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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

Study of On-Board Ammonia (NH3) Generation for SCR Operation

2010-04-12
2010-01-1071
Mechanisms of NH₃ generation using LNT-like catalysts have been studied in a bench reactor over a wide range of temperatures, flow rates, reformer catalyst types and synthetic exhaust-gas compositions. The experiments showed that the on board production of sufficient quantities of ammonia on board for SCR operation appeared feasible, and the results identified the range of conditions for the efficient generation of ammonia. In addition, the effects of reformer catalysts using the water-gas-shift reaction as an in-situ source of the required hydrogen for the reactions are also illustrated. Computations of the NH₃ and NOx kinetics have also been carried out and are presented. Design and impregnation of the SCR catalyst in proximity to the ammonia source is the next logical step. A heated synthetic-exhaust gas flow bench was used for the experiments under carefully controlled simulated exhaust compositions.
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

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

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

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

Development of a Diesel Emission Catalyst System for Meeting US SULEV Standards

2008-04-14
2008-01-0449
In recent years, catalyst systems such as a lean NOx trap (LNT) catalyst system and a urea selective catalytic reduction (SCR) system have been developed to obtain cleaner diesel emissions. At Nissan, we developed an emission control system for meeting Tier 2 Bin 5 requirements in 2003. On the basis of that technology, a new HC-NOx trap catalyst system has now been developed that complies with the SULEV standards without increasing the catalyst volume and precious metal loading. Compliance with the SULEV standards requires a further reduction of HC (NMHC) emissions by 84% and NOx by 60% compared with the emission performance Tier 2 Bin 5 compliant catalyst system. Consequently high conversion performance for both HCs and NOx is needed. An investigation of HC emission behavior under the FTP75 mode showed that a reduction of cold-phase HCs was critical for meeting the standard. Large quantities of HCs above C4 are emitted in the cold state.
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.
Technical Paper

Effects of NOx and Unburned Gasoline on Low Temperature Sludge Formation in Engine Oil

1991-02-01
910747
It is generally known that NOx reacts with unburned gasoline, olefins in particular, to form sludge precursors. In this study, the authors investigated the process by which NOx and unburned gasoline mix into the engine oil and analyzed the mechanism whereby stop and go driving accelerates sludge formation. It has been found that NOx detected in the engine oil as nitrite ions mixes into the oil in the crankcase. The NOx concentration in the engine oil increases rapidly when the crankcase gas temperature is nearly equal to the dew point of the water vapor in the crankcase. Unburned gasoline is mainly absorbed into the oil through the oil film on the cylinder walls and the oil in the ring grooves. During low-temperature engine operation in stop-go driving (i.e., when the vehicle is stopped), NOx and unburned gasoline are absorbed into the engine oil and, in high-temperature engine operation (i.e., when the vehicle is moving), NOx and unburned gasoline are released from the oil.
Journal Article

NOx Reduction Using a Dual-Stage Catalyst System with Intercooling in Vehicle Gasoline Engines under Real Driving Conditions

2018-04-03
2018-01-0335
Selective catalytic reduction (SCR) of nitrogen oxides (NOx) is used in diesel-fueled mobile applications where urea is an added reducing agent. We show that the Ultera® dual-stage catalyst, with intercooling aftertreatment system, intrinsically performs the function of the SCR method in nominally stoichiometric gasoline vehicle engines without the need for an added reductant. We present that NOx is reduced during the low-temperature operation of the dual-stage system, benefiting from the typically periodic transient operation (acceleration and decelerations) with the associated swing in the air/fuel ratio (AFR) inherent in mobile applications, as commonly expected and observed in real driving. The primary objective of the dual-stage aftertreatment system is to remove non-methane organic gases (NMOG) and carbon monoxide (CO) slip from the vehicle’s three-way catalyst (TWC) by oxidizing these constituents in the second stage catalyst.
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

Passive Hydrocarbon Trap to Enable SULEV-30 Tailpipe Emissions from a Flex-Fuel Vehicle on E85 Fuel

