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The performance of three way and NOx catalysts was evaluated on vehicles utilizing non-feedback fuel control and electronic feedback fuel control. The vehicles accumulated 80,450 km (50,000 miles) using fuels representing the extremes in hydrogen-carbon ratio available for commercial use. Feedback carburetion compared to non-feedback carburetion improved highway fuel economy by about 0.4 km/l (1 mpg) and reduced deterioration of NOx with mileage accumulation. NOx emissions were higher with the low H/C fuel in the three way catalyst system; feedback reduced the fuel effect on NOx in these cars by improving conversion efficiency with the low H/C fuel. Feedback had no measureable effect on HC and CO catalyst efficiency. Hydrocarbon emissions were lower with the low H/C fuel in all cars. Unleaded gasoline octane improver, MMT, at 0.015g Mn/l (0.06 g/gal) increased tailpipe hydrocarbon emissions by 0.05 g/km (0.08 g/mile).

Passive in-line catalyzed hydrocarbon (HC) traps have been used by some manufacturers in the automotive industry to reduce regulated tailpipe (TP) emissions of non-methane organic gas (NMOG) during engine cold-start conditions. However, most NMOG molecules produced during gasoline combustion are only weakly adsorbed via physisorption onto the zeolites typically used in a HC trap. As a consequence, NMOG desorption occurs at low temperatures resulting in the use of very high platinum group metal (PGM) loadings in an effort to combust NMOG before it escapes from a HC trap. In the current study, a 2.0 L direct-injection (DI) Ford Focus running on gasoline fuel was evaluated with full useful life aftertreatment where the underbody converter was either a three-way catalyst (TWC) or a HC trap. A new HC trap technology developed by Ford and Umicore demonstrated reduced TP NMOG emissions of 50% over the TWC-only system without any increase in oxides of oxygen (NOx) emissions.

Instrumentation of an exhaust system to measure surface temperature at multiple locations usually involves welding independent thermocouples to the surface of the system. This report describes a new type of thermocouple fabricated to measure temperature at a point or temperature difference between points on a metallic object utilizing the metal as one component of the new thermocouple. AISI 316 stainless steel is used in the current study to represent automotive exhaust pipe. The other component of the thermocouple is Nickel-Chromium (Chromel, Chromega), one of the two metals used in type K thermocouples, which are generally used for exhaust temperature measurements during emission tests. Use of the new thermocouple is contingent upon an accurate calibration of its response to changes in temperature.

The Variable Displacement Supercharger (VDS) is a twin helical screw style compressor that has a feature to change its displacement and its compression ratio actively during vehicle operation. This device can reduce the parasitic losses associated with supercharging and improve the relative fuel economy of a supercharged engine. Supercharging is a boosting choice with several advantages over turbocharging. There is fast pressure delivery to the engine intake manifold for fast engine torque response providing the fun to drive feel. The performance delivered by a supercharger can enable engine fuel economy actions to include engine downsizing and downspeeding. The cost and difficulty of engineering hot exhaust components is eliminated when using only an air side compressor. Faster catalyst warm up can be achieved when not warming the turbine housing of a turbocharger.

The aldehyde emissions of 1.6L and 5.0L flexible fuel vehicles (FFV) have been measured, with and without a catalyst, on a range of fuels. The “zero mile” catalyzed emission levels of formaldehyde when operating on M85 (85% methanol and 15% gasoline) are in the 5-15 mg/mi range, but as mileage accumulates they tend to be in the 30-50 mg/mi range. The feedgas levels are high and appear to correlate with engine displacement. The formaldehyde and methanol emissions are higher when operating on M100, compared to M85, but the non-oxygenated hydrocarbon emissions are about the same for both fuels, which suggests that the use of M85 may actually provide more air quality benefit than M100. High mileage control of aldehydes to the level of gasoline vehicles does not appear possible with current technology.

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 purpose of this work was to examine gasoline particle filters (GPFs) at high mileages. Soot levels for gasoline direct injection (GDI) engines are much lower than diesel engines; however, noncombustible material (ash) can cause increased backpressure, reduced power, and lower fuel economy. In this study, a post mortem was completed of two GPFs, one at 130,000 mi and the other at 150,000 mi, from two production 3.5L turbocharged GDI vehicles. The GPFs were ceramic wall-flow filters containing three-way catalytic washcoat and located downstream of conventional three-way catalysts. The oil consumption was measured to be approaching 23,000 mpqt for one vehicle and 30,000 mpqt for the other. The ash contained Ca, P, Zn, S, Fe, and catalytic washcoat. Approximately 50 wt% of the collected ash was non-lubricant derived. The filter capture efficiency of lubricant-derived ash was about 50% and the non-lubricant metal (mostly Fe) deposition rate was 0.9 to 1.2 g per 10,000 mi.

