Combined in situ analysis of Ni2P/MCM-41 under hydrodesulfurization conditions - Simultaneous observation of QXAFS and FTIR -

Supported Ni2P catalysts are efficient for the hydrodesulfurization (HDS) of liquid fuels. In situ extended x-ray absorption fine-structure (EXAFS) analysis of the Ni2P catalyst under realistic HDS conditions revealed the formation of Ni-S bonds in the catalyst system. In order to identify the origin of these bonds, a quick x-ray absorption fine structure (QXAFS) system was set up, which enabled measurement of one Ni K-edge EXAFS spectrum in 10 sec. In addition, a Fourier transform infrared (FTIR) unit was incorporated to the QXAFS system, which allowed simultaneous measurements of XAFS and IR spectra on the same sample. The catalyst (12.2 wt% Ni2P/MCM-41) was activated under H-2 at 723 K to regenerate an active phosphide phase. After activation, a reaction gas mixture (thiophene/He/H-2 = 0.1 / 1.9 / 98, at a total flow rate of 102 ml/min) was introduced. Under the reaction conditions, there was a change in the pre-edge area of XANES, which corresponded to the evolution of Ni-S bonds in EXAFS. The simultaneous measurements of XANES and IR revealed that this Ni-S could be attributed to the formation of a Ni phosphosulfide species rather than bonding between Ni and S of adsorbed thiophene. The combined in situ techniques proved to be an effective tool for the characterization of working catalysts.