High pressure cell for edge jumping X-ray absorption spectroscopy : Applications to industrial liquid sulfidation of hydrotreatment catalysts

C. Lesage (1, 2) , E. Devers (1) , C. Legens (1) , G. Fernandes (1) , O. Roudenko (2) , V. Briois (2)

1 IFPEN - IFP Energies nouvelles
2 SSOLEIL - Synchrotron SOLEIL

A new analytical cell to perform liquid sulfidation of HDS catalysts in industrial conditions was developed. It enables the alternate recording of time-resolved Mo and Co K edges X-ray Absorption spectra of bimetallic catalysts under high pressure (30 bar) and temperature (350°C) during the same reaction. Thanks to this cell, a comparative study of the species formed upon gas (1 bar, 15% H 2 S/H 2) and liquid sulfidation (30 bar, H 2 /gas oil/4% DMDS) of a CoMoP/Al 2 O 3 HDS catalyst was carried out, together with a discussion on the evolution of the concentration profiles upon activation. Different Mo and Co-based chemical species are involved during gas and liquid sulfidation. On one hand, in industrial liquid sulfidation, polymolybdate species are transformed into depolymerized oxides, then into an oxysulfide, a MoS x species and finally into MoS 2. On the other hand, gas sulfidation skips the depolymerization process because of the immediate supply of H 2 S at the beginning of the process and proceeds under a stepwise transformation of oxide into oxysulfide, itself into MoS 3 species and finally into MoS 2. Cobalt species under gas sulfidation goes through a CoS 2 intermediate whereas in liquid sulfidation, it is a 4-fold coordinated Co oxide species. Irrespective to the activation route, mixture of Co 9 S 8 and CoMoS is obtained at advanced sulfidation stage (T> 200°C). Graphical Abstract Quick XAS in situ cell Raman Probe H 2 Gas oil + DMDS 350 C 30 bar Synchrotron radiation Co K edge Mo K edge DMDS decomposition CH 4 H 2 S 232 C 284 C 2 Highlights  A high pressure cell has been developed to study the liquid sulfidation of HDS catalyst by X-ray Absorption Spectroscopy  Co and Mo local orders are studied alternatively during the same reaction  The sulfidation mechanism depends on the activation process  The sulfidation of Co and Mo in liquid phase mainly occurs when DMDS is decomposed into H 2 S between 225°C and 350°C. Gas sulfidation starts at room temperature and is completed at 400°C

Mots clés: Quick-XAS; Liquid sulfidation; high pressure; Analytical reactor; Glassy carbon; Gas sulfidation; CoMoP HDS catalyst

Domaines: Chimie; Catalyse

C. Lesage, E. Devers, C. Legens, G. Fernandes, O. Roudenko, et al.. High pressure cell for edge jumping X-ray absorption spectroscopy : Applications to industrial liquid sulfidation of hydrotreatment catalysts. Catalysis Today, 2019, 336, pp.63-73. ⟨10.1016/j.cattod.2019.01.081⟩. ⟨hal-02299215⟩