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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.
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

Cold Start Performance and Enhanced Thermal Durability of Vanadium SCR Catalysts

2009-04-20
2009-01-0625
For diesel applications, cold start accounts for a large amount of the total NOx emissions during a typical Federal Test Procedure (FTP) for light-duty vehicles and is a key focus for reducing NOx emissions. A common form of diesel NOx aftertreatment is selective catalytic reduction (SCR) technology. For cold start NOx improvement, the SCR catalyst would be best located as the first catalyst in the aftertreatment system; however, engine-out hydrocarbons and no diesel oxidation catalyst (DOC) upstream to generate an exotherm for desulfation can result in degraded SCR catalyst performance. Recent advances in vanadia-based SCR (V-SCR) catalyst technology have shown better low temperature NOx performance and improved thermal durability. Three V-SCR technologies were tested for their thermal durability and low-temperature NOx performance, and after 600°C aging, one technology showed low-temperature performance on par with state-of-the-art copper-zeolite SCR (Cu-SCR) technology.
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.
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

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.
Technical Paper

Influence of Hydrocarbon Storage on the Durability of SCR Catalysts

2008-04-14
2008-01-0767
Selective catalytic reduction (SCR) is a technology capable of meeting Tier 2 Bin 5 emissions levels of oxides of nitrogen (NOX) for diesel engines. Base metal zeolite catalysts show the best combination of thermal durability and NOX conversion activity. It is shown in this work that some base metal zeolite catalysts can store high levels of hydrocarbons (HCs). Also, base metal zeolite catalysts can catalyze oxidation of HCs under certain conditions. Oxidation of stored hydrocarbons can lead to permanent catalyst deactivation due to the exotherm generated in the SCR catalyst (over-temperature condition leading to SCR catalyst damage). This paper discusses a laboratory bench test to characterize hydrocarbon storage and burn-off characteristics of several SCR catalyst formulations, as well as engine dynamometer tests showing hydrocarbon storage and exotherm generation.
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

The Influence of Ammonia to NOX Ratio on SCR Performance

2007-04-16
2007-01-1581
It is likely that use of urea-based selective catalytic reduction (SCR) will be needed to meet U.S. Tier 2 diesel emission standards for oxides of nitrogen (NOx). The ideal ratio of ammonia (NH3) molecules to NOx molecules (known as alpha) is 1:1 based on urea consumption and having NH3 available for reaction of all of the exhaust NOx. However, SCR efficiency can be less than 100% at low temperatures in general, and at higher temperatures with high exhaust SCR catalyst space velocities. At the low temperatures where NOx conversion efficiency is low, it may be advantageous to reduce the alpha ratio to values less than one (less NH3 than is needed to convert 100% of the NOx emissions) to avoid NH3 slip. At higher space velocities and high temperatures, the NOx conversion efficiency may be higher with alpha ratios greater than 1. There is however concern that the additional NH3 will be slipped under these conditions.
Technical Paper

Laboratory Testing of Urea-SCR Formulations to Meet Tier 2 Bin 5 Emissions

2007-04-16
2007-01-1575
Urea-based Selective Catalytic Reduction (SCR) has the potential to meet U.S. Diesel Tier 2 Bin 5 emission standards for NOx in 2010. The operating and driving conditions of light-duty and heavy-duty vehicles make it necessary to customize catalyst features to the application. This paper reviews the selection of SCR catalyst technology for the U.S. and the appropriate aging and poisoning protocols for current supplier SCR catalysts. Generally, light-duty applications require SCR catalysts to function well at low temperature whereas heavy-duty applications require functionality at high temperature and high space velocity. One main durability requirement of SCR formulations involves withstanding the high temperature process of regenerating particulate filters from accumulated soot. Unrefined engine exhaust temperature control coupled with the inexact temperature measurement may also expose SCR catalysts to additional over-temperature conditions.
Technical Paper

Flow Uniformity Optimization for Diesel Aftertreatment Systems

2006-04-03
2006-01-1092
In 2007 emissions regulations for on-road light to heavy duty Diesel trucks will require the use of Diesel Particulate Filters (DPFs). The uniform distribution of soot on the DPF is critical for adequate long term performance of these DPFs. This is especially true when cordierite is used instead of silicon carbide for the DPF substrate, due to the reduced thermal conductivity and reduced peak temperature capability of cordierite. In addition to flow uniformity, an inverted flow pattern where more of the flow is forced radially outward on the substrate face could be beneficial to counteract thermal losses in the converter. This paper describes a dispersion device that can improve flow geometry with a low backpressure penalty. Computational fluid dynamics (CFD) results and experimental data are presented for this device. Additionally, cone design options are explored, and CFD analysis results of the cone design are presented.
Technical Paper

An Investigation of the Effect of Fuel-Air Mixedness on the Emissions from an HCCI Engine

