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An experimental study was performed to develop a more fundamental understanding of the effects of secondary air injection (SAI) on exhaust gas emissions and catalyst light-off characteristics during cold start of a modern SI engine. The effects of engine operating parameters and various secondary air injection strategies such as spark retardation, fuel enrichment, secondary air injection location and air flow rate were investigated to understand the mixing, heat loss, and thermal and catalytic oxidation processes associated with SAI. Time-resolved HC, CO and CO₂ concentrations were tracked from the cylinder exit to the catalytic converter outlet and converted to time-resolved mass emissions by applying an instantaneous exhaust mass flow rate model. A phenomenological model of exhaust heat transfer combined with the gas composition analysis was also developed to define the thermal and chemical energy state of the exhaust gas with SAI.

Ash, primarily derived from diesel engine lubricants, accumulates in diesel particulate filters directly affecting the filter's pressure drop sensitivity to soot accumulation, thus impacting regeneration frequency and fuel economy. After approximately 33,000 miles of equivalent on-road aging, ash comprises more than half of the material accumulated in a typical cordierite filter. Ash accumulation reduces the effective filtration area, resulting in higher local soot loads toward the front of the filter. At a typical ash cleaning interval of 150,000 miles, ash more than doubles the filter's pressure drop sensitivity to soot, in addition to raising the pressure drop level itself. In order to evaluate the effects of lubricant-derived ash on DPF pressure drop performance, a novel accelerated ash loading system was employed to generate the ash and load the DPFs under carefully-controlled exhaust conditions.

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.

Ash accumulation in diesel particulate filters, mostly from essential lubricant additives, decreases the filter's soot storage capacity, adversely affects fuel economy, and negatively impacts the filter's service life. While the adverse effects of ash accumulation on DPF performance are well known, the underlying mechanisms controlling these effects are not. To address these issues, results of detailed measurements with specially formulated lubricants, correlating ash properties to individual lubricant additives and their effects on DPF pressure drop, are presented. Investigations using the specially-formulated lubricants showed ash consisting primarily of calcium sulfates to exhibit significantly increased flow resistance as opposed to ash primarily composed of zinc phosphates. Furthermore, ash accumulated along the filer walls was found to be packed approximately 25% denser than ash accumulated in the channel end-plugs.

The effects of charge motion and laminar flame speeds on combustion and exhaust temperature have been studied by using an air jet in the intake flow to produce an adjustable swirl or tumble motion, and by replacing the nitrogen in the intake air by argon or CO₂, thereby increasing or decreasing the laminar flame speed. The objective is to examine the "Late Robust Combustion" concept: whether there are opportunities for producing a high exhaust temperature using retarded combustion to facilitate catalyst warm-up, while at the same time, keeping an acceptable cycle-to-cycle torque variation as measured by the coefficient of variation (COV) of the net indicated mean effective pressure (NIMEP). The operating condition of interest is at the fast idle period of a cold start with engine speed at 1400 RPM and NIMEP at 2.6 bar. A fast burn could be produced by appropriate charge motion. The combustion phasing is primarily a function of the spark timing.

Ammonia oxidation (AMOX) catalysts are critical parts of most diesel aftertreatment systems around the world. These catalysts are positioned downstream of selective catalytic reduction (SCR) catalysts and remove unreacted NH3 that passes through the SCR catalyst. In many configurations, the AMOX catalyst is situated after a diesel oxidation catalyst and catalyzed diesel particulate filter that oxidize CO and hydrocarbons. However, in Euro V and proposed Tier 4 final aftertreatment architectures there is no upstream oxidation catalyst. In this study, the impact of hydrocarbons is evaluated on two different types of AMOX catalysts. One has dual washcoat layers-SCR washcoat on top of PGM washcoat-and the other has only a PGM washcoat layer. Results are presented for NH3 and hydrocarbon oxidation, NOx and N2O selectivity, and hydrocarbon storage. The AMOX findings are rationalized in terms of their impact on the individual oxidation and SCR functions.

In this study, the formation and decomposition of ammonium nitrate (AN) on a state-of-the-art extruded vanadium-based SCR catalyst (V-SCR) under simulated exhaust conditions has been evaluated. Results show that AN readily forms and accumulates at temperatures below 200°C when exposed to NH3 and NO2. The rate of AN accumulation increases with decreasing temperature. A new low temperature NH3 release peak (not present following NH3 storage conditions with NH3 only) becomes apparent after AN accumulation at 100 and 125°C. This new NH3 release, with a peak release temperature of approximately 180°C, is evaluated in detail to better determine its origin. BET surface area, and thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), and reactor-based experiments are all used to characterize AN formed on the V-SCR catalyst in comparison to pure AN.

