Date of Award

12-2008

Degree Type

Thesis

Degree Name

Master of Science

Major

Mechanical Engineering

Major Professor

Ke Nguyen

Committee Members

Bruce G. Bunting, Todd J. Toops, J. Roger Parsons

Abstract

Selective catalytic reduction (SCR) of NOx with urea/NH3 is a leading candidate to the impending more stringent emissions regulations for diesel engines. Currently, there is no consensus on the durability and the deactivation mechanisms associated with zeolite-based SCR catalysts, nor is there an established protocol for rapidly aging zeolite-based SCR catalysts that replicates the catalyst deactivation associated with field service. A 517 cc single-cylinder, naturally-aspirated direct injection (NA/DI) diesel engine is used to perform accelerated thermal aging on Fe-zeolite SCR catalysts. The engine is fitted with an exhaust aftertreatment system consisting of a DOC, a SCR catalyst and a DPF. Accelerated aging protocol established for the SCR catalyst utilizes high temperature exhaust gases during the active regeneration of the DPF. Accelerated aging is carried out at exhaust gas temperatures of 650, 750 and 850°C at the SCR inlet and at a gas hourly space velocity (GHSV) of approximately 40,000 h-1. The engine is maintained at 1500 rpm and supplemental fuel is injected upstream of the DOC to alter the temperature of the aftertreatment system. The aged Fe-zeolite SCR catalysts are evaluated for NOx performance in a bench-flow reactor and characterized by multiple surface characterization techniques for materials changes.

The NOx performance of the front sections of the engine-aged catalysts is severely degraded. BET surface area measurements of the engine-aged catalyst indicate a severe reduction of catalyst surface area in the front sections of the catalysts aged at 750 and 850°C. However, the catalyst aged at 650°C has a catalyst surface area similar to that of a fresh catalyst; thereby ruling out reduction of catalyst surface area as the sole cause of the catalyst deactivation seen in the front sections of the engine-aged catalysts. The similar shape of the NOx conversion profiles observed with these catalyst sections even at different aging temperatures indicates some type of catalyst poisoning; however, the cause of catalyst degradation in these catalyst sections is not identified in this investigation.

There is a good relationship between the NOx performance and catalyst aging temperature for the rear sections of the engine-aged catalysts – NOx performance decreases with increasing aging temperature. XRD patterns and NO oxidation experiments reveal evidence of zeolite dealumination in the engine-aged catalysts. BET surface area measurements show that catalyst surface area decreases with increasing aging temperature, which further supports the suggestion of zeolite dealumination as the cause of catalyst deactivation in the rear sections of the engine-aged catalysts.

A comparison between the engine-aged and field-aged catalysts is conducted to assess the validity of the implemented accelerated thermal aging protocol in replicating the aging conditions observed in the field-aged catalyst. Bench-flow reactor evaluation is used to determine the NOx performance of the engine-aged and field-aged catalysts, and in depth surface studies are used to determine the deactivation mechanisms associated with each type of catalyst aging. SEM micrographs and BET surface area measurements of the aged catalysts show that the deactivation mechanism associated with catalyst aging is primarily physical damage to the zeolite washcoat for both the field-aged and engine-aged catalysts. Furthermore, X-ray diffraction and NO oxidation experiments identify zeolite dealumination as the underlying cause of the washcoat degradation. Finally, BFR evaluation shows that the NOx performance of the catalyst aged at 750°C for approximately 50 hours compares very well to that of the field-aged catalyst with a service life of 3 years. It is concluded that accelerated thermal aging on the engine bench is successful in bringing about similar catalyst changes to those seen with the field-aged catalyst.

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