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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.

A laboratory study was performed to assess the effects of sulfur poisoning and desulfation temperature on the NO conversion of a LNT+(Cu/SCR) in-situ system. Four LNT+(Cu/SCR) systems were aged for 4.5 hours without sulfur at 600, 700, 750, and 800°C using A/F ratio modulations to represent 23K miles of desulfations at different temperatures. NO conversion tests were performed on the LNT alone and on the LNT+SCR system using a 60 s lean/5 s rich cycle. The catalysts were then sulfur-poisoned at 400°C and desulfated four times and re-evaluated on the 60/5 tests. This test sequence was repeated 3 more times to represent 100K miles of desulfations. After simulating 23K miles of desulfations, the Cu-based SCR catalysts improved the NO conversion of the LNT at low temperatures (e.g., 300°C), although the benefit decreased as the desulfation temperature increased from 600°C to 800°C.

Engine and flow reactor experiments were conducted to determine the impact of biodiesel relative to ultra-low-sulfur diesel (ULSD) on inhibition of the selective catalytic reduction (SCR) reaction over an Fe-zeolite catalyst. Fe-zeolite SCR catalysts have the ability to adsorb and store unburned hydrocarbons (HC) at temperatures below 300°C. These stored HCs inhibit or block NOx-ammonia reaction sites at low temperatures. Although biodiesel is not a hydrocarbon, similar effects are anticipated for unburned biodiesel and its organic combustion products. Flow reactor experiments indicate that in the absence of exposure to HC or B100, NOx conversion begins at between 100° and 200°C. When exposure to unburned fuel occurs at higher temperatures (250°-400°C), the catalyst is able to adsorb a greater mass of biodiesel than of ULSD. Experiments show that when the catalyst is masked with ULSD, NOx conversion is inhibited until it is heated to 400°C.

Selective Catalytic Reduction (SCR) catalysts have been designed to reduce NOx with the assistance of an ammonia-based reductant. Diesel Particulate Filters (DPF) have been designed to trap and eventually oxidize particulate matter (PM). Combining the SCR function within the wall of a high porosity particulate filter substrate has the potential to reduce the overall complexity of the aftertreatment system while maintaining the required NOx and PM performance. The concept, termed Selective Catalytic Reduction Filter (SCRF) was studied using a synthetic gas bench to determine the NOx conversion robustness from soot, coke, and hydrocarbon deposition. Soot deposition, coke derived from propylene exposure, and coke derived from diesel fuel exposure negatively affected the NOx conversion. The type of soot and/or coke responsible for the inhibited NOx conversion did not contribute to the SCRF backpressure.

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.

A laboratory study was performed to assess the contributions of platinum and rhodium to the emissions performance of a lean NOx trap. Samples of a barium-only formulation were obtained with either 0.84 g/L of platinum, 0.51 g/L of rhodium, or 1.0 g/L of platinum and rhodium in ratios of 1/0/1 or 5/0/1. 60 s lean/5 s rich tests were performed on fresh samples and samples that were aged on high temperature durability cycles. The results indicate that platinum is necessary for the NOx storage performance of the trap at low temperatures (e.g., 250°C), whereas rhodium is needed for the NOx reduction capability and consequently the purgability of the trap at low temperatures. As a result, the bimetallic Pt/Rh samples provided the best overall NOx conversion at low temperatures fresh and after aging.

The effects of PGM zoning and washcoat staging have been investigated as a means to lower the cost and simultaneously improve the performance of a lean NOx trap system. It is shown that reverse PGM zoning can be used to reduce the cost of the LNT while essentially maintaining the NOx performance of a similarly-sized trap with a uniformly high PGM loading. In addition, the effective temperature window of the trap can be expanded by staging different NOx trap formulations that are optimized for different temperature ranges. Alternatively, LNT washcoat staging can be used to improve the hydrocarbon conversion of the trap while maintaining good NOx performance. Laboratory data and vehicle data are presented for several NOx trap system combinations that demonstrate the improved performance that can be obtained from a combination of reverse PGM zoning and washcoat staging.

Lean NOx Traps are used to treat the NOx emissions from lean-burn engines by storing the NOx under lean conditions and reducing the NOx during periodic rich excursions. However, sulfur poisons the adsorption sites of the traps. The sulfur can be removed from the NOx trap by operating rich at high temperatures for several minutes. This results in the release of some SO2 but also large quantities of H2S, which is a source of customer dissatisfaction that must be reduced or eliminated. This paper describes the use of a nickel-containing catalyst and air/fuel control to maximize the release of SO2 and minimize the emissions of H2S during the desulfation of a lean NOx trap. We present laboratory and vehicle data with a nickel-containing catalyst located downstream of a lean NOx trap during desulfations of the trap. The nickel effectively reduced the emissions of H2S during the desulfation while improving the robustness to fluctuations in the air/fuel control.

