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Technical Paper

Assessment of Condensation Particle Counter-Based Portable Solid Particle Number System for Applications with High Water Content in Exhaust

2024-04-22
2024-01-5048
The Particle Number–Portable Emission Measurement System (PN-PEMS) came into force with Euro VI Phase E regulations starting January 1, 2022. However, positive ignition (PI) engines must comply from January 1, 2024. The delay was due to the unavailability of the PN-PEMS system that could withstand high concentrations of water typically present in the tailpipe (TP) of CNG vehicles, which was detrimental to the PN-PEMS systems. Thus, this study was designed to evaluate the condensation particle counter (CPC)-based PN-PEMS measurement capabilities that was upgraded to endure high concentration of water. The PN-PEMS measurement of solid particle number (SPN23) greater than 23 nm was compared against the laboratory-grade PN systems in four phases. Each phase differs based upon the PN-PEMS and PN system location and measurements were made from three different CNG engines. In the first phase, systems measured the diluted exhaust through constant volume sampler (CVS) tunnel.
Technical Paper

Performance Comparison Analysis between Biodiesel and Diesel over a Commercial DOC Catalyst

2024-04-09
2024-01-2707
Biodiesel is a promising alternative to traditional diesel fuel due to its similar combustion properties to diesel and lower carbon emissions on a well-to-wheel basis. However, combusting biodiesel still generates hydrocarbon (HC), CO, NOx and particulate matter (PM) emissions, similar to those from traditional diesel fuel usage. Therefore, aftertreatment systems will be required to reduce these emissions to meet increasingly stringent emission regulations to minimize the impact to the environment. Diesel oxidation catalysts (DOC) are widely used in modern aftertreatment systems to convert unburned HC and CO, to partially convert NO to NO2 to enhance downstream selective catalytic reaction (SCR) catalyst efficiency via fast SCR and to periodically clean-up DPF via controlled soot oxidation. In this work, we focus on the performance difference between biodiesel and diesel over a commercial DOC catalyst to identify the knowledge gap during the transition from diesel fuel to biodiesel.
Technical Paper

Sulfur Impact on Methane Steam Reforming over the Stoichiometric Natural Gas Three-Way Catalyst

2024-04-09
2024-01-2633
The steam reforming of CH4 plays a crucial role in the high-temperature activity of natural gas three-way catalysts. Despite existing reports on sulfur inhibition in CH4 steam reforming, there is a limited understanding of sulfur storage and removal dynamics under various lambda conditions. In this study, we utilize a 4-Mode sulfur testing approach to elucidate the dynamics of sulfur storage and removal and their impact on three-way catalyst performance. We also investigate the influence of sulfur on CH4 steam reforming by analyzing CH4 conversions under dithering, rich, and lean reactor conditions. In the 4-Mode sulfur test, saturating the TWC with sulfur at low temperatures emerges as the primary cause of significant three-way catalyst performance degradation. After undergoing a deSOx treatment at 600 °C, NOx conversions were fully restored, while CH4 conversions did not fully recover.
Technical Paper

Experimental and Modeling Study on the Thermal Aging Impact on the Performance of the Natural Gas Three-Way Catalyst

2023-04-11
2023-01-0375
The prediction accuracy of a three-way catalyst (TWC) model is highly associated with the ability of the model to incorporate the reaction kinetics of the emission process as a lambda function. In this study, we investigated the O2 and H2 concentration profiles of TWC reactions and used them as critical inputs for the development of a global TWC model. We presented the experimental data and global kinetic model showing the impact of thermal degradation on the performance of the TWC. The performance metrics investigated in this study included CH4, NOx, and CO conversions under lean, rich, and dithering light-off conditions to determine the kinetics of oxidation reactions and reduction/reforming/water-gas shift reactions as a function of thermal aging. The O2 and H2 concentrations were measured using mass spectrometry to track the change in the oxidation state of the catalyst and to determine the mechanism of the reactions under these light-off conditions.
Technical Paper

Heavy-Duty Engines Exhaust Sub-23 nm Solid Particle Number Measurements

2021-02-24
2021-01-5024
The measurement of solid particles down to 10 nm is being incorporated into global technical regulations (GTR). This study explores the measurement of solid particles below 23 nm by using both current and proposed particle number (PN) systems having different volatile particle remover (VPR) methodologies and condensation particle counter (CPC) cutoff diameters. The measurements were conducted in dynamometer test cells using ten diesel and eight natural gas (NG) engines that were going under development for a variety of global emission standards. The PN systems measured solid PN from more than 700 test cycles. The results from the preliminary campaign showed a 10-280% increase in PN emissions with the inclusion of particles below 23 nm.
Technical Paper

