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As governmental agencies focus on low levels of the oxides of nitrogen (NOx) emissions compliance, new off-road applications are being reviewed for both regulated and unregulated emissions to understand the technological challenges and requirements for improved emissions performance. The California Air Resources Board (CARB) has declared its intention to pursue more stringent NOX standards for the off-road market. As part of this effort, CARB initiated a program to provide a detailed characterization of emissions meeting the current Tier 4 off-road standards [1]. This work focused on understanding the off-road market, establishing a current technology emissions baseline, and performing initial modeling on potential low NOx solutions. This paper discusses a part of this effort, focuses on the emissions characterization from two non-road engine platforms, and compares the emissions species from different approaches designed to meet Tier 4 emissions regulations.

Water injection is an effective method for knock control in spark-ignition engines. However, the requirement of a separate water source and the cost and complexity associated with a fully integrated system creates a limitation of this method to be used in volume production engines. The engine exhaust typically contains 10-15% water vapor by volume which could be condensed and potentially stored for future use. In this study, the exhaust condensate composition was assessed for its use as an effective replacement for distilled water. Specifically, condensate samples were collected pre and post-three-way catalyst (TWC) and analyzed for acidity and composition. The composition of the pre and post-TWC condensates was found to be similar however, the pre-TWC condensate was mildly acidic. The mild acidity has the potential to corrode certain components in the intake air circuit.

With the advancement of engine technologies and combustion strategies, aftertreatment architectures are expected to evolve as they continue to be the primary emissions mitigation hardware. Some of the engine approaches offer unique challenges and benefits that are not well understood beyond criteria pollutant emissions. As such, there continues to be a need to quantify engine emissions characteristics in pursuit of catalyst technology development and the use of advanced simulation tools. The following study discusses results from an extensive engine emissions assessment for current state-of-the-art technology and novel combustion regimes. The engines tested include a Tier 4 final compliant 6.8 L John Deere PSS 6068 diesel engine, a modified 15 L diesel engine, and a dual fuel 13 L natural gas-diesel engine. The dual fuel engine could operate in conventional positive ignition mode (CDF) or low temperature reactivity-controlled compression ignition mode (RCCI).

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.

Dual injection fuel systems combine the knock and fuel economy benefits of gasoline direct injection (GDI) technology with the lower particulate emissions of port fuel injection (PFI) systems. For many years, this technology was limited to smaller-volume, high-end, vehicle models, but these technologies are now becoming main stream. The combination of two fuel injection systems has an impact on the combustion emission composition as well as the consistency of control strategy and emissions. Understanding the impact of these changes is essential for fuel and fuel additive companies, automotive companies, and aftertreatment developers. This paper describes the effects of dual injection technology on both regulated and non-regulated combustion emissions from a 2018 Toyota Camry during several cold-start, 4-bag United States Federal Test Procedure (FTP) cycle.

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.

The objectives of this project were to investigate the corrosivity of condensate in a stoichiometric spark-ignited (SI) engine when running exhaust gas recirculation (EGR) and to determine the effects of sulfur-in-fuel on corrosion. A 2.0 L turbocharged direct-injected SI engine was operated with low-pressure EGR for this study. The engine was instrumented for visual, thermodynamic, and electrochemical analyses to determine the potential for corrosion at locations where condensation was deemed likely in a low-pressure loop EGR (LPL-EGR) engine. The electrochemical analysis was performed using multi-electrode array (MEA) corrosion probes. Condensate was also collected and analyzed. These analyses were performed downstream of both the charge air cooler (CAC) and the EGR cooler. It was found that while conditions existed for sulfuric acid to form with high-sulfur fuel, no sulfuric acid was detected by any of the measurement methods.

Semi-volatile organic compounds (SVOC) are a group of compounds in engine exhaust that either form during combustion or are part of the fuel and lubricating oil. Since these compounds occur at very low concentrations in diesel engine exhaust, the methods for sampling, handling, and analyzing these compounds are critical to obtaining good results. An improved dilute exhaust sampling method was used for sampling and analyzing SVOC in engine exhaust, and this method was performed during transient engine operation. A total of 22 different SVOC were measured using a 2012 medium-duty diesel engine. This engine was equipped with a stock diesel oxidation catalyst (DOC), a diesel particulate filter (DPF), and a selective catalytic reduction (SCR) catalyst in series. Exhaust concentrations for SVOC were compared both with and without exhaust aftertreatment. Concentrations for the engine-out SVOC were significantly higher than with the aftertreatment present.

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.

Ideally, complete decomposition of urea should produce only two products in active Selective Catalytic Reduction (SCR) systems: ammonia and carbon dioxide. In reality, urea decomposition reaction is a two-step process that includes the formation of ammonia and isocyanic acid as intermediate products via thermolysis. Being highly reactive, isocyanic acid can initiate the formation of larger molecular weight compounds such as cyanuric acid (CYN), biuret (BIU), melamine (MEL), ammeline (AML), ammelide (AMD), and dicyandimide (DICY). These compounds can be responsible for the formation of deposits on the walls of the decomposition reactor in urea SCR systems. Composition of these deposits varies with temperature exposure, and under certain conditions can create oligomers that are difficult to remove from exhaust pipes. Deposits can affect efficiency of the urea decomposition, and if large enough, can inhibit the exhaust flow and negatively impact ammonia distribution on the SCR catalyst.

