycle. The cumulative outlet NOx and the overall NOx conversion efficiency of the cycle are highest with a NO2/NOx ratio of 0.5. The outlet NH3 is lowest for the NO2/NOx ratio greater than 0.6. A combined engine experimental and simulation study was performed to quantify the NH3 maldistribution at the SCR inlet and its effects on the SCR performance and kinetics. The uniformity index (UI) of the SCR inlet NH3 and NH3/NOx ratio (ANR) was determined to be below 0.8 for the production system. The UI was improved to 0.9 after installation of a swirl mixer into the SCR inlet cone. A multi-channel model was developed to simulate the maldistribution effects. The results showed that reducing the UI of the inlet ANR from 1.0 to 0.7 caused a 5-10% decrease in NOx reduction efficiency and 10-20 ppm increase in the NH3 slip. The simulations of the steady-state engine data with the multi-channel model showed that the NH3 maldistribution is a factor causing the differences in the calibrations developed from the engine and the reactor data. The Reactor experiments were performed at ORNL using a Spaci-IR technique to study the thermal aging effects. The test results showed that the thermal aging (at 800°C for 16 hours) caused a 30% reduction in the NH3 stored on the catalyst under NH3 saturation conditions and different axial concentration profiles under SCR reaction conditions. The kinetics analysis showed that the thermal aging caused a reduction in total NH3 storage capacity (94.6 compared to 138 gmol/m3), different NH3 adsorption/desorption properties and a decrease in activation energy and the pre-exponential factor for NH3 oxidation, standard and fast SCR reactions. Both reduction in the storage capability and the change in kinetics of the major reactions contributed to the change in the axial storage and concentration profiles observed from the experiments.