Lean-burn natural gas (NG) engines are used world-wide for both stationary power generation and mobile applications ranging from passenger cars to Class 8 line-haul trucks. With the recent introduction of hydraulic fracturing gas extraction technology and increasing availability of natural gas, these engines are receiving more attention. However, the reduction of unburned hydrocarbon emissions from lean-burn NG and dual-fuel (diesel and natural gas) engines is particularly challenging due to the stability of the predominant short-chain alkane species released (e.g., methane, ethane, and propane). Supported Pd-based oxidation catalysts are generally considered the most active materials for the complete oxidation of low molecular weight alkanes at temperatures typical of lean-burn NG exhaust. However, these catalysts rapidly degrade under realistic exhaust conditions with high water vapor concentrations and traces of sulfur.

The oxidation of short-chain alkanes, such as methane, ethane, and propane, from the exhaust of lean-burn natural gas and lean-burn dual-fuel (natural gas and diesel) engines poses a unique challenge to the exhaust aftertreatment community. Emissions of these species are currently regulated by the US Environmental Protection Agency (EPA) as either methane (Greenhouse Gas Emissions Standards) or non-methane hydrocarbon (NMHC). However, the complete catalytic oxidation of short-chain alkanes is challenging due to their thermodynamic stability. The present study focuses on the oxidation of short-chain alkanes by vanadium-based and Cu/zeolite selective catalytic reduction (SCR) catalysts, generally utilized to control NOx emissions from lean-burn engines. Results reveal that these catalysts are active for short-chain alkane oxidation, albeit, at conversions lower than those generally reported in the literature for Pd-based catalysts, typically used for short-chain alkane conversion.

The increasing use of gasoline direct injection (GDI) engines coupled with the implementation of new particulate matter (PM) and particle number (PN) emissions regulations requires new emissions control strategies. Gasoline particulate filters (GPFs) present one approach to reduce particle emissions. Although primarily composed of combustible material which may be removed through oxidation, particle also contains incombustible components or ash. Over the service life of the filter the accumulation of ash causes an increase in exhaust backpressure, and limits the useful life of the GPF. This study utilized an accelerated aging system to generate elevated ash levels by injecting lubricant oil with the gasoline fuel into a burner system. GPFs were aged to a series of levels representing filter life up to 150,000 miles (240,000 km). The impact of ash on the filter pressure drop and on its sensitivity to soot accumulation was investigated at specific ash levels.

To meet future particle mass and particle number standards, gasoline vehicles may require particle control, either by way of an exhaust gas filter and/or engine modifications. Soot levels for gasoline engines are much lower than diesel engines; however, non-combustible material (ash) will be collected that can potentially cause increased backpressure, reduced power, and lower fuel economy. The purpose of this work was to examine the ash loading of gasoline particle filters (GPFs) during rapid aging cycles and at real time low mileages, and compare the filter performances to both fresh and very high mileage filters. Current rapid aging cycles for gasoline exhaust systems are designed to degrade the three-way catalyst washcoat both hydrothermally and chemically to represent full useful life catalysts. The ash generated during rapid aging was low in quantity although similar in quality to real time ash. Filters were also examined after a low mileage break-in of approximately 3000 km.

The increasing use of diesel and gasoline particulate filters requires advanced on-board diagnostics (OBD) to prevent and detect filter failures and malfunctions. Early detection of upstream (engine-out) malfunctions is paramount to preventing irreversible damage to downstream aftertreatment system components. Such early detection can mitigate the failure of the particulate filter resulting in the escape of emissions exceeding permissible limits and extend the component life. However, despite best efforts at early detection and filter failure prevention, the OBD system must also be able to detect filter failures when they occur. In this study, radio frequency (RF) sensors were used to directly monitor the particulate filter state of health for both gasoline particulate filter (GPF) and diesel particulate filter (DPF) applications.

Low-temperature (T ≤ 200°C) NOx conversion is receiving increasing research attention due to continued potential reductions in regulated NOx emissions from diesel engines. At these temperatures, ammonium salts (e.g., ammonium nitrate, ammonium (bi)sulfate, etc.) can form as a result of interactions between NH3 and NOx or SOx, respectively. The formation of these salts can reduce the availability of NH3 for NOx conversion, block active catalyst sites, and result in the formation of N2O, a regulated Greenhouse Gas (GHG). In this study, we investigate the effect of hydrothermal aging on the formation and decomposition of ammonium nitrate on a state-of-the-art Cu/zeolite selective catalytic reduction (SCR) catalyst. Reactor-based constant-temperature ammonium nitrate formation, temperature programmed oxidation (TPO), and NO titration experiments are used to characterize the effect of hydrothermal aging from 600 to 950°C.