Phosphorous poisoning on customer-aged catalysts was investigated by material analysis and performance testing. Most of the phosphorus was associated with the oxide components in the washcoat. These contaminants were roughly classified as aluminum phosphate, cerium phosphate, zinc-calcium phosphate. Deactivation of the catalyst with aluminum phosphate was strong and followed a linear correlation from oxalic acid testing. Phosphorus scavenging additives were researched to inhibit increase of aluminum phosphate. According to thermodynamic calculations, lower free energy of compounds of additive and phosphate is expected to prevent formation of aluminum phosphate.

In the development of HC traps (HCT) for reducing vehicle cold start hydrocarbon (HC)/nitrogen oxide (NOx) emissions, zeolite-based adsorbent materials were studied as key components for the capture and release of the main gasoline-type HC/NOx species in the vehicle exhaust gas. Typical zeolite materials capture and release certain HC and NOx species at low temperatures (<200°C), which is lower than the light-off temperature of a typical three-way catalyst (TWC) (≥250°C). Therefore, a zeolite alone is not effective in enhancing cold start HC/NOx emission control. We have found that a small amount of Pd (<0.5 wt%) dispersed in the zeolite (i.e., BEA) can significantly increase the conversion efficiency of certain HC/NOx species by increasing their release temperature. Pd was also found to modify the adsorption process from pure physisorption to chemisorption and may have played a role in the transformation of the adsorbed HCs to higher molecular weight species.

This study was performed by the Department of Emissions Research at Southwest Research Institute (SwRI®) in response to a request from the ASTM OPEST II (Oil Protection of Emissions Systems Test) Task Force. The objective of the study was to develop and demonstrate a preliminary catalyst oil-poisoning aging and screening procedure to evaluate and differentiate the effect of oils with varying levels of phosphorus on catalyst performance. The ultimate objective was to begin the groundwork for creating a procedure that could demonstrate the impact of engine oil formulations on catalyst performance. The oils used in this program were fully formulated oils referred to as ‘OilA’ and ‘OilB.’ OilA contained 0.11 and OilB contained 0.06 weight percent phosphorus, with both containing the same levels of ash-forming compounds. The procedure developed used a gasoline-fueled burner with an isolated oil injection subsystem.

The differences in hydrocarbons (HCs) emitted by gasoline (E0) and ethanol (EtOH) blend fuels from flex-fuel capable engines can lead to differences in the performance of aftertreatment devices. Vehicle emission results have shown either better performance on E0 compared to E85 or vice versa, dependent on the vehicle calibration. In order to separate the impact of the vehicle and the catalyst, a laboratory study was conducted to evaluate performance on a pulse-flame (pulsator) reactor and compare reactivity towards E0 and E85 (85% EtOH-15% E0) exhaust. The catalysts evaluated were substrate-only, washcoat-only and fully formulated catalysts that had been aged either on a pulsator reactor or dynamometer engine. Catalyst performance was evaluated with light-off tests utilizing both slow and fast temperature ramp rates.

An air-to-fuel ratio (A/F) modulation scheme is presented in which a linear feedback signal is generated from a heated exhaust gas oxygen (EGO) sensor. In this scheme, the engine A/F is modulated with a triangular waveform, and the mean value of the EGO output is obtained using a rolling average filter. The resulting output is linearly related to the exhaust A/F, and is used to provide closed-loop lean A/F operation following a cold start to enhance catalyst light-off and minimize vehicle exhaust emissions. Some engine-dynamometer results obtained using the method are presented.

For diesel applications, cold start accounts for a large amount of the total NOx emissions during a typical Federal Test Procedure (FTP) for light-duty vehicles and is a key focus for reducing NOx emissions. A common form of diesel NOx aftertreatment is selective catalytic reduction (SCR) technology. For cold start NOx improvement, the SCR catalyst would be best located as the first catalyst in the aftertreatment system; however, engine-out hydrocarbons and no diesel oxidation catalyst (DOC) upstream to generate an exotherm for desulfation can result in degraded SCR catalyst performance. Recent advances in vanadia-based SCR (V-SCR) catalyst technology have shown better low temperature NOx performance and improved thermal durability. Three V-SCR technologies were tested for their thermal durability and low-temperature NOx performance, and after 600°C aging, one technology showed low-temperature performance on par with state-of-the-art copper-zeolite SCR (Cu-SCR) technology.

