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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

Effect of Unburned Methyl Esters on the NOx Conversion of Fe-Zeolite SCR Catalyst

2009-11-02
2009-01-2777
Engine and flow reactor experiments were conducted to determine the impact of biodiesel relative to ultra-low-sulfur diesel (ULSD) on inhibition of the selective catalytic reduction (SCR) reaction over an Fe-zeolite catalyst. Fe-zeolite SCR catalysts have the ability to adsorb and store unburned hydrocarbons (HC) at temperatures below 300°C. These stored HCs inhibit or block NOx-ammonia reaction sites at low temperatures. Although biodiesel is not a hydrocarbon, similar effects are anticipated for unburned biodiesel and its organic combustion products. Flow reactor experiments indicate that in the absence of exposure to HC or B100, NOx conversion begins at between 100° and 200°C. When exposure to unburned fuel occurs at higher temperatures (250°-400°C), the catalyst is able to adsorb a greater mass of biodiesel than of ULSD. Experiments show that when the catalyst is masked with ULSD, NOx conversion is inhibited until it is heated to 400°C.
Journal Article

The Effects of Temperature, Shear Stress, and Deposit Thickness on EGR Cooler Fouling Removal Mechanism - Part 2

2016-04-05
2016-01-0186
Exhaust gas recirculation (EGR) coolers are used on diesel engines to reduce peak in-cylinder flame temperatures, leading to less NOx formation during the combustion process. There is an ongoing concern with soot and hydrocarbon fouling inside the cold surface of the cooler. The fouling layer reduces the heat transfer efficiency and causes pressure drop to increase across the cooler. A number of experimental studies have demonstrated that the fouling layer tends to asymptotically approach a critical height, after which the layer growth ceases. One potential explanation for this behavior is the removal mechanism derived by the shear force applied on the soot and hydrocarbon deposit surface. As the deposit layer thickens, shear force applied on the fouling surface increases due to the flow velocity growth. When a critical shear force is applied, deposit particles start to get removed.
Journal Article

Experimental and Numerical Study of Flame Kernel Formation Processes of Propane-Air Mixture in a Pressurized Combustion Vessel

2016-04-05
2016-01-0696
Fuel lean combustion and exhaust gas dilution are known to increase the thermal efficiency and reduce NOx emissions. In this study, experiments are performed to understand the effect of equivalence ratio on flame kernel formation and flame propagation around the spark plug for different low turbulent velocities. A series of experiments are carried out for propane-air mixtures to simulate engine-like conditions. For these experiments, equivalence ratios of 0.7 and 0.9 are tested with 20 percent mass-based exhaust gas recirculation (EGR). Turbulence is generated by a shrouded fan design in the vicinity of J-spark plug. A closed loop feedback control system is used for the fan to generate a consistent flow field. The flow profile is characterized by using Particle Image Velocimetry (PIV) technique. High-speed Schlieren visualization is used for the spark formation and flame propagation.
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

Rapidly Pulsed Reductants in Diesel NOx Reduction by Lean NOx Traps: Effects of Mixing Uniformity and Reductant Type

2016-04-05
2016-01-0956
Lean NOx Traps (LNTs) are one type of lean NOx reduction technology typically used in smaller diesel passenger cars where urea-based Selective Catalytic Reduction (SCR) systems may be difficult to package . However, the performance of lean NOx traps (LNT) at temperatures above 400 C needs to be improved. The use of Rapidly Pulsed Reductants (RPR) is a process in which hydrocarbons are injected in rapid pulses ahead of a LNT in order to expand its operating window to higher temperatures and space velocities. This approach has also been called Di-Air (diesel NOx aftertreatment by adsorbed intermediate reductants) by Toyota. There is a vast parameter space which could be explored to maximize RPR performance and reduce the fuel penalty associated with injecting hydrocarbons. In this study, the mixing uniformity of the injected pulses, the type of reductant, and the concentration of pulsed reductant in the main flow were investigated.
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.
Technical Paper

Investigation of Diesel-CNG RCCI Combustion at Multiple Engine Operating Conditions

