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Urea-selective catalytic reduction (SCR) catalysts are the leading aftertreatment technology for diesel engines, but there are major challenges associated with meeting future NOx emission standards, especially under transient drive cycle conditions that include large swings in exhaust temperatures. Here we present a simplified, transient, one-dimensional integral model of NOx reduction by NH₃ on a commercial small-pore Cu-zeolite urea-SCR catalyst for which detailed kinetic parameters have not been published. The model was developed and validated using data acquired from bench reactor experiments on a monolith core, following a transient SCR reactor protocol. The protocol incorporates NH₃ storage, NH₃ oxidation, NO oxidation and three global SCR reactions under isothermal conditions, at three space velocities and at three NH₃/NOx ratios.

In order to further characterize and optimize the performance of Selective Catalytic Reduction (SCR) aftertreatment systems used on heavy-duty diesel engines, an accurately calibrated high-fidelity multi-step global kinetic SCR model and a reduced order estimator for on-board diagnostic (OBD) and control are desirable. In this study, a Cu-zeolite SCR catalyst from a 2010 Cummins ISB engine was experimentally studied in a flow reactor using carefully designed protocols. A 2-site SCR model describing mass transfer and the SCR chemical reaction mechanisms is described in the paper. The model was calibrated to the reactor test data sets collected under temperatures from 200 to 425 °C and SCR space velocities of 60000, 90000, and 120000 hr-1. The model parameters were calibrated using an optimization code to minimize the error between measured and simulated NO, NO₂, N₂O, and NH₃ gas concentration time histories.

Lean gasoline engines offer greater fuel economy than the common stoichiometric gasoline engine, but the current three way catalyst (TWC) on stoichiometric engines is unable to control nitrogen oxide (NOX) emissions in oxidizing exhaust. For these lean gasoline engines, lean NOX emission control is required to meet existing Tier 2 and upcoming Tier 3 emission regulations set by the U.S. Environmental Protection Agency (EPA). While urea-based selective catalytic reduction (SCR) has proven effective in controlling NOX from diesel engines, the urea storage and delivery components can add significant size and cost. As such, onboard NH3 production via a passive SCR approach is of interest. In a passive SCR system, NH3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean operation, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst.

A commercial three-way catalyst (TWC) was evaluated for ammonia (NH3) generation on a 2.0-liter BMW lean burn gasoline direct injection engine as a component in a passive ammonia selective catalytic reduction (SCR) system. The passive NH3 SCR system is a potential low cost approach for controlling nitrogen oxides (NOX) emissions from lean burn gasoline engines. In this system, NH3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst. NH3 generation was evaluated at different air-fuel equivalence ratios at multiple engine speed and load conditions. Near complete conversion of NOX to NH3 was achieved at λ=0.96 for nearly all conditions studied. At the λ=0.96 condition, HC emissions were relatively minimal, but CO emissions were significant.

A hybrid LNT+SCR system is used to control NOx from a light-duty diesel engine with in-cylinder regeneration controls. A diesel oxidation catalyst and diesel particulate filter are upstream of the LNT and SCR catalysts. Ultraviolet (UV) adsorption spectroscopy performed directly in the exhaust path downstream of the LNT and SCR catalysts is used to characterize NH3 production and utilization in the system. Extractive exhaust samples are analyzed with FTIR and magnetic sector mass spectrometry (H2) as well. Furthermore, standard gas analyzers are used to complete the characterization of exhaust chemistry. NH3 formation increases strongly with extended regeneration (or “over regeneration”) of the LNT, but the portion of NOx reduction occurring over the SCR catalyst is limited by the amount of NH3 produced as well as the amount of NOx available downstream of the LNT. Control of lean-rich cycling parameters enables control of the ratio of NOx reduction between the LNT and SCR catalysts.

An optical-based sensor for detecting particulate matter (PM) in diesel engine exhaust has been demonstrated. The position of the sensor during the experiments was the exhaust manifold prior to the turbocharger. The sensor is constructed of fiber optics which transmit 532-nm laser light into the exhaust pipe and collect backscattered light in a 180° geometry. Due to the optical nature of the probe, PM sensing can occur at high temporal rates. Experiments conducted by changing the fuel injection properties of one cylinder of a four cylinder engine demonstrated that the sensor can resolve cycle dependent events. The feasibility of the probe for examining PM emissions in the exhaust manifold will be discussed.

Lean NOx Trap (LNT) catalysts are capable of reducing NOx in lean exhaust from diesel engines. NOx is stored on the catalyst during lean operation; then, under rich exhaust conditions, the NOx is released from and reduced by the catalyst. The process of NOx release and reduction is called regeneration. One method of obtaining the rich conditions for regeneration is to inject additional fuel into the engine cylinders while throttling the engine intake air flow to effectively run the engine at rich air:fuel ratios; this method is called “in-cylinder” regeneration. In-cylinder regeneration of LNT catalysts has been demonstrated and is a candidate emission control technique for commercialization of light-duty diesel vehicles to meet future emission regulations. In the study presented here, a 1.7-liter diesel engine with a LNT catalyst system was used to evaluate in-cylinder regeneration techniques.

