To highlight the deactivation mechanisms encountered by minerals impurities from biodiesel, the effects caused by Na, P or (Na+P) additions were studied over a model Cu-FER catalyst. Na, P or (Na+P) were added by wet-impregnation in water in a wide concentration range up to 2 wt-%. The catalytic behaviors were evaluated by NH3/NO oxidation and standard/fast NH3-SCR reactions. In addition, a combination of several characterization techniques (ICP-AES, N2 adsorption/desorption, XRD, NH3-TPD, NO adsorption monitored by FTIR and H2-TPR) was applied to provide useful information regarding the deactivation mechanism caused by the minerals addition. Sodium and phosphorus interacted differently with the Cu-FER catalyst. Na addition induced a loss of Brønsted acid sites and a back-exchange of Cu 2+ with Na + , with formation of external CuO species, thus favoring the oxidation of NO and NH3. After phosphorus addition, the exchanged Cu 2+ species remained moderately affected, but direct interactions with copper were evidenced which were primarily responsible for catalyst deactivation toward the oxidation reactions. After equimolar addition of phosphorus and sodium, both Na and P effects were observed. For the NH3-SCR process, the ammonia adsorption ability, which depends on both acidity and copper units, appeared the main key parameter driving the catalytic activity at low temperature (T ≤ 250 °C). Phosphorus appeared to be the major responsible for catalyst deactivation after (Na+P) co-poisoning.

Abstract:The effect of the sodium addition mode was investigated on model Cu/FER selective catalytic reduction (SCR) catalysts with two copper loadings (2.8 wt. % and 6.1 wt. %) in order to compare samples with or without over-exchanged copper. Na was added by wet-impregnation using two solvents: water or ethanol. Catalysts were evaluated in Standard and Fast-SCR conditions, as well as in NO and NH 3 oxidation. They were characterized by H 2 -TPR, NO and NH 3 adsorption monitored by FT-IR. As expected, whatever the copper loading, ammonia adsorption capacity was decreased by Na additions. Interestingly, characterizations also showed that Na impregnation in water favors the migration of the Cu-exchanged species, leading to the formation of CuO extra-framework compounds. Consequently, for both copper loadings, Na impregnation in water led to a stronger catalyst deactivation than impregnation in ethanol. Finally, the NO x conversion at low temperature (250 • C) appeared mainly affected by the loss in NH 3 adsorption capacity whereas the deNO x deactivation at high temperature (500 • C) was rather governed by the decrease in the exchanged copper ratio, which also induced a partial inhibition of NO and NH 3 oxidation behaviors.