Diagnostics of Field-Aged Three-Way Catalyst (TWC) on Stoichiometric Natural Gas Engines

2019-04-02
2019-01-0998
Three-way catalysts have been used in a variety of stoichiometric natural gas engines for emission control. During real-world operation, these catalysts have experienced a large number of temporary and permanent deactivations including thermal aging and chemical contamination. Thermal aging is typically induced either by high engine-out exhaust temperatures or the reaction exotherm generated on the catalysts. Chemical contamination originates from various inorganic species such as Phosphorous (P) and Sulfur (S) that contain in engine fluids, which can poison and/or mask the catalyst active components. Such deactivations are quite difficult to simulate under laboratory conditions, due to the fact that multiple deactivation modes may occur at the same time in the real-world operations. In this work, a set of field-aged TWCs has been analyzed through detailed laboratory research in order to identify and quantify the real-world aging mechanisms.
Technical Paper

Experimental and Kinetic Modeling of Degreened and Aged Three-way Catalysts: Aging Impact on Oxygen Storage Capacity and Catalyst Performance

2018-04-03
2018-01-0950
The aging impact on oxygen storage capacity (OSC) and catalyst performance was investigated on one degreened and one aged (hydrothermally aged at 955 °C for 50 h) commercial three-way catalyst (TWC) by experiments and modeling. The difference of OSC between the degreened and aged TWCs was dependent on catalyst temperature. The largest difference was found at 600 °C, at which the amount of OSC decreased by 45.5%. Catalyst performance was evaluated through lightoff tests at two simulated engine exhaust conditions (lean and rich) on a micro-reactor. The aging impact on the catalyst performance was different under lean and rich environments and investigated separately. At the lean condition, oxidation of CO and C3H6 was significantly suppressed while oxidation of C3H8 was relatively less degraded. At the rich condition, the inhibition effect was more pronounced on the aged TWC and inhibiting hydrocarbon species from C3H6 partial oxidation can survive at temperatures up to 450 °C.
Journal Article

Effect of Transition Metal Ion Properties on the Catalytic Functions and Sulfation Behavior of Zeolite-Based SCR Catalysts

2017-03-28
2017-01-0939
Copper- and Iron- based metal-zeolite SCR catalysts are widely used in US and European diesel aftertreatment systems to achieve drastic reduction in NOx emission. These catalysts are highly selective to N2 under wide range of operating conditions. Nevertheless, the type of transition metal has a significant impact on the key performance and durability parameters such as NOx conversion, selectivity towards N2O, hydrothermal stability, and sensitivity to fuel sulfur content. In this study, we explained the differences in the performance characteristics of these catalysts based on their relative acidic-basic nature of transition metal present in these catalysts using practically relevant gas species present in diesel exhaust such as NO2, SOx, and NH3. These experiments show that Fe-zeolite has relatively acidic nature as compared to Cu-zeolite that causes NH3 inhibition and hence explains low NOx conversion on Fe-zeolite at low temperature under standard SCR conditions.
Technical Paper

Lean Breakthrough Phenomena Analysis for TWC OBD on a Natural Gas Engine using a Dual-Site Dynamic Oxygen Storage Capacity Model

2017-03-28
2017-01-0962
Oxygen storage capacity (OSC) is one of the most critical characteristics of a three-way catalyst (TWC) and is closely related to the catalyst aging and performance. In this study, a dynamic OSC model involving two oxygen storage sites with distinct kinetics was developed. The dual-site OSC model was validated on a bench reactor and a natural gas engine. The model was capable of predicting temperature dependence on OSC with H2, CO and CH4 as reductants. Also, the effects of oxygen concentration and space velocity on the amount of OSC were captured by the model. The validated OSC model was applied to simulate lean breakthrough phenomena with varied space velocities and oxygen concentrations. It is found that OSC during lean breakthrough is not a constant for a particular TWC catalyst and is dependent on space velocity and oxygen concentration. Specifically, breakthrough time exhibits a non-linear, inverse correlation to oxygen flux.
Technical Paper

Development of a Kinetic Model to Evaluate Water Storage on Commercial Cu-Zeolite SCR Catalysts during Cold Start

