In the search for active catalysts for the conversion of refractory sulfur
compounds in diesel fuel, the activity, the role of the support, and the na
ture of the active sites on Pt/ASA catalysts in deep HDS reactions were stu
died and compared to Pt/gamma-Al2O3 and Pt/XVUSY (stabilised Y zeolite). Pt
/ASA appears to be much more active than Pt/gamma-Al2O3 but is initially le
ss active than Pt/XVUSY. The latter however, showed strong deactivation aft
er short reaction times. It is concluded that an appropriate tuning of the
support acidity is crucial for this reaction. In contrast to the activity,
the H2S sensitivity of the tested Pt based catalysts is hardly influenced b
y acidity of the support. Adsorption of H2S on these sulfur vacancies leads
to strong competitive adsorption with the reacting sulfur compound. It is
proposed that the stabilisation of small platinum clusters in the presence
of H2S is an important effect of acidic supports. In addition, the strength
and nature of the acidic sites on the support may affect the Pt-S bond str
ength of the active sites on small platinum particles. It is concluded that
no sulfur-free platinum metal sites are present under the applied reaction
conditions. It is therefore proposed that the conversion of 4-E,6-MDBT ove
r Pt/ASA proceeds over sulfur vacancies on small platinum particles. The cr
eation of sulfur vacancies on these small platinum particles may be related
to their electron-deficient character on acidic supports. (C) 1999 Elsevie
r Science B.V. All rights reserved.