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Diesel oxidation catalyst (DOC) is one of the critical catalyst components in modern diesel aftertreatment systems. It mainly converts unburned hydrocarbon (HC) and CO to CO2 and H2O before they are released to the environment. In addition, it also oxidizes a portion of NO to NO2, which improves the NOx conversion efficiency via fast SCR over the downstream selective catalytic reduction (SCR) catalyst. HC light-off tests, with or without the presence of NOx, has been typically used for DOC evaluation in laboratory. In this work, we aim to understand the influences of DOC light-off experimental conditions, such as initial temperature, initial holding time, HC species, with or without the presence of NOx, on the DOC HC light-off behavior. The results indicate that light-off test with lower initial temperature and longer initial holding time (at its initial temperature) leads to higher DOC light-off temperature.

Two methods of sampling exhaust emissions are typically used for characterizing emissions from diesel engines: total dilution which uses a constant volume sampling (CVS) system and partial flow dilution which relies on proportionally diluting a small part from the main exhaust stream. The CVS dilutes the entire exhaust flow to a constant volumetric flowrate which allows for proportional sampling of the exhaust species during transient engine operation. For partial dilution sampling during transient engine operation, obtaining a proportional sample is more rigorous and dilution of the extracted sample must be continuously changed throughout the cycle in order for the extracted sample flowrate to be proportional to the continuously changing exhaust flow. Typically, regulated emissions measured using both methods for an engine platform have shown good correlation. The focus for this work was on the experimental investigation of the two methods for the measurement of unregulated species.

Gasoline direct injection (GDI) has changed the exhaust composition in comparison with the older port fuel injection (PFI) systems. More recently, light-duty vehicle engine manufactures have combined these two technologies to take advantage of the knock benefits and fuel economy of GDI with the low particulate emission of PFI. These dual injection strategy engines have made a change in the combustion emission composition produced by these engines. Understanding the impact of these changes is essential for automotive companies and aftertreatment developers. A novel sampling system was designed to sample the exhaust generated by a dual injection strategy gasoline vehicle using the United States Federal Test Procedure (FTP). This sampling system was capable of measuring the regulated emissions as well as collecting the entire exhaust from the vehicle for measuring unregulated emissions.

Since the conception of the internal combustion engine, smoky and ill-smelling exhaust was prevalent. Over the last century, significant improvements have been made in improving combustion and in treating the exhaust to reduce these effects. One group of compounds typically found in exhaust, polycyclic aromatic hydrocarbons (PAH), usually occurs at very low concentrations in diesel engine exhaust. Some of these compounds are considered carcinogenic, and most are considered hazardous air pollutants (HAP). Many methods have been developed for sampling, handling, and analyzing PAH. For this study, an improved method for dilute exhaust sampling was selected for sampling the PAH in diesel engine exhaust. This sampling method was used during transient engine operation both with and without aftertreatment to show the effect of aftertreatment.

Gasoline direction injection (GDI) engines have been widely used by light-duty vehicle manufacturers in recent years to meet stringent fuel economy and emissions standards. Particulate Matter (PM) mass emissions from current GDI engines are primarily composed of soot particles or black carbon with a small fraction (15% to 20%) of semi-volatile hydrocarbons generated from unburned/partially burned fuel and lubricating oil. Between 2017 and 2025, PM mass emissions regulations in the USA are expected to become progressively more stringent going down from current level of 6 mg/mile to 1 mg/mile in 2025. As PM emissions are reduced through soot reduction, lubricating oil derived semi-volatile PM is expected to become a bigger fraction of total PM mass emissions.

Plug flow reactors, simulating engine exhaust gas, are widely used in emissions control research to gain insight into the reaction mechanisms and engineering aspects that controls activity, selectivity, and durability of catalyst components. The choice of relevant hydrocarbon (HC) species is one of the most challenging factor in such laboratory studies, given the variety of compositions that can be encountered in different application scenarios. Furthermore, this challenge is amplified by the experimental difficulties related to introducing heavier and multi-component HCs and analyzing the reaction products.

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.

Advanced combustion strategies used to improve efficiency, emissions, and performance in internal combustion engines (IC) alter the chemical composition of engine-out emissions. The characterization of exhaust chemistry from advanced IC engines requires an analytical system capable of measuring a wide range of compounds. For many years, the widely accepted Coordinating Research Council (CRC) Auto/Oil procedure[1,2] has been used to quantify hydrocarbon compounds between C1 and C12 from dilute engine exhaust in Tedlar polyvinyl fluoride (PVF) bags. Hydrocarbons greater than C12+ present the greatest challenge for identification in diesel exhaust. Above C12, PVF bags risk losing the higher molecular weight compounds due to adsorption to the walls of the bag or by condensation of the heavier compounds. This paper describes two specialized exhaust gas sampling and analytical systems capable of analyzing the mid-range (C10 - C24) and the high range (C24+) hydrocarbon in exhaust.