2020-04-14
2020-01-0801
Past experimental studies conducted by the current authors on a 13 liter 16.7:1 compression ratio heavy-duty diesel engine have shown that diesel-Compressed Natural Gas (CNG) Reactivity Controlled Compression Ignition (RCCI) combustion targeting low NOx emissions becomes progressively difficult to control as the engine load is increased. This is mainly due to difficulty in controlling reactivity levels at higher loads. For the current study, CFD investigations were conducted in CONVERGE using the SAGE combustion solver with the application of the Rahimi mechanism. Studies were conducted at a load of 5 bar BMEP to validate the simulation results against RCCI experimental data. In the low load study, it was found that the Rahimi mechanism was not able to predict the RCCI combustion behavior for diesel injection timings advanced beyond 30 degCA bTDC. This poor prediction was found at multiple engine speed and load points.
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

Technical Advantages of Vanadium SCR Systems for Diesel NOx Control in Emerging Markets

2008-04-14
2008-01-1029
Selective catalytic reduction (SCR) is a promising technology for diesel aftertreatment to meet NOx emissions targets in several countries. In established markets such as the US and Europe, zeolite SCR systems are expected to be used due to their ability to survive the exhaust gas temperatures seen in an active diesel particulate filter regeneration. In emerging markets where the fuel sulfur level may be as high as 2000 parts per million, zeolite SCR catalysts may have durability issues. In these markets, low sulfur fuel is needed overall to meet emissions standards and to avoid high sulfate emissions, but the aftertreatment system must be durable to high sulfur levels because there is a risk of exposure to high sulfur fuel. Also, emissions standards may be met without a DPF in some applications, so that the exhaust system would not see temperatures of 600°C or higher.
Journal Article

Model-Based Estimation and Control System Development in a Urea-SCR Aftertreatment System

2008-04-14
2008-01-1324
In this paper, a model-based linear estimator and a non-linear control law for an Fe-zeolite urea-selective catalytic reduction (SCR) catalyst for heavy duty diesel engine applications is presented. The novel aspect of this work is that the relevant species, NO, NO2 and NH3 are estimated and controlled independently. The ability to target NH3 slip is important not only to minimize urea consumption, but also to reduce this unregulated emission. Being able to discriminate between NO and NO2 is important for two reasons. First, recent Fe-zeolite catalyst studies suggest that NOx reduction is highly favored by the NO 2 based reactions. Second, NO2 is more toxic than NO to both the environment and human health. The estimator and control law are based on a 4-state model of the urea-SCR plant. A linearized version of the model is used for state estimation while the full nonlinear model is used for control design.
Journal Article

Combined Fe-Cu SCR Systems with Optimized Ammonia to NOx Ratio for Diesel NOx Control

2008-04-14
2008-01-1185
Selective catalytic reduction (SCR) is a viable option for control of oxides of nitrogen (NOx) from diesel engines. Currently, copper zeolite (Cu-zeolite) SCR catalysts are favored for configurations where the exhaust gas temperature is below 450°C for the majority of operating conditions, while iron zeolite (Fe-zeolite) SCR catalysts are preferred where NOx conversion is needed at temperatures above 450°C. The selection of Cu-zeolite or Fe-zeolite SCR catalysts is based on the different performance characteristics of these two catalyst types. Cu-zeolite catalysts are generally known for having efficient NOx reduction at low temperatures with little or no NO2, and they tend to selectively oxidize ammonia (NH3) to N2 at temperatures above 400°C, leading to poor NOx conversion at elevated temperatures.
Journal Article

Selective Catalytic Reduction for Treating the NOx Emissions from Lean-Burn Gasoline Engines: Durability Assessment

2008-04-14
2008-01-0811
A laboratory study was performed to assess the potential of using selective catalytic reduction (SCR) with NH3 to treat the NOx emissions from lean-burn gasoline engines. A primary concern was the potential for hot rich exhaust conditions on the vehicle, as such conditions could degrade the zeolite-based SCR catalysts being developed for automotive applications. Samples of an iron/zeolite formulation were aged for 34 hours behind samples of a three-way catalyst (TWC) on a pulse-flame combustion reactor using different A/F ratio schedules that exposed the catalysts to either continuously lean operation, mostly stoichiometric operation, or mostly rich operation. For each A/F ratio schedule, separate SCR samples were aged with inlet temperatures of 750°C, 800°C, or 850°C. The aged SCR samples were evaluated for NOx conversion at 25K hr-1 during lean temperature ramps with 500 ppm NO and NH3.
Journal Article

