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Journal Article

Laboratory Study of Soot, Propylene, and Diesel Fuel Impact on Zeolite-Based SCR Filter Catalysts

2009-04-20
2009-01-0903
Selective Catalytic Reduction (SCR) catalysts have been designed to reduce NOx with the assistance of an ammonia-based reductant. Diesel Particulate Filters (DPF) have been designed to trap and eventually oxidize particulate matter (PM). Combining the SCR function within the wall of a high porosity particulate filter substrate has the potential to reduce the overall complexity of the aftertreatment system while maintaining the required NOx and PM performance. The concept, termed Selective Catalytic Reduction Filter (SCRF) was studied using a synthetic gas bench to determine the NOx conversion robustness from soot, coke, and hydrocarbon deposition. Soot deposition, coke derived from propylene exposure, and coke derived from diesel fuel exposure negatively affected the NOx conversion. The type of soot and/or coke responsible for the inhibited NOx conversion did not contribute to the SCRF backpressure.
Journal Article

Modeling of Thermophoretic Soot Deposition and Hydrocarbon Condensation in EGR Coolers

2009-06-15
2009-01-1939
EGR coolers are effective to reduce NOx emissions from diesel engines due to lower intake charge temperature. EGR cooler fouling reduces heat transfer capacity of the cooler significantly and increases pressure drop across the cooler. Engine coolant provided at 40–90 C is used to cool EGR coolers. The presence of a cold surface in the cooler causes particulate soot deposition and hydrocarbon condensation. The experimental data also indicates that the fouling is mainly caused by soot and hydrocarbons. In this study, a 1-D model is extended to simulate particulate soot and hydrocarbon deposition on a concentric tube EGR cooler with a constant wall temperature. The soot deposition caused by thermophoresis phenomena is taken into account the model. Condensation of a wide range of hydrocarbon molecules are also modeled but the results show condensation of only heavy molecules at coolant temperature.
Journal Article

Analysis of High Mileage Gasoline Exhaust Particle Filters

2016-04-05
2016-01-0941
The purpose of this work was to examine gasoline particle filters (GPFs) at high mileages. Soot levels for gasoline direct injection (GDI) engines are much lower than diesel engines; however, noncombustible material (ash) can cause increased backpressure, reduced power, and lower fuel economy. In this study, a post mortem was completed of two GPFs, one at 130,000 mi and the other at 150,000 mi, from two production 3.5L turbocharged GDI vehicles. The GPFs were ceramic wall-flow filters containing three-way catalytic washcoat and located downstream of conventional three-way catalysts. The oil consumption was measured to be approaching 23,000 mpqt for one vehicle and 30,000 mpqt for the other. The ash contained Ca, P, Zn, S, Fe, and catalytic washcoat. Approximately 50 wt% of the collected ash was non-lubricant derived. The filter capture efficiency of lubricant-derived ash was about 50% and the non-lubricant metal (mostly Fe) deposition rate was 0.9 to 1.2 g per 10,000 mi.
Journal Article

Analysis of Ash in Low Mileage, Rapid Aged, and High Mileage Gasoline Exhaust Particle Filters

2017-03-28
2017-01-0930
To meet future particle mass and particle number standards, gasoline vehicles may require particle control, either by way of an exhaust gas filter and/or engine modifications. Soot levels for gasoline engines are much lower than diesel engines; however, non-combustible material (ash) will be collected that can potentially cause increased backpressure, reduced power, and lower fuel economy. The purpose of this work was to examine the ash loading of gasoline particle filters (GPFs) during rapid aging cycles and at real time low mileages, and compare the filter performances to both fresh and very high mileage filters. Current rapid aging cycles for gasoline exhaust systems are designed to degrade the three-way catalyst washcoat both hydrothermally and chemically to represent full useful life catalysts. The ash generated during rapid aging was low in quantity although similar in quality to real time ash. Filters were also examined after a low mileage break-in of approximately 3000 km.
Journal Article

Enhanced Durability of a Cu/Zeolite Based SCR Catalyst

2008-04-14
2008-01-1025
Passenger and light duty diesel vehicles will require up to 90% NOx conversion over the Federal Test Procedure (FTP) to meet future Tier 2 Bin 5 standards. This accomplishment is especially challenging for low exhaust temperature applications that mostly operate in the 200 - 350°C temperature regime. Selective catalytic reduction (SCR) catalysts formulated with Cu/zeolites have shown the potential to deliver this level of performance fresh, but their performance can easily deteriorate over time as a result of high temperature thermal deactivation. These high temperature SCR deactivation modes are unavoidable due to the requirements necessary to actively regenerate diesel particulate filters and purge SCRs from sulfur and hydrocarbon contamination. Careful vehicle temperature control of these events is necessary to prevent unintentional thermal damage but not always possible. As a result, there is a need to develop thermally robust SCR catalysts.
Journal Article