2017-03-28
2017-01-0968
Commercial Cu-Zeolite SCR catalyst can store and subsequently release significant amount of H2O. The process is accompanied by large heat effects. It is critical to model this phenomenon to design aftertreatment systems and to provide robust tuning strategies to meet cold start emissions and low temperature operation. The complex reaction mechanism of water adsorption and desorption over a Cu-exchanged SAPO-34 catalyst at low temperature was studied through steady state and transient experiments. Steady state isotherms were generated using a gravimetric method and then utilized to predict water storage interactions with respect to feed concentration and catalyst temperature. Transient temperature programmed desorption (TPD) experiments provided the kinetic information required to develop a global kinetic model from the experimental data. The model captures fundamental characteristics of water adsorption and desorption accompanied by the heat effects.
Technical Paper

Automotive Selective Catalytic Reduction System Model-Based Estimators for On-ECU Implementation: A Brief Overview

2016-04-05
2016-01-0972
The amount of ammonia stored on the walls of the catalyst (or ammonia storage) is a parameter with significant impact on NOx reduction efficiency and undesired ammonia slip of Selective Catalytic Reduction catalysts. This makes the ammonia storage interesting for utilization in urea injection control. However, ammonia storage is not directly measurable onboard vehicles, it can only be estimated. Model-based online estimation requires models that are capable of capturing the main phenomena of the SCR and at the same time can be computed onboard vehicle. While the modeling of SCR and model-based control is well present in the literature, it is apparent that few attempts of implementing the models on production ECUs were published. This paper reviews literature on ammonia storage, outlet NH3 and NOx concentration estimation in SCR and SCR/DPF systems-including the estimation of NOx sensor cross-sensitive to NH3-in order to present the state of the art.
Technical Paper

New Insights into the Unique Operation of Small Pore Cu-Zeolite SCR Catalyst: Overlapping NH3 Desorption and Oxidation Characteristics for Minimizing Undesired Products

2014-04-01
2014-01-1542
An operational challenge associated with SCR catalysts is the NH3 slip control, particularly for commercial small pore Cu-zeolite formulations as a consequence of their significant ammonia storage capacity. The desorption of NH3 during increasing temperature transients is one example of this challenge. Ammonia slipping from SCR catalyst typically passes through a platinum based ammonia oxidation catalyst (AMOx), leading to the formation of the undesired byproducts NOx and N2O. We have discovered a distinctive characteristic, an overlapping NH3 desorption and oxidation, in a state-of-the-art Cu-zeolite SCR catalyst that can minimize NH3 slip during temperature transients encountered in real-world operation of a vehicle.
Technical Paper

The Effects of Thermal Degradation on the Performance of a NOX Storage/Reduction Catalyst

2009-04-20
2009-01-0631
The performance characteristics of a commercial lean-NOX trap catalyst were evaluated between 200 and 500°C, using H2, CO, and a mixture of both H2 and CO as reductants before and after different high-temperature aging steps, from 600 to 750°C. Tests included NOX reduction efficiency during cycling, NOX storage capacity (NSC), oxygen storage capacity (OSC), and water-gas-shift (WGS) and NO oxidation reaction extents. The WGS reaction extent at 200 and 300°C was negatively affected by thermal degradation, but at 400 and 500°C no significant change was observed. Changes in the extent of NO oxidation did not show a consistent trend as a function of thermal degradation. The total NSC was tested at 200, 350 and 500°C. Little change was observed at 500°C with thermal degradation but a steady decrease was observed at 350°C as the thermal degradation temperature was increased.
Journal Article

Effects of Methyl Ester Biodiesel Blends on NOx Emissions

2008-04-14
2008-01-0078
Effects of methyl ester biodiesel fuel blends on NOx emissions are studied experimentally and analytically. A precisely controlled single cylinder diesel engine experiment was conducted to determine the impact of a 20% blend of soy methyl ester biodiesel (B20) on NOx emissions. The data were then used to calibrate KIVA chemical kinetics models which were used to determine how the biodiesel blend affects NOx production during the combustion process. In addition, the impact on the engine control system of the lower specific energy content of biodiesel was determined. Both factors, combustion and controls, must be taken into account when determining the net NOx effect of biodiesel compared to conventional diesel fuel. Because the magnitude and even direction of NOx effect changes with engine load, the NOx effect associated with burning biodiesel blends over a duty cycle depends on the duty cycle average power and fuel cetane number.
Technical Paper

An Evaluation of Glycerin (Glycerol) as a Heavy Duty Engine Antifreeze/Coolant Base

