Preparation of highly active MCM-41 supported Ni_2P catalysts and its dibenzothiophene HDS performance

Highly active MCM-41 supported nickel phosphide catalysts for hydrodesulfurization （HDS） were synthesized by two different phosphorus sources, in which the surface of Ni2P catalysts were modified by air instead of being passivated by O2/N2 mixture. In addition, the catalysts need not be activated with flowing H2 （30 ml·min^-1） at 500℃ for 2 h prior to reaction as traditional method. X-ray diffraction （XRD）, X-ray photoelectro spectroscopy （XPS）, N2-adsorption specific surface area measurements and CO chemisorption were used to characterize the resulting catalysts. The effect of modification with air on the surface of the catalysts for HDS performance was investigated. Results showed that the surface modification with air can promote the formation of smaller Ni2P particles and more active Ni sites on surface of catalysts. At 3.0 MPa and 613 K, the dibenzothiophene （DBT） conversion of the catalysts modified with air was 98.7%, which was 7.1% higher than that of catalyst passivated by O2/N2 mixture. The higher activities of Ni2P（x）/M41-O catalysts can be attributed to the smaller Ni2P particles sizes and the increased hydrogen dissociation activity due to the surface modification.

Co-or Ni-modified Sn-MnO_(x) low-dimensional multi-oxides for high-efficient NH_(3)-SCR De-NO_(x):Performance optimization and reaction mechanism

NH_(3)-SCR performances were explored to the relationship between structure morphology and physio-chemical properties over low-dimensional ternary Mn-based catalysts prepared by one-step synthesis method.Due to its strong oxidation performance,Sn-MnO_(x) was prone to side reactions between NO,NH_(3)and O_(2),resulting in the generation of more NO_(2)and N_(2)O,here most of N_(2)O was driven from the non-selective oxidation of NH_(3),while a small part generated from the side reaction between NH_(3)and NO_(2).Co or Ni doping into Sn-MnO_(x) as solid solution components obviously stronged the electronic interaction for actively mobilization and weakened the oxidation performance for signally reducing the selective tendency of side reactions to N_(2)O.The optimal modification resulted in improving the surface area and enhancing the strong interaction between polyvalent cations in Co/Ni-Mn-SnO_(2)to provide more surface adsorbed oxygen,active sites of Mn^(3+) and Mn^(4+),high-content Sn^(4+) and plentiful Lewis-acidity for more active intermediates,which significantly broadened the activity window of Sn-MnOx,improved the N^(2) selectivity by inhibiting N_(2)O formation,and also contributed to an acceptable resistances to water and sulfur.At low reaction temperatures,the SCR reactions over three catalysts mainly obeyed the typical Elye-rideal(E-R)routs via the reactions of adsorbed L-NH_(x)(x=3,2,1)and B-NH_(4)^(+) with the gaseous NO to generate N_(2) but also N_(2)O by-products.Except for the above basic E-R reactions,as increasing the reaction temperature,the main adsorbed NO_(x)-species were bidentate nitrates that were also active in the Langmuir-Hinshelwood reactions with adsorbed L-NH_(x) species over Co/Ni modified Mn-SnO_(2) catalyst.