Gilbert Blanchard

HC-SCR on Silver-Based Catalyst: From Synthetic Gas Bench to Real Use

ABSTRACT The challenge for decreasing the emissions of compression ignition engines now remains mainly on NOx control. If the Lean NOx Trap (LNT) and Selective Catalytic Reduction by Urea (Urea-SCR) are very efficient, their extra-cost and management are a major issue for the OEMs. In that context, the selective catalytic reduction by hydrocarbons (HC-SCR) appears to be an interesting alternative solution, with a more limited NOx conversion efficiency but an easier packaging (diesel fuel as a reductant) and a limited price (reasonable coating cost / no PGM). In the framework of the RedNOx project, a prototype catalyst made of 2% silver on Alumina coated on cordierite was manufactured and tested on a synthetic gas bench. In parallel, an exhaust implementation study has been led to ensure the most suited conditions for injection. Thanks to SGB and simulation results, adapted engine tests have been designed and performed. If the results on SGB are consistent with the literature with a maximum NOx conversion reaching about 70% and an operating range between 300 and 500°C, first engine results were very disappointing showing efficiencies lower than 15% for all the operating points. Three guidelines for improving these results were identified and studied: • The way the reductant is introduced in the exhaust, especially the discontinued HC delivery due to the injection pattern • The gas velocity: unusual small GHSV values for automotive applications are needed to ensure a good NOx conversion rate. • The nature of the used reductant. Diesel fuel (ULSD) compared with decane lowers the efficiency, but synthetic Diesel fuel (SD) and, moreover, ethanol, largely improve it, especially for high GHSV.

Analysis of the Coupling of HC–SCR by Ethanol and NH3–SCR on Real Engine Emissions

Selective catalytic reduction by ethanol on silver-based catalysts was proved to be very effective to abate the nitrogen oxides emitted at the exhaust of an automotive engine. Moreover, the selectivity to ammonia of this reaction may be exploited to further enhance the NOx reduction using a dedicated transition metal exchanged zeolite catalyst. This coupling between HC– and NH3–SCR is called Dual SCR. In order to control the silver-based catalyst efficiency via ethanol injection, a NOx sensor is located downstream of it, as usually done for urea–SCR on series vehicles. Furthermore, based on the cross-sensitivity of this NOx sensor, large amounts of ammonia were estimated that would help to reduce the remaining NOx on the zeolite based catalyst. However, when measured by FTIR technique, the concentrations of ammonia produced by the HC–SCR catalyst were surprisingly not as high as expected, while large amounts of acetaldehyde were detected and, in a lesser extent, formaldehyde and hydrogen cyanide. NOx were partly reduced over the iron-exchanged zeolite catalyst, improving the overall deNOx efficiency by up to 15 points, while acetaldehyde to formaldehyde ratio reversed and ammonia concentration remains unchanged. The cross-sensitivity of the NOx sensor was further investigated on synthetic gas bench. If its partial dependence on the ammonia concentration is rather well known, the influence of aldehydes and hydrogen cyanide in presence of ammonia had not yet been investigated. The NOx sensor’s signal remains unchanged whatever the aldehydes concentration and a strong sensitivity to the hydrogen cyanide was highlighted.