2007-10-29
2007-01-4000
In the early years of antifreeze/coolants (1920s & 30s) glycerin saw some usage, but because of higher cost and weaker freeze point depression, it was not competitive with ethylene glycol. Glycerin is a by-product of the manufacture of biodiesel (fatty acid methyl esters) made by reacting natural vegetable or animal fats with methanol. Biodiesel fuel is becoming increasingly important and is expected to gain a large market share in the next several years. Regular diesel fuels blended with 2%, 5%, and 20% biodiesel are now commercially available. The large amount of glycerin generated from high volume usage of biodiesel fuel has resulted in this chemical becoming cost competitive with the glycols currently used in engine coolants. For this reason, and lower toxicity comparable to that of propylene glycol, glycerin deserves to be reconsidered as a base for antifreeze/coolant.
Technical Paper

Quantification of Biodiesel Content in Fuels and Lubricants by FTIR and NMR Spectroscopy

2006-10-16
2006-01-3301
The use of biodiesel requires the development of proper quantification procedures for biodiesel content in blends and in lubricants (fuel dilution in oil). Although the ester carbonyl stretch at 1746 wavenumbers (cm-1) is the most prominent band in the IR spectrum of biodiesel, it is difficult to use for quantification purposes due to a severe fluctuation of absorption strength from sample to sample, even at the same biodiesel content. We have demonstrated that the ester carbonyl fluctuation is not caused by variation in the ester alkyl chain length; but is most likely caused by the degree of hydrogen bonding of the ester functional group with water in the sample. Water molecules can form complexes with the ester compound affecting the strength of the ester carbonyl band. The impact of water on quantification of the biodiesel content of blends was significant, even for B100 samples that met the proposed ASTM D6751 water limit of 500 ppm by D6304 (Karl Fischer Methdod).
Technical Paper

Development of a Compression Ignition Heavy Duty Pilot-Ignited Natural Gas Fuelled Engine for Low NOx Emissions

2004-10-25
2004-01-2954
A heavy-duty compression ignition engine using EGR and pilot-ignited directly injected natural gas fueling was calibrated for low NOx emissions. A Cummins ISX engine using cooled EGR was fitted with a Westport HPDI™ fuel system and an oxidation catalyst. The base engine hardware was modified to increase EGR rates (up to 40%). The engine, rated at 336 kW (450 hp) and 2236Nm (1650 ft-lbs), was calibrated and tested over steady state and transient test cycles. Steady state testing over the ESC 13-mode test cycle resulted in weighted composite NOx emissions of 0.36 g/bhp-hr and particulate matter emissions of 0.04 g/bhp-hr. Transient testing over the US EPA specified FTP cycle resulted in average NOx emissions of 0.6 g/bhp-hr and PM emissions of 0.03 g/bhp-hr.
Technical Paper

E-diesel Effects on Engine Component Temperature and Heat Balance in a Cummins C8.3 Engine

2002-10-21
2002-01-2847
Heat rejection, liner temperature, exhaust valve seat temperature, and head gasket temperature data were recorded during a full load torque sweep of a compression ignition engine when fueled by No. 2 diesel and an ethanol/diesel fuel blend containing 10% ethanol by volume. Heat balances were calculated for engine operation at various load-speed combinations. The results of this study indicated that a greater than expected volume of E-diesel was required to operate the compression ignition engine at the same torque-speed compared to No. 2 diesel. More E-diesel fuel was required due to lower brake thermal efficiencies for E-diesel. Other than exhaust seat temperatures, there were no appreciable differences in component temperatures measured throughout the engine or the results of the heat balances calculated for the No. 2 diesel and E-diesel fuels.
Technical Paper

An Emission and Performance Comparison of the Natural Gas Cummins Westport Inc. C-Gas Plus Versus Diesel in Heavy-Duty Trucks

2002-10-21
2002-01-2737
Cummins Westport Inc. (CWI) released for production the latest version of its C8.3G natural gas engine, the C Gas Plus, in July 2001. This engine has increased ratings for horsepower and torque, a full-authority engine controller, wide tolerance to natural gas fuel (the minimum methane number is 65), and improved diagnostics capability. The C Gas Plus also meets the California Air Resources Board optional low-NOx (2.0 g/bhp-h) emission standard for automotive and urban buses. Two pre-production C Gas Plus engines were operated in a Viking Freight fleet for 12 months as part of the U.S. Department of Energy's Fuels Utilization Program. In-use exhaust emissions, fuel economy, and fuel cost were collected and compared with similar 1997 Cummins C8.3 diesel tractors. CWI and the West Virginia University developed an ad-hoc test cycle to simulate the Viking Freight fleet duty cycle from in-service data collected with data loggers.
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