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Cu- and Fe-zeolite SCR catalysts emerged in recent years as the primary candidates for meeting the increasingly stringent lean exhaust emission regulations, due to their outstanding activity and durability characteristics. It is commonly known that Cu-zeolite catalysts possess superior activity to Fe-zeolites, in particular at low temperatures and sub-optimal NO₂/NOx ratios. In this work, we elucidate some underlying mechanistic differences between these two classes of catalysts, first based on their NO oxidation abilities, and then based on the relative properties of the two types of exchanged metal sites. Finally, by using the ammonia coverage-dependent NOx performance, we illustrate that state-of-the-art Fe-zeolites can perform better under certain transient conditions than in steady-state.

Fuel lean combustion and exhaust gas dilution are known to increase the thermal efficiency and reduce NOx emissions. In this study, experiments are performed to understand the effect of equivalence ratio on flame kernel formation and flame propagation around the spark plug for different low turbulent velocities. A series of experiments are carried out for propane-air mixtures to simulate engine-like conditions. For these experiments, equivalence ratios of 0.7 and 0.9 are tested with 20 percent mass-based exhaust gas recirculation (EGR). Turbulence is generated by a shrouded fan design in the vicinity of J-spark plug. A closed loop feedback control system is used for the fan to generate a consistent flow field. The flow profile is characterized by using Particle Image Velocimetry (PIV) technique. High-speed Schlieren visualization is used for the spark formation and flame propagation.

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.

Future light duty vehicles in the United States are required to be certified on the FTP-75 cycle to meet Tier 3 or LEV III emission standards [1, 2]. The cold phase of this cycle is heavily weighted and mitigation of emissions during this phase is crucial to meet the low tail pipe emission targets [3, 4]. In this work, a novel aftertreatment architecture and controls to improve Nitrogen Oxides (NOx) and Hydrocarbon (HC) or Non Methane Organic gases (NMOG) conversion efficiencies at low temperatures is proposed. This includes a passive NOx & HC adsorber, termed the diesel Cold Start Concept (dCSC™) catalyst, followed by a Selective Catalytic Reduction catalyst on Filter (SCRF®) and an under-floor Selective Catalytic Reduction catalyst (SCR). The system utilizes a gaseous ammonia delivery system capable of dosing at two locations to maximize NOx conversion and minimize parasitic ammonia oxidation and ammonia slip.

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.

Past experimental studies conducted by the current authors on a 13 liter 16.7:1 compression ratio heavy-duty diesel engine have shown that diesel-Compressed Natural Gas (CNG) Reactivity Controlled Compression Ignition (RCCI) combustion targeting low NOx emissions becomes progressively difficult to control as the engine load is increased. This is mainly due to difficulty in controlling reactivity levels at higher loads. For the current study, CFD investigations were conducted in CONVERGE using the SAGE combustion solver with the application of the Rahimi mechanism. Studies were conducted at a load of 5 bar BMEP to validate the simulation results against RCCI experimental data. In the low load study, it was found that the Rahimi mechanism was not able to predict the RCCI combustion behavior for diesel injection timings advanced beyond 30 degCA bTDC. This poor prediction was found at multiple engine speed and load points.

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.

Regeneration of diesel particulate filters poses major challenges in developing the particulate matter emission control technology to meet EPA 2007/2010 emissions regulations. The problem areas are multifold due to the complexity involved in designing the filter system, developing regeneration strategies and controlling the regeneration process. This paper discusses the need for active regeneration systems. It also addresses several key limitations and trade-offs between the regeneration strategy, chemical kinetics, exhaust gas temperature and the regeneration efficiency. Passive regeneration of diesel particulate filter systems is known to be highly dependent on the engine-out [NOx/PM] ratio as well as exhaust temperature over the duty cycle. Using catalytic oxidation of auxiliary fuel injected into the system, the exhaust gas temperature can be successfully enhanced for filter regeneration.

Mitigation of ammonia slip from SCR system is critical to meeting the evolving NH₃ emission standards, while achieving maximum NOx conversion efficiency. Ammonia slip catalysts (ASC) are expected to balance high activity, required to oxidize ammonia across a broad range of operating conditions, with high selectivity of converting NH₃ to N₂, thus avoiding such undesirable byproducts as NOx or N₂O. In this work, new insights into the behavior of an advanced ammonia slip catalyst have been developed by using accelerated progressive catalyst aging as a tool for catalyst property interrogation. The overall behavior was deconstructed to several underlying functions, and referenced to an active but non-selective NH₃ oxidation function of a diesel oxidation catalyst (DOC) and to the highly selective but minimally active NH₃ oxidation function of an SCR catalyst.

Production NO sensors have a strong cross-sensitivity to ammonia which limits their use for closed-loop SCR control and diagnostics since increases in sensor output can be caused by either gas component. Recently, Ammonia/NO Ratio (ANR) perturbation methods have been proposed for determining the dominant component in the post-SCR exhaust as part of the overall SCR control strategy, but these methods or the issue of sensor cross-sensitivity have not been critically evaluated or studied in their own right. In this paper the dynamic sensor direct- and cross-sensitivities are estimated from experimental FTIR data (after compensating for the dynamics of the gas sampling system) and compared to nominal values provided by the manufacturer. The ANR perturbation method and the use of different input excitations are then discussed within an analytical framework, and applied to experimental data from a large diesel engine.