Hydrocarbons and Particulate Matter in EGR Cooler Deposits: Effects of Gas Flow Rate, Coolant Temperature, and Oxidation Catalyst

2008-10-06
2008-01-2467
Compact heat exchangers are commonly used in diesel engines to reduce the temperature of recirculated exhaust gases, resulting in decreased NOx emissions. These exhaust gas recirculation (EGR) coolers experience fouling through deposition of particulate matter (PM) and hydrocarbons (HCs) that reduces the effectiveness of the cooler. Surrogate tubes have been used to investigate the impacts of gas flow rate and coolant temperature on the deposition of PM and HCs. The results indicate that mass deposition is lowest at high flow rates and high coolant temperatures. An oxidation catalyst was investigated and proved to effectively reduce deposition of HCs, but did not reduce overall mass deposition to near-zero levels. Speciation of the deposit HCs showed that a range of HCs from C15 - C25 were deposited and retained in the surrogate tubes.
Journal Article

Diesel EGR Cooler Fouling

2008-10-06
2008-01-2475
The buildup of deposits in EGR coolers causes significant degradation in heat transfer performance, often on the order of 20-30%. Deposits also increase pressure drop across coolers and thus may degrade engine efficiency under some operating conditions. It is unlikely that EGR cooler deposits can be prevented from forming when soot and HC are present. The presence of cooled surfaces will cause thermophoretic soot deposition and condensation of HC and acids. While this can be affected by engine calibration, it probably cannot be eliminated as long as cooled EGR is required for emission control. It is generally felt that “dry fluffy” soot is less likely to cause major fouling than “heavy wet” soot. An oxidation catalyst in the EGR line can remove HC and has been shown to reduce fouling in some applications. The combination of an oxidation catalyst and a wall-flow filter largely eliminates fouling. Various EGR cooler designs affect details of deposit formation.
Technical Paper

Low Volatility ZDDP Technology: Part 2 - Exhaust Catalysts Performance in Field Applications

2007-10-29
2007-01-4107
Phosphorus is known to reduce effectiveness of the three-way catalysts (TWC) commonly used by automotive OEMs. This phenomenon is referred to as catalyst deactivation. The process occurs as zinc dialkyldithiophosphate (ZDDP) decomposes in an engine creating many phosphorus species, which eventually interact with the active sites of exhaust catalysts. This phosphorous comes from both oil consumption and volatilization. Novel low-volatility ZDDP is designed in such a way that the amounts of volatile phosphorus species are significantly reduced while their antiwear and antioxidant performances are maintained. A recent field trial conducted in New York City taxi cabs provided two sets of “aged” catalysts that had been exposed to GF-4-type formulations. The trial compared fluids formulated with conventional and low-volatility ZDDPs. Results of field test examination were reported in an earlier paper (1).
Technical Paper

Laboratory Studies and Mathematical Modeling of Urea SCR Catalyst Performance

2007-04-16
2007-01-1573
This paper presents the development of an analytical model that complements laboratory based experiments to provide a tool for Selective Catalyst Reduction (SCR) applications. The model calibration is based on measured data from NOx reduction performance tests as well as ammonia (NH3) adsorption/desorption tests over select SCR catalyst formulations in a laboratory flow reactor. Only base metal/zeolite SCR samples were evaluated. Limited validations are presented that show the model agrees well with vehicle data from Environmental Protection Agency Federal Test Procedure (EPA FTP) emission assessments. The model includes energy and mass balances, several different NH3 reactions with NOx, NH3 adsorption and desorption algorithms, and NH3 oxidation.
Technical Paper

The Influence of Ammonia Slip Catalysts on Ammonia, N2O and NOX Emissions for Diesel Engines