A series of tests were performed on a gasoline powered engine with a Dedicated EGR® (D-EGR®) system. The results showed that changes in engine performance, including improvements in burn rates and stability and changes in emissions levels could not be adequately accounted for solely due to the presence of reformate in the EGR stream. In an effort to adequately characterize the engine's behavior, a new parameter was developed, the Total Inert Dilution Ratio (TIDR), which accounts for the changes in the EGR quality as inert gases are replaced by reactive species such as CO and H2.

Exposure of hydrocarbons (HCs) and particulate matter (PM) under certain real-world operating conditions leads to carbonaceous deposit formation on V-SCR catalysts and causes reversible degradation of its NOx conversion. In addition, uncontrolled oxidation of such carbonaceous deposits can also cause the exotherm that can irreversibly degrade V-SCR catalyst performance. Therefore carbonaceous deposit mitigation strategies, based on their characterization, are needed to minimize their impact on performance. The nature and the amount of the deposits, formed upon exposure to real-world conditions, were primarily carried out by the controlled oxidation of the deposits to classify these carbonaceous deposits into three major classes of species: i) HCs, ii) coke, and iii) soot. The reversible NOx conversion degradation can be largely correlated to coke, a major constituent of the deposit, and to soot which causes face-plugging that leads to decreased catalyst accessibility.

In this study, the criteria pollutant emissions from a light duty vehicle equipped with Dedicated EGR® technology were compared with emissions from an identical production GDI vehicle without externally cooled EGR. In addition to the comparison of criteria pollutant mass emissions, an analysis of the gaseous and particulate chemistry was conducted to understand how the change in combustion system affects the optimal aftertreatment control system. Hydrocarbon emissions from the vehicle were analyzed usin g a variety of methods to quantify over 200 compounds ranging in HC chain length from C1 to C12. The particulate emissions were also characterized to quantify particulate mass and number. Gaseous and particulate emissions were sampled and analyzed from both vehicles operating on the FTP-75, HWFET, US06, and WLTP drive cycles at the engine outlet location.

Exhaust emissions of non-methane hydrocarbon (NMHC) and methane were measured from a Tier 3 dual-fuel demonstration locomotive running diesel-natural gas blend. Measurements were performed with the typical flame ionization detector (FID) method in accordance with EPA CFR Title 40 Part 1065 and with an alternative Fourier-Transform Infrared (FTIR) Spectroscopy method. Measurements were performed with and without oxidation catalyst exhaust aftertreatment. FTIR may have potential for improved accuracy over the FID when NMHC is dominated by light hydrocarbons. In the dual fuel tests, the FTIR measurement was 1-4% higher than the FID measurement of. NMHC results between the two methods differed considerably, in some cases reporting concentrations as much as four times those of the FID. However, in comparing these data it is important to note that the FTIR method has several advantages over the FID method, so the differences do not necessarily represent error in the FTIR.

This paper covers work performed for the California Air Resources Board and US Environmental Protection Agency by Southwest Research Institute. Emission measurements were made on four in-use off-road two-stroke motorcycles and all-terrain vehicles utilizing oxygenated and non-oxygenated fuels. Emission data was produced to augment ARB and EPA's off-road emission inventory. It was intended that this program provide ARB and EPA with emission test results they require for atmospheric modeling. The paper describes the equipment and engines tested, test procedures, emissions sampling methodologies, and emissions analytical techniques. Fuels used in the study are described, along with the emissions characterization results. The fuel effects on exhaust emissions and operation due to ethanol content and fuel components is compared.

The dual-fuel combustion process of ethanol and n-heptane was characterized experimentally in an optically accessible engine and numerically through a chemical kinetic 3D-CFD investigation. Previously reported formaldehyde PLIF distributions were used as a tracer of low-temperature oxidation of straight-chained hydrocarbons and the numerical results were observed to be in agreement with the experimental data. The numerical and experimental evidence suggests that a change in the speed of flame propagation is responsible for the observed behavior of the dual-fuel combustion, where the energy release duration is increased and the maximum rate of pressure rise is decreased. Further, an explanation is provided for the asymmetrical energy release profile reported in literature which has been previously attributed to an increase in the diffusion-controlled combustion phase.

