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22 2 Temperature-Programmed Techniques
22 2 Temperature-Programmed Techniques
and H2 O produced, while no uptake of H2 is detected. This suggests that the pre-
vailing reaction at low temperatures is the exchange of sulfur for oxygen:
At higher temperatures, the catalyst continues to exchange oxygen for sulfur until
all molybdenum is present as MoS2 :
Although Eqs. (2-8) to (2-11) explain the results satisfactorily, one needs to be
aware that TP studies detect only those reactions in the catalyst that are accompa-
nied by a net production or consumption of gases. Suppose, for instance, that Eq.
(2-11) is the result of two consecutive steps:
If Eq. (2-13) follows Eq. (2-12) instantaneously, the effect will not be noticeable in
the H2 signal [12]. Despite these limitations, it is concluded that TPS with mass
spectrometric detection is a highly useful technique for studying the sulfidation
of hydrotreating catalysts. We return to the sulfidation of molybdenum oxides in
Chapter 3 (photoemission), Chapter 4 (ion spectroscopy), and also in a case study
on hydrodesulfurization catalysts (Chapter 9).
2.4
Temperature-Programmed Reaction Spectroscopy