Diesel particulate filters are designed to reduce the mass emissions of diesel particulate matter and have been proven to be effective in this respect. Not much is known, however, about their effects on other unregulated chemical species. This study utilized source dilution sampling techniques to evaluate the effects of a catalyzed diesel particulate filter on a wide spectrum of chemical emissions from a heavy-duty diesel engine. The species analyzed included both criteria and unregulated compounds such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), inorganic ions, trace metallic compounds, elemental and organic carbon (EC and OC), polycyclic aromatic hydrocarbons (PAHs), and other organic compounds. Results showed a significant reduction for the emissions of PM mass, CO, HC, metals, EC, OC, and PAHs.

Titanium dioxide supported vanadium oxide catalysts have been successfully utilized for the selective catalytic reduction (SCR) of nitrogen oxides emitted from both stationary and mobile sources. Because of their cost and performance advantages in certain applications, vanadium-based SCR catalysts are now also being considered for integration into some U.S. Tier IV off-highway aftertreatment systems. However, concern exists that toxic vanadium compounds, such as vanadium pentoxide, could be released from these catalysts as a result of mechanical attrition or high temperature volatility. An experimental study has been conducted to compare various techniques for measuring the release of particle and vapor-phase vanadium from SCR catalysts. Previous research has utilized a powder reactor-based method to measure the vapor-phase release of vanadium, but there are inherent limitations to this technique.

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.

Natural gas-powered engines are widely used due to their low fuel cost and in general their lower emissions than conventional diesel engines. In order to comply with emissions regulations, an aftertreatment system is utilized to treat exhaust from natural gas engines. Stoichiometric burn natural gas engines use three-way catalyst (TWC) technology to simultaneously remove NOx, CO, and hydrocarbon (HC). Removal of methane, one of the major HC emissions from natural gas engines, is difficult due to its high stability, posing a challenge for existing TWC technologies. In this work, degreened (DG), standard bench cycle (SBC)-aged TWC catalysts and a DG Pd-based oxidation catalyst (OC) were evaluated and compared under a variety of lean/rich gas cycling conditions, simulating stoichiometric natural gas engine emissions.

The accumulation of soot and lubrication-derived ash particles in a diesel particulate filter (DPF) increases exhaust flow restriction and negatively impacts engine efficiency. Previous studies have described the macroscopic phenomenon and general effects of soot and ash accumulation on filter pressure drop. In order to enhance the fundamental understanding, this study utilized a novel apparatus that of a dual beam scanning electron microscope (SEM) and focused ion beam (FIB), to investigate microscopic details of soot and ash accumulation in the DPF. Specifically, FIB provides a minimally invasive technique to analyze the interactions between the soot, ash, catalyst/washcoat, and DPF substrate with a high degree of measurement resolution. The FIB utilizes a gallium liquid metal ion source which produces Ga+ ions of sufficient momentum to directionally mill away material from the soot, ash, and substrate layers on a nm-μm scale.

Current CJ-4 lubricant specifications place chemical limits on diesel engine oil formulations to minimize the accumulation of lubricant-derived ash in diesel particulate filters (DPF). While lubricant additive chemistry plays a strong role in determining the amount and type of ash accumulated in the DPF, a number of additional factors play important roles as well. Relative to soot particles, whose residence time in the DPF is short-lived, ash particles remain in the filter for a significant fraction of the filter's useful life. While it is well-known that the properties (packing density, porosity, permeability) of soot deposits are primarily controlled by the local exhaust conditions at the time of particle deposition in the DPF, the cumulative operating history of the filter plays a much stronger role in controlling the properties and distribution of the accumulated ash.

A simple 1-dimensional filter model, with symmetric and asymmetric channels, has been developed to investigate the fundamental behavior and performance of ceramic partial diesel particulate filters (PFs). The governing equations of mass and momentum are similar to those of a full DPF [7, 15]. A standard DPF with the plugs at its inlet face removed has been referred to as a ‘rear-plugged PF’ while, one with the plugs at the outlet face removed has been referred to as a ‘front-plugged PF’ in the present study. Removal of some of the plugs from a standard ceramic DPF reduces the (i) overall pressure drop (ΔP) across the filter, (ii) filtration efficiency (FE) of the DPF, and (iii) manufacturing cost. Partial filters stand a high chance of being deployed in diesel exhaust after-treatment systems for the emerging markets (Brazil, Russia, India, China) that follow Euro 4 emission regulations.