2018-04-03
2018-01-0944
Future LEV-III tailpipe (TP) emission regulations pose an enormous challenge forcing the fleet average of light-duty vehicles produced in the 2025 model year to perform at the super ultralow emission vehicle (SULEV-30) certification levels (versus less than 20% produced today). To achieve SULEV-30, regulated TP emissions of non-methane organic gas (NMOG) hydrocarbons (HCs) and oxygenates plus oxides of nitrogen (NOx) must be below a combined 30 mg/mi (18.6 mg/km) standard as measured on the federal emissions certification cycle (FTP-75). However, when flex-fuel vehicles use E85 fuel instead of gasoline, NMOG emissions at cold start are nearly doubled, before the catalytic converter is active. Passive HC traps (HCTs) are a potential solution to reduce TP NMOG emissions. The conventional HCT design was modified by changing the zeolite chemistry so as to improve HC retention coupled with more efficient combustion during the desorption phase.
Journal Article

Benefits of Pd Doped Zeolites for Cold Start HC/NOx Emission Reductions for Gasoline and E85 Fueled Vehicles

2018-04-03
2018-01-0948
In the development of HC traps (HCT) for reducing vehicle cold start hydrocarbon (HC)/nitrogen oxide (NOx) emissions, zeolite-based adsorbent materials were studied as key components for the capture and release of the main gasoline-type HC/NOx species in the vehicle exhaust gas. Typical zeolite materials capture and release certain HC and NOx species at low temperatures (<200°C), which is lower than the light-off temperature of a typical three-way catalyst (TWC) (≥250°C). Therefore, a zeolite alone is not effective in enhancing cold start HC/NOx emission control. We have found that a small amount of Pd (<0.5 wt%) dispersed in the zeolite (i.e., BEA) can significantly increase the conversion efficiency of certain HC/NOx species by increasing their release temperature. Pd was also found to modify the adsorption process from pure physisorption to chemisorption and may have played a role in the transformation of the adsorbed HCs to higher molecular weight species.
Journal Article

A New Catalyzed HC Trap Technology that Enhances the Conversion of Gasoline Fuel Cold-Start Emissions

2018-04-03
2018-01-0938
Passive in-line catalyzed hydrocarbon (HC) traps have been used by some manufacturers in the automotive industry to reduce regulated tailpipe (TP) emissions of non-methane organic gas (NMOG) during engine cold-start conditions. However, most NMOG molecules produced during gasoline combustion are only weakly adsorbed via physisorption onto the zeolites typically used in a HC trap. As a consequence, NMOG desorption occurs at low temperatures resulting in the use of very high platinum group metal (PGM) loadings in an effort to combust NMOG before it escapes from a HC trap. In the current study, a 2.0 L direct-injection (DI) Ford Focus running on gasoline fuel was evaluated with full useful life aftertreatment where the underbody converter was either a three-way catalyst (TWC) or a HC trap. A new HC trap technology developed by Ford and Umicore demonstrated reduced TP NMOG emissions of 50% over the TWC-only system without any increase in oxides of oxygen (NOx) emissions.
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

Effect of Intake Primary Runner Blockages on Combustion Characteristics and Emissions with Stoichiometric and EGR-diluted Mixtures in SI Engines

2007-10-29
2007-01-3992
In-cylinder charge motion is known to significantly increase turbulence intensity, accelerate combustion rate, and reduce cyclic variation. This, in turn, extends the tolerance to exhaust gas recirculation (EGR), while the introduction of EGR results in much lowered nitrogen oxide (NOx) emissions and reduced fuel consumption. The present study investigates the effect of charge motion in a spark ignition engine on fuel consumption, combustion, and engine-out emissions with stoichiometric and EGR-diluted mixtures under part-load operating conditions. Experiments have been performed with a Chrysler 2.4L 4-valve I4 engine under 2.41 bar brake mean effective pressure at 1600 rpm over a spark range around maximum brake torque timing. The primary intake runners are partially blocked to create different levels of tumble, swirl, and cross-tumble (swumble) motion in the cylinder before ignition.
Technical Paper

Summary report of Japan Clean Air Program diesel and diesel fuel activities

2007-07-23
2007-01-1952
Diesel emissions are significant issue worldwide, and emissions requirements have become so tough that. the application of after-treatment systems is now indispensable in many countries To meet even more stringent future emissions requirements, it has become apparent that the improvement of market fuel quality is essential as well as the development in engine and exhaust after-treatment technology. Japan Clean Air Program II (JCAP II) is being conducted to assess the direction of future technologies through the evaluation of current automobile and fuel technologies and consequently to realize near zero emissions and carbon dioxide (CO2) emission reduction. In this program, effects of fuel properties on the performance of diesel engines and a vehicle equipped with two types of diesel NOx emission after-treatment devices, a Urea-SCR system and a NOx storage reduction (NSR) catalyst system, were examined.
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