Measuring axial exhaust species concentration distributions within a wall-flow aftertreatment device provides unique and significant insights regarding the performance of complex devices like the SCR-on-filter. In this particular study, a less complex aftertreatment configuration which includes a DOC followed by two uncoated partial flow filters (PFF) was used to demonstrate the potential and challenges. The PFF design in this study was a particulate filter with alternating open and plugged channels. A SpaciMS [1] instrument was used to measure the axial NO2 profiles within adjacent open and plugged channels of each filter element during an extended passive regeneration event using a full-scale engine and catalyst system. By estimating the mass flow through the open and plugged channels, the axial soot load profile history could be assessed.

One challenge in meeting emission regulations with catalytic aftertreatment systems is maintaining the proper catalyst temperatures that enable the catalytic devices to perform the emissions reduction. In this study, in-cylinder techniques are used to actively control the temperature of a catalyzed diesel particulate filter (DPF) in order to raise the DPF temperature to induce particulate oxidation. The performance of four strategies is compared for two different starting DPF temperatures (150°C and 300°C) on a 4-cylinder 1.7-liter diesel engine. The four strategies include: (1) addition of extra fuel injection early in the combustion cycle for all four cylinders, (2) addition of extra fuel injection late in the combustion cycle for all four cylinders, (3) operating one-cylinder with extra fuel injection early in the combustion cycle, and (4) operating one-cylinder with extra fuel injection late in the combustion cycle.

Lean NOx trap (LNT) catalysts with different formulations have been characterized on a light-duty diesel engine platform. Two in-cylinder regeneration strategies were used during the study. The reductant chemistry differed for both strategies with one strategy having high levels of CO and H2 and the other strategy having a higher hydrocarbon component. The matrix of LNT catalysts that were characterized included LNTs with various sorbate loads and varying ceria content; the sorbate was Ba. Intra-catalyst measurements of exhaust gas composition were obtained at one quarter, one half, and three quarters of the length of the catalysts to better understand the affect of formulation on performance. Exhaust analysis with FTIR allowed measurement of NH3 and thereby, a measurement of N2 selectivity for the catalysts. Although overall NOx conversion increased with increasing sorbate load, the formation of NH3 increased as well.

Widespread implementation of homogeneous charge compression ignition (HCCI) engines is presently hindered by stability, control, and load range issues. Although the operable HCCI speed/load range is expanding, it is likely that the initial HCCI engines will rely on conventional combustion for part of the operating cycle. In the present study, we have investigated the role of fuel properties and chemistry on the operation of a spark-assisted gasoline HCCI engine. The engine employed is a single cylinder, 500 cc, port fuel injected research engine, operating near lambda = 1.0 and equipped with hydraulic variable valve actuation. HCCI is initiated by early exhaust valve closing to retain exhaust in the cylinder, thereby increasing the cylinder gas temperature. This is also referred to as a ‘negative overlap’ strategy.

Reliable means for on-board detection of particulate filter failures or malfunctions are needed to meet diagnostics (OBD) requirements. Detecting these failures, which result in tailpipe particulate matter (PM) emissions exceeding the OBD limit, over all operating conditions is challenging. Current approaches employ differential pressure sensors and downstream PM sensors, in combination with particulate filter and engine-out soot models. These conventional monitors typically operate over narrowly-defined time windows and do not provide a direct measure of the filter’s state of health. In contrast, radio frequency (RF) sensors, which transmit a wireless signal through the filter substrate provide a direct means for interrogating the condition of the filter itself.

The poisoning of diesel oxidation catalysts (DOCs) by the engine oil additive zinc dialkyldithiophosphate (ZDDP) is investigated in the present study. A 517cc single-cylinder diesel engine is used to accelerate the phosphorus poisoning of DOCs by artificially increasing the ZDDP consumption to approximately 700 times normal operation by three different methods. These include lube-oil doped fuel, intake manifold, and exhaust manifold injection with lube-oil containing an elevated level of ZDDP. The deactivation of DOCs under these conditions is characterized by a variety of physical and chemical techniques. Surface composition and structure of the poisoned catalysts analyzed with SEM-EDS show differences depending on the method of ZDDP introduction. Exhaust manifold injection produces a zinc phosphate glaze which masks the surface to species diffusion. Fuel and intake manifold injection methods produce chemically absorbed phosphorus on the catalyst washcoat surface.