Cu/CHA catalysts have been widely used in the industry, due to their desirable performance characteristics including the unmatched hydrothermal stability. While broadly recognized for their outstanding activity at or above 200°C, these catalysts may not show desired levels of NOx conversion at lower temperatures. To achieve high NOx conversions it is desirable to have NO2/NOx close to 0.5 for fast SCR. However even under such optimal gas feed conditions, sustained use of Cu/CHA below 200°C leads to ammonium nitrate formation and accumulation, resulting in the inhibition of NOx conversion. In this contribution, the formation and decomposition of NH4NO3 on a commercial Cu/CHA catalyst have been investigated systematically. First, the impact of NH4NO3 self-inhibition on SCR activity as a function of temperature and NO2/NOx ratios was investigated through reactor testing.

It has long been recognized that the key to achieving stringent emission standards such as ULEV is the control of cold-start hydrocarbons. This paper describes a new approach for achieving excellent cold-start hydrocarbon control. The most important component in the system is a catalyst that is highly active at ambient temperature for the exothermic CO oxidation reaction in an exhaust stream under net lean conditions. This catalyst has positive order kinetics with respect to CO for CO oxidation. Thus, as the concentration of CO in the exhaust is increased, the rate of this reaction is increased, resulting in a faster temperature rise over the catalyst.

The molecular filtration of sulfur components in ultra low sulfur diesel (ULSD) fuel is described. A comprehensive screening of potential sulfur removal chemistries has yielded a sorbent which has the capability to efficiently remove organo-sulfur components in ULSD fuel. This sorbent has been used to treat ULSD fuel on a heavy duty engine equipped with NOx adsorber after-treatment technology and has been shown to lengthen the time between desulfation steps for the NOx adsorber. The fuel properties, cetane number and aromatics content, etc., have not been changed by the removal of the sulfur in the fuel with the exception of the lubricity which is reduced.

With concerns continuing to grow with respect to global warming from greenhouse gases, further regulations are being examined, developed and are expected for the emission of CO2 as an automobile exhaust. Renewable alternate fuels offer the potential to significantly reduce the CO2 impact of transportation. Hydrogen as a spark - ignition (SI) engine fuel provides this potential for significant CO2 reduction when generated from renewable resources. In addition, hydrogen has advantageous combustion properties including a wide flammable mixture range which facilitates lean burning and high dilution, fast combustion energy release and zero CO2 emissions. However, the high burning rates and fast energy release can lead to excessive in-cylinder pressures and temperatures resulting in combustion knock and high NOx emissions at stoichiometric operation.

The SNR-technique is a new NOx aftertreatment system for lean burn gasoline and diesel applications. The objective of SNR is NOx removal from lean exhaust gas by NOx adsorption and subsequent selective external recirculation and decomposition of NOx in the combustion process. The SNR-project is composed of two major parts. Firstly the development of NOx adsorbents which are able to store large quantities of NOx in lean exhaust gas, and secondly the NOx decomposition by the combustion process. Emphasis of this paper is the investigation of NOx reduction in the combustion process, including experimental investigation and numerical simulation. The NOx decomposition process has been proven in diesel and lean-burn gasoline engines. Depending on the type of engine NOx-conversion rates up to 90 % have been observed. Regarding the complete SNR-system, including the efficiency of the adsorbing material and the NOx decomposition by the combustion, a NOx removal of more than 50% is achievable.

Selective NOx recirculation (SNR), involving adsorption, selective external recirculation and decomposition of the NOx by the combustion process, is itself a promising technique to abate NOx emissions. Three types of materials containing Ba: barium aluminate, barium tin perovskite and barium Y-zeolites have been developed to adsorb NOx under lean-burn or Diesel conditions, with or without the presence of S02. All these materials adsorb NO2 selectively (lean-burn conditions), and store it as nitrate/nitrite species. The desorption takes place by decomposition of these species at higher temperatures. Nitrate formation implies also sulfate formation in the presence of SO2 and SO3, while the NO2/SO2 competition governs the poisoning of such catalysts.

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.

A one-dimensional model simulating the oxidation of CO, HC, and NO was developed to predict the gaseous emissions downstream of a diesel oxidation catalyst (DOC). The model is based on the conservation of mass, species, and energy inside the DOC and draws on past research literature. Steady-state experiments covering a wide range of operating conditions (exhaust temperatures, flow rates and gaseous emissions) were performed, and the data were used to calibrate and validate the model. NO conversion efficiencies of 50% or higher were obtained at temperatures between 300°C and 350°C. CO conversion efficiencies of 85% or higher and HC conversion efficiencies of 75% or higher were found at every steady state condition above 200°C. The model agrees well with the experimental results at temperatures from 200°C to 500°C, and volumetric flow rates from 8 to 42 actual m3/min.

Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure.

Future US emissions limits are likely to mean a sophisticated nitrogen oxide (NOx) reduction technique is required for all vehicles with a diesel engine, which is likely to be either NOx trap or selective catalytic reduction (SCR) technology. To investigate the potential of SCR for NOx reduction on a light duty vehicle, a current model vehicle (EUII M1 calibration), of inertia weight 1810 kg, was equipped with an urea-based SCR injection system and non-vanadium, non-zeolitic SCR catalysts. To deal with carbon monoxide (CO), hydrocarbon (HC) and volatile organic fraction (VOF), a diesel oxidation catalyst was also incorporated into the system for most tests. Investigations into the effect of placing the oxidation catalyst at different positions in the system, changing the volume of the SCR catalysts, increasing system temperature through road load changes, varying the SCR catalyst composition, and changing the urea injection calibration are discussed.