Detection, Origin and Effect of Ultra-Low Platinum Contamination on Diesel-SCR Catalysts

2008-10-06
2008-01-2488
This paper discusses the poisoning of a selective catalytic reduction (SCR) catalyst by trace levels of platinum originating from an upstream diesel oxidation catalyst (DOC). A diesel aftertreatment system consisting of a DOC, urea based SCR Catalyst and a DPF was aged and evaluated on a 6.4 liter diesel engine dynamometer. The SCR catalyst system consisted of an Fe-zeolite catalyst followed by a Cu-zeolite catalyst. After approximately 400 hours of engine operation at varied exhaust flow rates and temperatures, deactivation of the SCR catalyst was observed. A subsequent detailed investigation revealed that the Cu catalyst was not deactivated and the front half of the Fe-based catalyst showed severe deactivation. The deactivated portion of the catalyst showed high activity of NH3 conversion to NOx and N2O formation. The cause of the deactivation was identified to be the presence of trace Pt contamination.
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.
Journal Article

The Effect of Hydrocarbons on the Selective Catalyzed Reduction of NOx over Low and High Temperature Catalyst Formulations

2008-04-14
2008-01-1030
Selective Catalytic Reduction of NOx is a promising technology to enable diesel engines to meet certification under Tier 2 Bin 5 emissions requirements. SCR catalysts for vehicle use are typically zeolitic materials known to store both hydrocarbons and ammonia. Ammonia storage on the zeolite has a beneficial effect on NOx conversion; hydrocarbons however, compete with ammonia for storage sites and may also block access to the interior of the zeolites where the bulk of the catalytic processes take place. This paper presents the results of laboratory studies utilizing surrogate hydrocarbon species to simulate engine-out exhaust over catalysts formulated to operate in both low (≈175-500°C) and high temperature (≈250-600°C) regimes. The effects of hydrocarbon exposure of these individual species on the SCR reaction are examined and observations are made as to necessary conditions for the recovery of SCR activity.
Journal Article

A Comparison of Combustion and Emissions of Diesel Fuels and Oxygenated Fuels in a Modern DI Diesel Engine

2012-09-10
2012-01-1695
Two oxygenated fuels were evaluated on a single-cylinder diesel engine and compared to three hydrocarbon diesel fuels. The oxygenated fuels included canola biodiesel (canola methyl esters, CME) and CME blended with dibutyl succinate (DBS), both of which are or have the potential to be bio-derived. DBS was added to improve the cold flow properties, but also reduced the cetane number and net heating value of the resulting blend. A 60-40 blend of the two (60% vol CME and 40% vol DBS) provided desirable cold flow benefits while staying above the U.S. minimum cetane number requirement. Contrary to prior vehicle test results and numerous literature reports, single-cylinder engine testing of both CME and the 60-40 blend showed no statistically discernable change in NOx emissions relative to diesel fuel, but only when constant intake oxygen was maintained.
Journal Article

Tier 2 Test Fuel Impact to Tier 3 Aftertreatment Systems and Calibration Countermeasures

2018-04-03
2018-01-0941
During the course of emissions and fuel economy (FE) testing, vehicles that are calibrated to meet Tier 3 emissions requirements currently must demonstrate compliance on Tier 3 E10 fuel while maintaining emissions capability with Tier 2 E0 fuel used for FE label determination. Tier 3 emissions regulations prescribe lower sulfur E10 gasoline blends for the U.S. market. Tier 3 emissions test fuels specified by EPA are required to contain 9.54 volume % ethanol and 8-11 ppm sulfur content. EPA Tier 2 E0 test fuel has no ethanol and has nominal 30 ppm sulfur content. Under Tier 3 rules, Tier 2 E0 test fuel is still used to determine FE. Tier 3 calibrations can have difficulty meeting low Tier 3 emissions targets while testing with Tier 2 E0 fuel. Research has revealed that the primary cause of the high emissions is deactivation of the aftertreatment system due to sulfur accumulation on the catalysts.
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