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.

Ideally, complete thermal decomposition of urea should produce only two products in active Selective Catalytic Reduction (SCR) systems: ammonia and carbon dioxide. In reality, urea thermal decomposition reaction includes the formation of isocyanic acid as an intermediate product. Being highly reactive, isocyanic acid can initiate the formation of larger molecular weight compounds such as cyanuric acid, biuret, melamine, ammeline, ammelide, and dicyandimide [1,2,3,4]. These compounds can be responsible for the formation of deposits on the walls of the decomposition reactor in urea SCR systems. Composition of these deposits varies with temperature exposure, and under certain conditions, can create oligomers such as melam, melem, and melon [5, 6] that are difficult to remove from exhaust systems. Deposits can affect the efficiency of the urea decomposition, and if large enough, can inhibit the exhaust flow.

Semi-volatile organic compounds (SVOC) are a group of compounds that may form during combustion and/or are present in the unburned portion of the fuel and lubricating oil which ultimately become part of the exhaust. Many of these compounds are considered toxic or carcinogenic. Since these compounds are present in very low concentrations in diesel engine exhaust, the methods for sampling, handling, and analyzing these compounds are critical to obtaining representative and repeatable results. Engine testing is typically performed using a dilution tunnel. With a dilution tunnel, the collection of a representative sample is important. Experiments were performed with a modified EPA Method TO-9A to determine the equilibration time and other sampling parameters required for the measurement of SVOC in dilute exhaust. The results show that representative results can be obtained with this method.

This paper discusses a method developed to counter the variability of media interferences for the measurement of aldehydes and ketones in automotive exhaust. Dinitrophenylhydrazine (DNPH) Derivatization Methodology for the collection of aldehyde and ketone compounds in vehicle exhaust has been in use for over thirty years. These carbonyl compounds are captured by passing diluted exhaust gas through a sample medium containing DNPH. The sampling medium can take the form of DNPH dispersed on a solid sorbent or as a DNPH solution in a solvent such as acetonitrile. Carbonyl compounds react readily to form DNPH derivatives which are stable and which absorb ultra-violet (UV) light, facilitating quantitative measurement. However, when the procedure was developed, emissions rates from vehicles were much higher than the current (2010) emissions levels.

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.

Sulfur and aromatic compounds in diesel fuel impact the emissions profile of current diesel engines. Fuels that do not contain these components can be made from natural gas using Fischer-Tropsch chemistry. Very little data has been presented comparing the emissions characteristics of current low sulfur diesel to fuels with ultra low levels of sulfur and aromatics in passenger car diesel engines. This study reports on an exhaust emission comparison of currently available conventional diesel fuel to Fischer Tropsch diesel fuel free of aromatics and sulfur comparisons included regulated emissions, air toxics, aldehydes and ketones, particle size distribution, and greenhouse gas emissions. Testing was conducted on a current model diesel passenger car using a chassis dynamometer. Regulated emissions were analyzed according to the Code of Federal Regulations (CFR) Title 40 specifications and requirements of the Environmental Protection Agency (EPA) Federal Test Procedure (FTP).

This study compared four different candidate fuels which were prepared by blending different components with a typical No. 2 diesel. Two fuels were blended with a synthetic diesel prepared from natural gas condensate, and all candidate fuels were splash blended with a proprietary additive package from International Fuel Technology Inc. (IFT). These fuels were then compared to the No. 2 diesel and to a California Air Resources Board (CARB) equivalent diesel fuel. The comparisons included fuel properties such as sulfur content, aromatics, cetane, lubricity, distillation; emissions; and fuel consumption. Emission testing was conducted on a 1991 Detroit Diesel Series 60. The Environmental Protection Agency (EPA) transient cycle was utilized for emissions, fuel characterization was performed according to ASTM standards, and fuel consumption was calculated by the carbon balance method.

This study compared diesel exhaust emission from four different diesel fuels: a conventional low sulfur D2 diesel (0.03% sulfur, 28% aromatics), California Air Resources Board (CARB) diesel (0.015% sulfur, 8% aromatics), “Swedish” diesel (<0.001% sulfur, 4% aromatics), and a Fischer-Tropsch (F-T) diesel (<0.0001% sulfur, <0.1% aromatics) fuel. The comparison included regulated emissions, hydrocarbon speciation, air toxics, aldehydes and ketones, particle size distribution, and greenhouse gas emissions. Testing was conducted using a Cummins B-Series engine installed both in a heavy light-duty truck operating on a chassis dynamometer and on an engine dynamometer. The chassis driving cycles included city, highway, and aggressive driving operation. Engine dynamometer tests included the U.S. transient cycle.