Desulfation characteristics of several model and fully-formulated monolithic lean NOx trap materials were studied in a laboratory flow reactor employing a chemical ionization mass spectrometer. For all samples, desulfation at elevated temperatures under reducing conditions resulted in appearance of sulfur dioxide (SO2) followed by carbonyl sulfide (COS) and hydrogen sulfide (H2S). The data appear consistent with a desulfation mechanism involving elimination of SO2 from stored sulfates under reducing conditions, followed by reaction of the SO2 with CO and H2 to produce COS and H2S, respectively. Based on these observations, several cyclic and multistage desulfation strategies were devised which greatly decreased H2S emissions while achieving relatively rapid and complete sulfur removal.

A laboratory aging study was performed on samples of a lean NOx trap with platinum group metal (PGM) loadings of 0.53, 1.06, 2.12, and 3.18 g/liter. The LNT samples were aged at inlet temperatures of 650°C, 750°C, 800°C, and 850°C behind samples of a three-way catalyst that were aged on a pulse-flame combustion reactor with a Ford-proprietary durability schedule representing 80,000 km of customer use. For all aging temperatures, higher PGM loadings were beneficial for low temperature NOx performance, attributable to an increase in the oxidation of NO to NO2. Conversely, lower PGM loadings were beneficial for high temperature NOx performance after aging at 650°C and 750°C, as higher loadings promoted the decomposition of the nitrates during lean operation and thereby decreased the NOx storage capability at high temperatures. Also, higher PGM loadings increased the OSC of the trap and thereby increased the purge requirements.

This paper summarizes results from a study on the effects of aging temperature and A/F ratio on the NOx storage capacity of a lean NOx trap. When aged at stoichiometry at 700°C, the NOx storage capacity of the NOx trap dropped considerably during the first 200 hours of aging and then at a much slower rate beyond 200 hours. The NOx storage capacity dropped more rapidly as the aging temperature increased, with the drop in capacity particularly evident between 900°C and 1000°C. The drop in NOx capacity was significantly larger for samples aged with part-time lean operation and/or part-time rich operation than for samples aged continuously at stoichiometry. The detrimental effects of lean and rich operation increased as the temperature increased. A Pt/Al2O3 model catalyst was exposed to reducing conditions at temperatures ranging from 670°C to 1041°C and then to oxidizing conditions over the same temperature range, and in-situ XRD was used to investigate Pt particle coarsening.

This paper summarizes results from a large study on the release of NOx from a lean NOx trap during rich purges. Under certain purge conditions, some NOx trap formulations have the propensity to release some of the NOx stored during previous lean operation without reducing it. This purge NOx release was examined for different NOx trap formulations. The purge NOx release was evaluated for one of the formulations as a function of several variables, including the aging condition of the trap, the trap temperature, the trap volume, the purge A/F ratio, the purge flow rate, and the amount of NOx stored. The effect of hot lean pretreatments on the purge NOx release was studied. In addition, the effect of the rhodium level on the purge NOx release was examined. Mechanisms for the NOx release are proposed that are consistent with the observed data. The results indicate that the purge NOx release is very low for thermally aged traps and is primarily a concern for fresh or stabilized traps.

A study was performed on a lean NOx trap in which the loading of a ceria-containing mixed oxide in the washcoat was varied. After a mild stabilization of the traps, the time required to purge the NOx trap generally increased with increasing amount of mixed oxide. The purge NOx release also increased with increasing mixed oxide level but was greatly diminished after thermal aging. The sulfur tolerance of the NOx trap improved as the mixed oxide content was increased from 0% to 37%. The sample with 0% mixed oxide was more difficult to desulfate than the other samples due to poor water-gas-shift capability. After thermal aging, the NOx reduction efficiency on a 60 second lean/5 second rich cycle was highest for the samples with 0% to 37% mixed oxide at evaluation temperatures of 400°C to 500°C.

This paper summarizes results from a large study on the desulfation characteristics of lean NOx traps. Degreened and thermally aged NOx trap formulations were poisoned with SO2 multiple times in a flow reactor. The effect of desulfation time and temperature on the recovery of NOx trapping efficiency was evaluated after the poisonings. The relative effectiveness of the reducing agents (CO and H2) used during the desulfation was evaluated for one of the formulations. The results indicate that the high temperatures required for desulfation (e.g., 700°C and above) result in thermal degradation of NOx traps that had been degreened at a lower temperature (e.g., 600°C), and therefore desulfation studies should be performed with traps that have already been exposed to the desulfation temperatures or higher prior to the poisoning.