The accelerated ash loading of diesel particulate filters (DPFs) with diesel oxidation catalysts (DOCs) mounted upstream by lube-oil derived products was investigated using a single cylinder diesel engine and fuel blended with 5% lube oil. An ash loading protocol is developed which combines soot loading, active soot regeneration, and periodic shutdowns for filter weighing. Active regeneration is accomplished by exhaust injection of diesel fuel, initiated by a backpressure criteria and providing DPF temperatures up to 700°C. In developing this protocol, five DPFs of various combinations of substrates (cordierite, silicon carbide, and mullite) and washcoats (none, low PGM, and high PGM) are used and evaluated. The initial backpressure and rate of backpressure increase with ash varied with each of the DPFs and ash was observed to have an effect on the active soot light-off temperature for the catalyzed DPFs.

This paper reports the test results from the DPF (diesel particulate filter) portion of the DECSE (Diesel Emission Control - Sulfur Effects) Phase 1 test program. The DECSE program is a joint government and industry program to study the impact of diesel fuel sulfur level on aftertreatment devices. A systematic investigation was conducted to study the effects of diesel fuel sulfur level on (1) the emissions performance and (2) the regeneration behavior of a continuously regenerating diesel particulate filter and a catalyzed diesel particulate filter. The tests were conducted on a Caterpillar 3126 engine with nominal fuel sulfur levels of 3 parts per million (ppm), 30 ppm, 150 ppm and 350 ppm.

A prototype three-way catalyst (TWC) with NOX storage component was evaluated for ammonia (NH3) generation on a 2.0-liter BMW lean burn gasoline direct injection engine as a component in a passive ammonia selective catalytic reduction (SCR) system. The passive NH3 SCR system is a potential approach for controlling nitrogen oxides (NOX) emissions from lean burn gasoline engines. In this system, NH3 is generated over a close-coupled TWC during periodic slightly-rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst. Adding a NOX storage component to a TWC provides two benefits in the context of a passive SCR system: (1) enabling longer lean operation by storing NOX upstream and preserving NH3 inventory on the downstream SCR catalyst; and (2) increasing the quantity and rate of NH3 production during rich operation.

In this study, high-temperature deactivation of a fully-formulated lean NOx trap (LNT) is investigated with an accelerated aging protocol where accelerated aging is accomplished by rapid temperature cycling and by higher temperatures. Thermal aging is carried out in a bench-flow reactor at nominal temperatures of 700, 800, 900, and 1000°C using an aging cycle consisting of a 130s lean-phase and a 50s rich-phase. After a prescribed number of lean/rich aging cycles, the NOx conversion of the aged LNT is evaluated at 200, 300, and 400°C. The NOx performance is obtained at a GHSV of 30,000 h−1 using an evaluation cycle consisting of a 60s lean-phase and 5s rich-phase. The effects of aging on the LNT washcoat are determined with EPMA, XRD, STEM/EDS, and BET. Aging at 700 and 800°C has a minimal effect on LNT performance and material properties.

Greenhouse gas regulations and global economic growth are expected to drive a future demand shift towards diesel fuel in the transportation sector. This may create a market opportunity for cost-effective fuels in the light distillate range if they can be burned as efficiently and cleanly as diesel fuel. In this study, the emission performance of a low cetane number, low research octane number naphtha (CN 34, RON 56) was examined on a production 6-cylinder heavy-duty on-highway truck engine and aftertreatment system. Using only production hardware, both the engine-out and tailpipe emissions were examined during the heavy-duty emission testing cycles using naphtha and ultra-low-sulfur diesel (ULSD) fuels. Without any modifications to the hardware and software, the tailpipe emissions were comparable when using either naphtha or ULSD on the heavy duty test cycles.

For renewable fuels to displace petroleum, they must be compatible with emissions control devices. Pure biodiesel contains up to 5 ppm Na + K and 5 ppm Ca + Mg metals, which have the potential to degrade diesel emissions control systems. This study aims to address these concerns, identify deactivation mechanisms, and determine if a lower limit is needed. Accelerated aging of a production exhaust system was conducted on an engine test stand over 1001 h using 20% biodiesel blended into ultra-low sulfur diesel (B20) doped with 14 ppm Na. This Na level is equivalent to exposure to Na at the uppermost expected B100 value in a B20 blend for the system full-useful life. During the study, NOx emissions exceeded the engine certification limit of 0.33 g/bhp-hr before the 435,000-mile requirement.

Three established mechanical test specimen geometries and test methods used to evaluate mechanical properties of brittle materials are adapted to the diesel particulate filter (DPF) architecture to evaluate failure initiation stress and apparent elastic modulus of the ceramics comprising DPFs. The three custom-designed test coupons are harvested out of DPFs to promote a particular combination of orientation of crack initiation and crack plane. The testing of the DPF biaxial flexure disk produces a radial tensile stress and a crack plane parallel with the DPF's longitudinal axis. The testing of the DPF sectored flexural specimen produces axial tension at the DPF's OD and a crack plane perpendicular to the DPF's longitudinal axis. The testing of the DPF o-ring specimen produces hoop tension at the DPF's original outer diameter (OD) and at the inner diameter of the test coupon, and a crack plane parallel to the DPF's longitudinal axis.