RESUMO
The acid and redox sites of the MnCo catalysts are simultaneously fine-tuned by the addition of V. A dual-function catalyst, designated as V0.5Mn5Co5, has been constructed for the synergistic removal of NOx and volatile organic compounds under coke-oven flue gas conditions, which exhibits > 95 % NOx conversion and > 80 % N2 selectivity at 180-300 °C. Meanwhile, it removes 70 % of ethylene at 240 °C. Besides it has excellent sulfur and water resistance. The characterization results indicate that this acid-redox dual sites modulation strategy appropriately weakens the oxidation capacity of the catalysts while increasing the surface acidity of the catalysts. The catalyst mainly performs SCR reaction through the E-R mechanism, and N2O is generated through the transition dehydrogenation of NH3 and NSCR reaction. Ethylene is first adsorbed on the catalyst surface then oxidized to form carbonate species, and finally decomposed to CO2. Ethylene oxidation follows the MvK mechanism. There is a competitive adsorption between NH3 and C2H4, and a mutual inhibition between the SCR reaction and the ethylene oxidation reaction. V0.5Mn5Co5 exhibits excellent synergistic removal of NOx and VOCs in coke oven flue gas compared with commercial VWTi catalysts, which indicates great promise for industrial application.
RESUMO
Alkali metal poisoning has been an intricate and unsolved issue confining the catalytic activity of NH3-SCR catalysts up to now. Herein, the effect of NaCl and KCl on catalytic activity of CrMn catalyst for NH3-SCR of NOx was systematically investigated to clarify the alkali metal poisoning by combined experiments and theoretical calculations. It unveiled that NaCl/KCl could deactivate CrMn catalyst due to the decrease in specific surface area, electron transfer (Cr5++Mn3+âCr3++Mn4+), redox ability and oxygen vacancy and NH3/NO adsorption. In addition, NaCl cut off E-R mechanism reactions by inactivating surface Brønsted/Lewis acid sites. DFT calculations revealed that (1) Na and K could weaken MnO bond, (2) competitive adsorption between Cl and NH3 was a main reason weakening Lewis acid, (3) Cl adsorption was also a major cause diminishing Brønsted acid and oxygen vacancy, (4) Both Na and K seriously impeded NO adsorption/activation, (5) NaCl/KCl increased the reaction heat of H2O desorption (rate-determining step) in E-R mechanism reactions and KCl elevated its energy barrier in L-H mechanism reactions. Thus, this study provides the deep understanding of alkali metal poisoning and a well strategy to synthesize NH3-SCR catalysts with outstanding alkali metal resistance.
RESUMO
The facet-dependent reactivity of CrMn catalysts was still unclear, hindering the further enhancement of their low-temperature SCR performance. Herein, the facet-dependent reactivity of CrMn1.5O4 catalyst for NH3-SCR of NOx was innovatively illustrated by numerous characterizations and density functional theory (DFT) calculations. Exposed (100) facet of CrMn1.5O4 catalyst exhibited best low-temperature SCR activity with ≥90 % NO conversion within 148-296 °C and 2.86 × 10-3 mol/(g·s) reaction rate within 160-240 °C. The characterizations revealed that (100) facet could induce the increase of BET specific area, electron transfer, concentration of Mn4+ and Oα, surface acidity, redox ability, NH3 and NOx adsorption/activation capacity. Subsequently, DFT calculations demonstrated that (100) facet exhibited the strongest affinity for NH3 and NO due to its unique 3O3c-Mn5c-2O4c bond and abundant charges transfer near the active adsorption sites, and Brønsted acid and oxygen vacancies were most easily formed on (100) facet. Furthermore, H2O formation as the rate determining step easily occurred on (100) facet. Eventually, we successfully improved the low-temperature SCR activity of CrMn1.5O4 catalyst by further tailoring highly active (100) facet from 0.754 to 0.865. This work provides the deeper understanding of facet-dependent reactivity and a good strategy to improve the catalytic activity of the catalysts.
