Middle distillate hydrotreatment zeolite catalysts containing Pt/Pd or Ni



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A study on middle distillate hydrotreatment zeolite catalysts containing Pt/Pd and/or Ni was performed. The effect of the addition of the corresponding CoMo, CoMoPd, CoMoPtPd and CoMoNi in PdNiPt-zeolite, Pt-zeolite, Ni-zeolite, and PdPt-zeolite was studied. The catalysts were characterized physically and chemically by methods and techniques such as Brunauer-Emmett-Teller (BET), Barret-Joyner-Hallenda (BJH), and neutron activation analysis. The structures of the Ni and Pt containing zeolite were studied by X-ray Photoelectron Spectroscopy (XPS). An experimental apparatus was constructed to investigate the activity of the experimental catalysts. The catalysts activity measured in terms of conversion of dibenzothiophene (DBT), substituted dibenzothiophenes (sDBT) and phenanthrene as well as molar-averaged conversion was evaluated in a continuous flow Robinson Mahoney reactor with stationary basket in the hydrodesulfurization and hydrogenation of heavy gas oil which contains sulphur refractory compounds such as 4- methyldibenzotiophene (4-MDBT) and 4,6- dimethyldibenzothiophene (4,6-DMDBT). DBT, 4-MDBT, 3-MDBT, 1-EDBT, 3-EDBT, 4,6-DMDBT, 3,6-DMDBT, 2,8- DMDBT and 4-methylnaphtho[2,1-b]thiophene were selected to calculate the molaraveraged conversion. The conversions of the sulfur containing compounds and phenanthrene were determined as a function of the operating variables: space time (W/Fo DBT), temperature, H2/HC mol ratio and pressure. The Conversions of DBT and 4,6-DMDBT into their reaction products such as Biphenyl (BPH), Cyclohexylbenzene (CHB), Bicyclohexyl (BCH) and 3,4-Dimethylbiyphenyl (3,4-DMBPH) were determined only as a function of space time in the interval of 4000-6000 kgcath/kmol. The results of this work showed that Pt-HY and PdPt-HY are good noble metals catalysts for the hydrodesulfurization of heavy gas oil. Moreover, this study showed that CoMoPd/Pt-HY and CoMoNi/PdPt-HY catalysts are good candidates for deep HDS and hydrogenation of heavy gas oil. It was found that the conversions of sulfur compounds were higher than the conversions provided by the conventional CoMo/Al2O3 catalyst. Also higher hydrogenation of phenanthrene was observed. Deactivation of the catalysts was not observed during the operation. Finally, the study not only contributed to define the technical bases for the preparation of the noble metal catalysts for hydrodesulfurization of heavy gas oil at pilot scale, but also provided technical information for developing the kinetic modeling of the hydrodesulfurization of heavy gas oil with the noble metal catalysts.