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When performing catalyst modeling and parameter tuning it is desirable that the experimental data contain both transient and stationary points and can be generated over a short period of time. Here a method of creating such concentration transients for a full scale engine rig system is presented. The paper describes a valuable approach for changing the composition of engine exhaust gas going to a DOC (or potentially any other device) by conditioning the exhaust gas with an additional upstream DOC and/or SCR. By controlling the urea injection and the DOC bypass a wide range of exhaust compositions, not possible by only controlling the engine, could be achieved. This will improve the possibilities for parameter estimation for the modeling of the DOC.

The increasing severity in emission standards around the world has been accompanied by the development of more active, durable catalysts. With a view to investigating the effects of high thermal aging on the catalyst performance and structure, the relationships of washcoat composition, washcoat structure, and PGM location with respect to catalyst activity were clarified using a model gas test, as well as physical and chemical characterization methods. The influence of newly developed washcoat components and PGM location on catalyst performance are also demonstrated by engine bench tests. The results obtained in this study indicate the newly developed Pt/Rh catalyst techologies are appropriate for future applications in which the catalyst will be exposed to extremely high temperature and flowrates.

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.

H2S emissions from a three-way catalyst are suppressed by incorporating copper or manganese oxide into a section downstream of the three-way 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.

The implementations of the Tier 2 and LEVII emission levels require fast catalyst light-off and fast closed loop control through high-speed engine management. The paper describes the development of innovative catalyst designs. During the development thermal and mechanical boundary conditions were collected and component tests conducted on test rigs to identify the emission and durability performance. The products were evaluated on a Super Imposed Test Setup (SIT) where thermal and mechanical loads are applied to the test piece simultanously and results are compared to accelerated vehicle power train endurance runs. The newly developed light-off catalyst with Perforated Foil Technology (PE) showed superior emission light-off characteristic and robustness.

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.

A catalyst system, consisting of two different catalyst technologies within a single canister, was developed for MDV2 (Medium-Duty Vehicles, Class 2) to meet ULEV targets. The catalyst volume versus engine displacement is less than 50%. Three approaches taken: substrate study, PM loading study and new catalyst technology development are illustrated here. The most promising system features new catalyst technologies coated on high cell density substrates.

Many studies suggest that lean-NOx SCR proceeds via oxidation of NO to NO2 by oxygen, followed by the reaction of the NO2 with hydrocarbons. On catalysts that are not very effective in catalyzing the equilibration of NO+O2 and NO2, the rate of N2 formation is substantially higher when the input NOx is NO2 instead of NO. The apparent bifunctional mechanism in the SCR of NOx has prompted the use of mechanically mixed catalyst components, in which one component is used to accelerate the oxidation of NO to NO2, and another component catalyzes the reaction between NO2 and the hydrocarbon. Catalysts that previously were regarded as inactive for NOx reduction could therefore become efficient when mixed with an oxidation catalyst. Preconverting NO to NO2 opens the opportunity for a wider range of SCR catalysts and perhaps improves the durability of these catalysts. This paper describes the use of a non-thermal plasma as an efficient means for selective partial oxidation of NO to NO2.

Traditional approaches to pollution control have been to develop benign non-polluting processes or to abate emissions at the tailpipe or stack before emitting to the atmosphere. A new technology called PremAir®* Catalyst Systems takes a different approach and directly reduces ambient ground level ozone. This technology can be applied to both mobile and stationary applications. For automotive applications, the new system involves placing a catalytic coating on the car's radiator or air conditioner condenser. As air passes over the radiator or condenser, the catalyst converts the ozone into oxygen. Three Volvo vehicles with a catalyst coating on the radiator were tested on the road during the 1997 summer ozone season in southern California to assess performance. Studies were also conducted in Volvo's laboratory to determine the effect of the catalyst coating on the radiator's performance with regard to corrosion, heat transfer and pressure drop.

