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Catalyst poisoning from engine oil additives is a complicated process that depends in part on the pathway by which the oil is consumed in the engine. Engine studies were conducted to assess the relative impact of three major modes of oil consumption - through the PCV system, past the piston rings, and through the valve guides. Minimal phosphorus poisoning was observed with oil consumed through the PCV system and piston rings, whereas oil consumed through the intake valve guides demonstrated severe catalyst poisoning. The former produces effects characteristic of complete combustion of the ZDDP additive previously shown to produce relatively innocuous washcoat overlayers of porous zinc phosphate. In contrast, the latter produces effects characteristic of incomplete combustion (i.e., spray of oil additive into the exhaust and, most notably a washcoat pore-plugging effect accompanied by a marked decrease in washcoat surface area.

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.

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.

The relationship between engine oil formulations and catalyst performance was investigated by comparatively testing five engine oils. In addition to one baseline production oil with a calcium plus magnesium detergent system, the remaining four oils were specifically formulated with different additive combinations including: one worst case with no detergent and production level zinc dialkyldithiophosphate (ZDTP), one with calcium-only detergent and two best cases with zero phosphorus. Emissions performance, phosphorus loss from the engine oil, phosphorus-capture on the catalyst and engine wear were evaluated after accumulating 100,000 miles of taxi service in twenty vehicles. The intent of this comparative study was to identify relative trends.

A series of ceria and ceria-zirconia supported Pd model automotive catalysts were prepared and aged under air or redox conditions at 1050°C for 12 h. The supports were manufactured by different methods and represent a range of compositions. The samples were characterized before and after aging by BET, X-ray diffraction, mercury porosimetry, XPS, H2 temperature-programmed reduction, and oxygen storage capacity measurements. Oxygen storage measurements revealed that the behavior of the catalysts varied according to aging conditions and temperature of measurement. Pd/ceria-zirconia catalysts showed higher oxygen storage characteristics after 1050°C aging than Pd/ceria catalysts, and the phase purity of the ceria-zirconia was shown to positively affect the amount of oxygen storage. The initial rates of oxygen release from the model catalysts at 350°C were shown to depend on the preparation conditions of the supports.

Bench reactor experiments were carried out to investigate the effects of operating temperature, precious metal loading, space velocity, and air-fuel (A/F) ratio on the performance of palladium (Pd) catalysts under simulated natural gas vehicle (NGV) exhaust conditions. The performance of these catalysts under simulated gasoline vehicle (GV) conditions was also investigated. In the case of simulated NGV exhaust, where methane was used as the prototypical hydrocarbon (HC) species, peak three-way conversion was obtained under richer conditions than required with simulated GV exhaust (propane and propene HC species). Moreover, the hydrocarbon efficiency of the catalyst under simulated NGV exhaust conditions was more sensitive to both A/F ratio and perturbations in A/F ratio than the HC efficiency under GV exhaust conditions.

Regeneration characteristics of three catalyzed wall-flow monolith (WFH) diesel particulate filters (one commercial filter and two experimental filters designated GMR-Pt and GMR-Ag, respectively) were compared in dynamometer tests with a GM 4.3 L diesel engine, All three filters regenerated at temperatures below 540°C, the lowest exhaust temperature at which an uncatalyzed filter could be regenerated. Momentary throttling of the engine intake air increased both the rate and extent of the commercial trap regeneration, but had little affect on the experimental traps. The results of this study indicate that exhaust temperatures of 500°C or above are required for rapid regeneration of all three traps. Such temperatures are not readily attained with GM 4.3 L and 6.2 L vehicles. More active catalytic filters and additional modifications to the engine operation are required before catalyzed wall-flow monolith filters can be effectively employed on GM diesel engines.

Diesel soot samples, containing Cu, Pb, or mixed Mn-Cu additives, were generated in 4.3 and 5.7 L engines under idle and 65 km/h road-load conditions. The soot was collected on ceramic fiber filters, samples of which were subsequently transferred to a controlled atmosphere laboratory flow reactor for analysis of soot oxidation characteristics. Ignition temperatures and propagation speed of the combustion zone were measured by infrared pyrometry and photography, respectively, as a function of additive type, O2 concentration, and gas flow rate. Soot containing Cu additive showed the lowest ignition temperature in room air (ca 300 C). A mathematical analysis is presented which predicts the effects of O2 concentration and superficial velocity on ignition temperature. The model demonstrates that the most important heat transfer terms affecting the ignition temperature are those of convection and heat of reaction (as controlled by the rate of O2 supply).