Investigation of co-effect of 12-tungstophosphoric heteropolyacid, nickel citrate and carbon-coated alumina in preparation of NiW catalysts for HDS, HYD and HDN reactions

Abstract

Effects of activated carbon in a carbon-coated alumina (CCA) support, active phase morphology and its composition of Ni6-PW12S/Cx/Al2O3 catalysts in hydrotreating of model compounds were studied. The catalysts were synthesized using 12-tungstophosphoric heteropolyacid, nickel citrate and CCA and characterized with multiple methods: N2 physisorption, X-ray powder diffraction, H2 temperature programmed reduction, temperature-programmed desorption of ammonia, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. The catalytic properties were determined using a fixed-bed microreactor in hydrotreating of dibenzothiophene, naphthalene and quinoline. It was found that with the increase of carbon content in the CCA up to 5wt.%, reducible reactivity, sulphidation degree, average length and stacking number of WS2 crystallites in the catalysts increased. Observed changes can be explained by weakening interaction between metal oxide species and carbon-coated support. Full promotion of the NiWS edges by nickel was achieved in the catalysts supported on the CCA with carbon content equal 0.3wt.% and more. Activities of the catalysts in dibenzothiophene hydrodesulphurization, naphthalene hydrogenation and quinoline hydrodenitrogenation were essentially depended on the carbon content in the CCA-support. Ni6-PW12S/C1/Al2O3 catalyst showed maximal conversions of the substrates in studied reactions. This result was achieved due to an optimal balance between turnover frequency value of the active sites and their content.