The objective of this effort was to develop an understanding of how different converter substrate cell structures impact tailpipe emissions and pressure drop from a total systems perspective. The cell structures studied were the following: The catalyst technologies utilized were a new technology palladium only catalyst in combination with a palladium/rhodium catalyst. A 4.0-liter, 1997 Jeep Cherokee with a modified calibration was chosen as the test platform for performing the FTP test. The experimental design focused on quantifying emissions performance as a function of converter volume for the different cell structures. The results from this study demonstrate that the 93 square cell/cm2 structure has superior performance versus the 62 square cell/cm2 structure and the 46 triangle cell/cm2 structure when the converter volumes were relatively small. However, as converter volume increases the emissions differences diminish.

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.

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.

Gasoline engine oils contain a variety of additives including phosphorous-based compounds, for maintaining their characteristics. During the life of the vehicle, oil is consumed via piston ring blowby or leakage from valve stem guides. Phosphorous compounds from the consumed oil end up being deposited on the three way conversion catalysts resulting in a degradation of the conversion efficiencies of all three pollutants, hydrocarbons, carbon monoxide and nitrogen oxides. To simulate this deterioration in performance, an accelerated aging cycle has been developed which replicates the effect of the interaction between the phosphorous species and the washcoat components. This paper describes the poison aging protocol and the effect of aging temperature, poison level and duration of aging. In this paper, we will we also discuss some of the catalyst deactivation mechanisms and methods to simulate them using dynamometer-mounted engines.

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.

The application of SCR deNOx aftertreatment was studied on two about 12 liter class heavy-duty diesel engines within a consortium project. Basically, the system consists of a dosage system for aqueous urea injection and a vanadia based SCR catalyst, without an upstream or downstream oxidation catalyst. The urea injection system for a DAF and a Renault V.I. (Véhicules Industriels) diesel engine was calibrated on the engine test bench taking into account dynamic effects of the catalyst. For both engine applications NOx reduction was 81% to 84% over the ESC and 72% over the ETC. CO emission increased up to 27%. PM emission is reduced by 4 to 23% and HC emission is reduced by more than 80%. These results are achieved with standard diesel fuel with about 350 ppm sulfur. The test engines and SCR deNOx systems were built into a DAF FT95 truck and a Renault V.I. Magnum truck.

A recently completed program was developed to evaluate ultra-low sulfur diesel fuels and passive diesel particle filters (DPF) in several different truck and bus fleets operating in Southern California. The primary test fuels, ECD and ECD-1, are produced by ARCO, a BP company, and have less than 15 ppm sulfur content. A test fleet comprised of heavy-duty trucks and buses were retrofitted with one of two types of catalyzed diesel particle filters, and operated for one year. As part of this program, a chemical characterization study was performed in the spring of 2001 to compare the exhaust emissions using the test fuels with and without aftertreatment. A detailed speciation of volatile organic hydrocarbons (VOC), polycyclic aromatic hydrocarbons (PAH), nitro-PAH, carbonyls, polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzo-p-furans (PCDF), inorganic ions, elements, PM10, and PM2.5 in diesel exhaust was performed for a select set of vehicles.

A program has been completed to evaluate ultra-low sulfur diesel fuels and passive diesel particulate filters (DPFs) in truck and bus fleets operating in southern California. The fuels, ECD and ECD-1, are produced by ARCO (a BP Company) and have less than 15 ppm sulfur content. Vehicles were retrofitted with two types of catalyzed DPFs, and operated on ultra-low sulfur diesel fuel for over one year. Exhaust emissions, fuel economy and operating cost data were collected for the test vehicles, and compared with baseline control vehicles. Regulated emissions are presented from two rounds of tests. The first round emissions tests were conducted shortly after the vehicles were retrofitted with the DPFs. The second round emissions tests were conducted following approximately one year of operation. Several of the vehicles retrofitted with DPFs accumulated well over 100,000 miles of operation between test rounds.

A study was performed in the spring of 2001 to chemically characterize exhaust emissions from trucks and buses fueled by various test fuels and operated with and without diesel particle filters. This study was part of a multi-year technology validation program designed to evaluate the emissions impact of ultra-low sulfur diesel fuels and passive diesel particle filters (DPF) in several different heavy-duty vehicle fleets operating in Southern California. The overall study of exhaust chemical composition included organic compounds, inorganic ions, individual elements, and particulate matter in various size-cuts. Detailed descriptions of the overall technology validation program and chemical speciation methodology have been provided in previous SAE publications (2002-01-0432 and 2002-01-0433).