Real-world operation of diesel oxidation catalysts (DOCs), used in a variety of aftertreatment systems, subjects these catalysts to a large number of permanent and temporary deactivation mechanisms. These include thermal damage, induced by generating exotherm on the catalyst; exposure to various inorganic species contained in engine fluids; and the effects of soot and hydrocarbons, which can mask the catalyst in certain operating modes. While some of these deactivation mechanisms can be accurately simulated in the lab, others are specific to particular engine operation regimes. In this work, a set of DOCs, removed from prolonged service in the field, has been subjected to a detailed laboratory study. Samples obtained from various locations in these catalysts were used to characterize the extent and distribution of deactivation.

The spark ignition (SI) engine has been known to exhibit several different abnormal combustion phenomena, such as knock or pre-ignition, which have been addressed with improved engine design or control schemes. However, in highly boosted SI engines, Low-Speed Pre-Ignition (LSPI), a pre-ignition event typically followed by heavy knock, has developed into a topic of major interest due to its potential for engine damage. Previous experiments associated increases in hydrocarbon emissions with the blowdown event of an LSPI cycle [1]. Also, the same experiments showed that there was a dependency of the LSPI activity on fuel and/or lubricant compositions [1]. Based on these findings it was hypothesized that accumulated hydrocarbons play a role in LSPI and are consumed during LSPI events. A potential source for accumulated HC is the top land piston crevice.

A solid particle number measurement system (SPNMS) was developed using a catalytic stripper (CS) technology instead of an evaporation tube (ET). The ET is used in commercially available systems, compliant with the Particle Measurement Program (PMP) protocol developed for European Union (EU) solid particle number regulations. The catalytic stripper consists of a small core of a diesel exhaust oxidation catalyst. The SPNMS/CS met all performance requirements under the PMP protocol. It showed a much better performance in removing large volatile tetracontane particles down to a size well below the PMP lower cut-size of 23 nm, compared to a SPNMS equipped with an ET instead of a CS. The SPNMS/CS also showed a similar performance to a commercially available system when used on a gasoline direct injection (GDI) engine exhaust.

Newly designed Teflon® O-rings along with XAD-2 resin, stainless steel screens, lock rings, and glass cartridges were used to construct a new semi-volatile organic compounds (SVOC's) sampling device. This new sampling device allows direct and repeated sampling, extraction, and cleaning without ever having to be disassembled or reassembled. This new XAD-2 glass cartridge (X2) was compared with three other sampling methods namely Empore® membrane (EM), hexane impinger (HI), and “Cold Trap” (CT) for SVOC sampling efficiency on diesel engine exhaust emissions. The X2 method showed the highest overall SVOC collection efficiency, followed by the EM and HI methods. The X2 method has higher trapping efficiency for the oxygenates, polycyclic aromatic hydrocarbons (PAH's), alkyl cyclohexanes, and the alkyl aromatics than the other three SVOC sampling methods. The HI method has the highest trapping efficiency for the normal alkanes.

A two-phase study was performed to establish a standard diesel exhaust composition which could be used in the future development of light-duty diesel exhaust aftertreatment. In the first phase, a literature review created a database of diesel engine-out emissions. The database consisted chiefly of data from heavy-duty diesel engines; therefore, the need for an emission testing program for light- and medium-duty engines was identified. A second phase was conducted to provide additional light-duty vehicle emissions data from current technology vehicles. Engine-out diesel exhaust from four 2004 model light-duty vehicles with a variety of engine displacements was collected and analyzed. Each vehicle was evaluated using five steady-state engine operating conditions and two transient test cycles (the Federal Test Procedure and the US06). Regulated emissions were measured along with speciation of both volatile and semi-volatile components of the hydrocarbons.

This paper analyzes the aging of zeolite based hydrocarbon traps to guide development of diagnostic algorithms. Previous research has shown the water adsorption ability of zeolite ages along with the hydrocarbon adsorption ability, and this leads to a possible diagnostic algorithm: the water concentration in the exhaust can be measured and related to aging. In the present research, engine experiments demonstrate that temperature measurements are also related to aging. To examine the relationship between temperature-based and moisture-based diagnostic algorithms, a transient, nonlinear heat and mass transfer model of the exhaust during cold-start is developed. Despite some idealizations, the model replicates the qualitative behavior of the exhaust system. A series of parametric studies reveals the sensitivity of the system response to aging and various noise factors.