Selective catalytic reduction (SCR) is a viable option for control of oxides of nitrogen (NOx) from diesel engines. Currently, copper zeolite (Cu-zeolite) SCR catalysts are favored for configurations where the exhaust gas temperature is below 450°C for the majority of operating conditions, while iron zeolite (Fe-zeolite) SCR catalysts are preferred where NOx conversion is needed at temperatures above 450°C. The selection of Cu-zeolite or Fe-zeolite SCR catalysts is based on the different performance characteristics of these two catalyst types. Cu-zeolite catalysts are generally known for having efficient NOx reduction at low temperatures with little or no NO2, and they tend to selectively oxidize ammonia (NH3) to N2 at temperatures above 400°C, leading to poor NOx conversion at elevated temperatures.

The following paper highlights the results of a vehicle emission improvement program with emphasis on two main points: In the initial phase, various combinations of Pd and Pt-based three-way catalyst technologies were evaluated on a TLEV and a LEV calibrated vehicle in order to generate ULEV exhaust gas levels. One goal in this portion of the study was to achieve technical equivalence between a viable Pd-based technology and a newly developed Pt-based technology. A combination of the Pd- and Pt-based technologies was able to meet the ULEV and part of the ULEV II regulations in the test vehicle after a catalyst aging cycle that resembles 50,000 miles of vehicle driving. In the later phase, a mathematical algorithm based on the original TLEV and LEV vehicle data was developed in order to conduct computer modeling of the exhaust gas aftertreatment system. This algorithm described the kinetic behavior of the individual catalysts over a broad range of reaction conditions.

For the past seven years, the Ford Motor Company has been working on the development of catalytic exhaust treating systems designed to minimize the emission of certain vehicle exhaust gas constituents. In 1959, the development of a low-temperature, catalytic-converter system for the oxidation of exhaust gas hydrocarbons was described in a paper presented to the SAE. That system, which used vanadium pentoxide as the catalyst, has since been extensively developed in a program that included 250,000 miles of converter evaluation on vehicles. Many of the basic system requirements and problems covered in those tests are relevant in vehicle applications of a catalytic converter system with any type of catalyst. With the insertion of a carbon monoxide limit in the California Exhaust Standard, work on the low-temperature, catalytic converter system was discontinued since this system did not, and was not designed to, oxidize carbon monoxide.

This paper discusses the poisoning of a selective catalytic reduction (SCR) catalyst by trace levels of platinum originating from an upstream diesel oxidation catalyst (DOC). A diesel aftertreatment system consisting of a DOC, urea based SCR Catalyst and a DPF was aged and evaluated on a 6.4 liter diesel engine dynamometer. The SCR catalyst system consisted of an Fe-zeolite catalyst followed by a Cu-zeolite catalyst. After approximately 400 hours of engine operation at varied exhaust flow rates and temperatures, deactivation of the SCR catalyst was observed. A subsequent detailed investigation revealed that the Cu catalyst was not deactivated and the front half of the Fe-based catalyst showed severe deactivation. The deactivated portion of the catalyst showed high activity of NH3 conversion to NOx and N2O formation. The cause of the deactivation was identified to be the presence of trace Pt contamination.

Urea selective catalytic reduction (SCR) catalysts have the capability to deliver the high NOx conversion efficiencies required for future emission standards. However, the potential for the occasional over-temperature can lead to the irreversible deactivation of the SCR catalyst. On-board diagnostics (OBD) compliance requires monitoring of the SCR function to make sure it is operating properly. Initially, SCR catalyst performance metrics such as NOx conversion, NH3 oxidation, NH3 storage capacity, and BET surface area are within normal limits. However, these features degrade with high temperature aging. In this work, a laboratory flow reactor was utilized to determine the impact on these performance metrics as a function of aging condition. Upon the completion of a full time-at-temperature durability study, four performance criteria were established to help determine a likely SCR failure.

The high conversion efficiency required by the modern three-way catalyst (TWC) is dependent on oxygen storage material functionality and capacity. To successfully model a TWC, it is critical that the oxygen storage function in the catalyst be adequately represented. The original oxygen storage model (a simple “bucket” model) included in one of Ford's TWC models, SIMTWC, was developed for vehicle programs meeting LEV emission standards. Application of SIMTWC to test data from vehicles targeting more stringent emission standards, such as ULEV and PZEV, revealed limitations in the accuracy of the original bucket model. To address these limitations, an improved kinetic model of oxygen storage is being developed. This new model is more kinetically-detailed than the old model.

Regulatory authorities are actively revising and updating the rules for on board diagnostics of diesel powertrains. Diesel oxidation catalysts are among the parts that will have to be monitored. This paper discusses some of the issues related to the feasibility of monitoring these catalysts. We concentrate on the effect of real world noise factors on the ability to distinguish marginal from threshold catalysts and demonstrate that with current sensor and catalyst technology the separation between the two is poor.