2007-04-16
2007-01-1572
The use of urea-based selective catalytic reduction (SCR) is a promising method for achieving U.S. Tier 2 diesel emission standards for NOx. To meet the Tier 2 standards for Particulate Matter (PM), a catalyzed diesel particulate filter (CDPF) will likely be present and any ammonia (NH3) that is not consumed over an SCR catalyst would pass over the CDPF to make nitrous oxide (N2O) emissions and/or oxides of nitrogen (NOx), or exit the exhaust system as NH3. N2O is undesirable due to its high greenhouse gas potential, while NOx production from the slipped NH3 would reduce overall system NOx conversion efficiency. This paper reviews certain conditions where NH3 slip past an SCR system may be a concern, looks at what would happen to this slipped NH3 over a CDPF, and evaluates the performance of various supplier NH3 slip catalysts under varied space velocities, temperatures and concentrations of NH3 and NOx.
Technical Paper

Modeling Study of Urea SCR Catalyst Aging Characteristics

2007-04-16
2007-01-1580
This paper presents a study of urea SCR catalyst aging characteristics and implementation into an analytical model that complements laboratory based experiments for a dynamometer-aged SCR brick. The model calibration is based on measured data taken from a 120k-mile simulated dynamometer-aged base metal/zeolite SCR. Dynamometer aging led to non-uniform axial deterioration with more severe deactivation toward the front of the SCR brick compared to the rear. Data from a 120k-mile simulated hydrothermally oven-aged SCR (uniform axial aging) is used to establish baseline aged NOx performance and NH3 adsorption/desorption behavior. An axial deterioration factor is applied to the baseline model to account for differences between oven and dynamometer aging. The model is exercised using engine out vehicle data to examine how different aging processes (oven vs. dynamometer) affect overall NOx performance during the EPA FTP (Environmental Protection Agency Federal Test Procedure).
Technical Paper

Verification of Accelerated PM Loading for DPF Qualification Studies

2009-04-20
2009-01-1089
High gas prices combined with demand for improved fuel economy have prompted increased interest in diesel engine applications for both light-duty and heavy-duty vehicles. The development of aftertreatment systems for these vehicles requires significant investments of capital and time. A reliable and robust qualification testing procedure will allow for more rapid development with lower associated costs. Qualification testing for DPFs has its basis in methods similar to DOCs but also incorporates a PM loading method and regeneration testing of loaded samples. This paper examines the effects of accelerated loading using a PM generator and compares PM generator loaded DPFs to engine dynamometer loaded samples. DPFs were evaluated based on pressure drop and regeneration performance for samples loaded slowly and for samples loaded under accelerated conditions. A regeneration reactor was designed and built to help evaluate the DPFs loaded using the PM generator and an engine dynamometer.
Technical Paper

Development of Emission Transfer Functions for Predicting the Deterioration of a Cu-Zeolite SCR Catalyst

2009-04-20
2009-01-1282
Urea selective catalytic reduction (SCR) catalysts have the capability to deliver the high NOx conversion efficiencies required for future emission standards. However, the potential for the occasional over-temperature can lead to the irreversible deactivation of the SCR catalyst. On-board diagnostics (OBD) compliance requires monitoring of the SCR function to make sure it is operating properly. Initially, SCR catalyst performance metrics such as NOx conversion, NH3 oxidation, NH3 storage capacity, and BET surface area are within normal limits. However, these features degrade with high temperature aging. In this work, a laboratory flow reactor was utilized to determine the impact on these performance metrics as a function of aging condition. Upon the completion of a full time-at-temperature durability study, four performance criteria were established to help determine a likely SCR failure.
Technical Paper

Cu/Zeolite SCR on High Porosity Filters: Laboratory and Engine Performance Evaluations

2009-04-20
2009-01-0897
Selective catalytic reduction (SCR) is expected to be used extensively in the U.S. for diesel vehicle NOx control. Much progress has been made on improving performance and reducing complexity of SCR systems for vehicles in the past several years. SCR system complexity can be reduced further by implementation of SCR-coated diesel particulate filters (SCRFs). In this system, a high porosity (> 50%) filter substrate is coated with an SCR formulation, ideally in the pores of the filter walls, so that the DPF and SCR functions can be combined into a single catalyst. Two state-of-the-art Cu/zeolite SCR formulations and three types of high porosity filter substrates were included in this study. Laboratory and engine-dynamometer tests were performed to measure NOx conversion under a variety of conditions to assess the impact of ammonia oxidation, inlet NO2/NOx ratio, ammonia/NOx ratio, oxygen level, space velocity, soot loading, and ammonia loading level.
Journal Article

Impact and Prevention of Ultra-Low Contamination of Platinum Group Metals on SCR Catalysts Due to DOC Design