2002-05-06
2002-01-1758
This research work has focused on measuring the effect of fuel/air mixing on performance and emissions for a homogeneous charge compression ignition engine running on propane. A laser instrument with a high-velocity extractive probe was used to obtain time-resolved measurements of the fuel concentration both at the intake manifold and from the cylinder for different levels of fuel-air mixing. Cylinder pressure and emissions measurements have been performed at these mixing levels. From the cylinder pressure measurements, the IMEP and peak cylinder pressure were found. The fuel-air mixing level was changed by adding the fuel into the intake system at different distances from the intake valve (40 cm and 120 cm away). It was found that at the intake manifold, the fuel and air were better mixed for the 120 cm fuel addition location than for the 40 cm location.
Technical Paper

Current Research in HCCI Combustion at UC Berkeley and LLNL

2001-08-20
2001-01-2511
This paper describes the Homogeneous charge compression ignition (HCCI) research activities being currently pursued at Lawrence Livermore National Laboratory and at the University of California Berkeley. Current activities include analysis as well as experimental work. HCCI is an old combustion technology that may now be developed with expectations of high efficiency, low NOx, and low particulate matter emissions; in short, an alternative to diesel engines. On analysis, we have developed two powerful tools: a single zone model and a multi-zone model. The single zone model has proven very successful in predicting start of combustion and providing reasonable estimates for peak cylinder pressure, indicated efficiency and NOX emissions. This model is being applied to develop detailed engine performance maps and control strategies, and to analyze the problem of engine startability.
Technical Paper

1.9-Liter Four-Cylinder HCCI Engine Operation with Exhaust Gas Recirculation

2001-05-07
2001-01-1894
We present the effect of EGR, at a set fuel flow rate and intake temperature, on the operating parameters of timing of combustion, duration of combustion, power output, thermal efficiency, and NOx emission; which is remarkably low. We find that addition of EGR at constant inlet temperature and constant fuel flow rate has little effect on HCCI parameter of start of combustion (SOC). However, burn duration is highly dependent on the amount of EGR inducted. The experimental setup at UC Berkeley uses a 1.9-liter 4-cylinder diesel engine with a compression ratio of 18.8:1 (offered on a 1995 VW Passat TDI). The engine was converted to run in HCCI mode by addition of an 18kW air pre-heater installed in the intake system. Pressure traces were obtained using four water-cooled quartz pressure transducers, which replaced the Diesel fuel injectors. Gaseous fuel (propane or butane) flowed steadily into the intake manifold.
Technical Paper

Operation of a Four-Cylinder 1.9L Propane Fueled Homogeneous Charge Compression Ignition Engine: Basic Operating Characteristics and Cylinder-to-Cylinder Effects

2001-05-07
2001-01-1895
A four-cylinder 1.9 Volkswagen TDI Engine has been converted to run in Homogeneous Charge Compression Ignition (HCCI) mode. The stock configuration is a turbo-charged direct injection Diesel engine. The combustion chamber has been modified by discarding the in-cylinder Diesel fuel injectors and replacing them with blank inserts (which contain pressure transducers). The stock pistons contain a reentrant bowl and have been retained for the tests reported here. The intake and exhaust manifolds have also been retained, but the turbocharger has been removed. A heater has been installed upstream of the intake manifold and fuel is added just downstream of this heater. The performance of this engine in naturally aspirated HCCI operation, subject to variable intake temperature and fuel flow rate, has been studied. The engine has been run with propane fuel at a constant speed of 1800 rpm.
Technical Paper

HCCI in a CFR Engine: Experiments and Detailed Kinetic Modeling

2000-03-06
2000-01-0328
Single cylinder engine experiments and chemical kinetic modeling have been performed to study the effect of variations in fuel, equivalence ratio, and intake charge temperature on the start of combustion and the heat release rate. Neat propane and a fuel blend of 15% dimethyl-ether in methane have been studied. The results demonstrate the role of these parameters on the start of combustion, efficiency, imep, and emissions. Single zone kinetic modeling results show the trends consistent with the experimental results.
Technical Paper

A Study of the Character and Deposition Rates of Sulfur Species in the EGR Cooling System of a Heavy-Duty Diesel Engine

1999-10-25
1999-01-3566
Various measurement techniques were employed to quantify sulfuric acid deposition levels and concentration of sulfuric acid in the condensate from the recirculated exhaust gas heat exchanger of a 1995 Cummins M11 heavy-duty diesel engine. Methods employed included a modified version of the sulfur species sampling system developed by Kreso et al. (1)*, rinsing the heat exchanger, and experiments employing a condensate collection device (CCD). The modified sampling system was applied to the inlet and outlet of the heat exchanger in order to quantify the changes in various sulfur compounds. Doped sulfur fuel (3300 to 4000 ppm S) was used to increase the concentrations of the various oxides of sulfur (SOx). These tests were performed at mode 9 of the old EPA 13-mode test cycle (1800 RPM, 932N*m) with 17-20% exhaust gas recirculation (EGR) at two EGR outlet temperatures: 160°C and 103°C.
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