2009-04-20
2009-01-0627
Diesel aftertreatment systems configured with a diesel oxidation catalyst (DOC) upstream of an urea selective catalytic reduction (SCR) catalyst run the risk of precious metal contamination. During active diesel particulate filter (DPF) regeneration events, the DOC bed temperature can reach up to 850°C. Under these conditions, precious metal (especially Pt) can be volatized and then deposited on a downstream SCR catalyst. In this paper, the impact of ultra-low contamination of platinum group metals (PGM) on the SCR catalyst was studied. A method based on precious metal volatilization of a Pt-rich DOC at 850°C and under lean gas conditions was employed to contaminate downstream FeSCR and CuSCR formulations. The contamination resulted in poor NOx conversion (via NOx remake) and excessive N2O formation. The precious metal volatilization method was employed to screen various Pt/Pd based DOCs to avoid contamination of the downstream FeSCR.
Technical Paper

The Development of Low Temperature Three-Way Catalysts for High Efficiency Gasoline Engines of the Future: Part II

2018-04-03
2018-01-0939
It is anticipated that future gasoline engines will have improved mechanical efficiency and consequently lower exhaust temperatures at low load conditions, although the exhaust temperatures at high load conditions are expected to remain the same or even increase due to the increasing use of downsized turbocharged engines. In 2014, a collaborative project was initiated at Ford Motor Company, Oak Ridge National Lab, and the University of Michigan to develop three-way catalysts with improved performance at low temperatures while maintaining the durability of current TWCs. This project is funded by the U.S. Department of Energy and is intended to show progress toward the USDRIVE target of 90% conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) at 150 °C after high mileage aging. The testing protocols specified by the USDRIVE ACEC team for stoichiometric S-GDI engines were utilized during the evaluation of experimental catalysts at all three facilities.
Technical Paper

Numerical Modeling and Experimental Investigations of EGR Cooler Fouling in a Diesel Engine

2009-04-20
2009-01-1506
EGR coolers are mainly used on diesel engines to reduce intake charge temperature and thus reduce emissions of NOx and PM. Soot and hydrocarbon deposition in the EGR cooler reduces heat transfer efficiency of the cooler and increases emissions and pressure drop across the cooler. They may also be acidic and corrosive. Fouling has been always treated as an approximate factor in heat exchanger designs and it has not been modeled in detail. The aim of this paper is to look into fouling formation in an EGR cooler of a diesel engine. A 1-D model is developed to predict and calculate EGR cooler fouling amount and distribution across a concentric tube heat exchanger with a constant wall temperature. The model is compared to an experiment that is designed for correlation of the model. Effectiveness, mass deposition, and pressure drop are the parameters that have been compared. The results of the model are in a good agreement with the experimental data.
Technical Paper

High Cell Density Flow Through Substrate for New Regulations

2023-04-11
2023-01-0359
This paper, written in collaboration with Ford, evaluates the effectiveness of higher cell density combined with higher porosity, lower thermal mass substrates for emission control capability on a customized, RDE (Real Driving Emissions)-type of test cycle run on a chassis dynamometer using a gasoline passenger car fitted with a three-way catalyst (TWC) system. Cold-start emissions contribute most of the emissions control challenge, especially in the case of a very rigorous cold-start. The majority of tailpipe emissions occur during the first 30 seconds of the drive cycle. For the early engine startup phase, higher porosity substrates are developed as one part of the solution. In addition, further emission improvement is expected by increasing the specific surface area (GSA) of the substrate. This test was designed specifically to stress the cold start performance of the catalyst by using a short, 5 second idle time preceding an aggressive, high exhaust mass flowrate drive cycle.
Journal Article

Effects of Oil Formulation, Oil Separator, and Engine Speed and Load on the Particle Size, Chemistry, and Morphology of Diesel Crankcase Aerosols

2016-04-05
2016-01-0897
The recirculation of gases from the crankcase and valvetrain can potentially lead to the entrainment of lubricant in the form of aerosols or mists. As boost pressures increase, the blow-by flow through both the crankcase and the valve cover increases. The resulting lubricant can then become part of the intake charge, potentially leading to fouling of intake components such as the intercooler and the turbocharger. The entrained aerosol which can contain the lubricant and soot may or may not have the same composition as the bulk lubricant. The complex aerodynamic processes that lead to entrainment can strip out heavy components or volatilize light components. Similarly, the physical size and numbers of aerosol particles can be dependent upon the lubricant formulation and engine speed and load. For instance, high rpm and load may increase not only the flow of gases but the amount of lubricant aerosol.
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