Ig. Bajusz et al., METHANATION ON K-MODIFIED PT()SIO2 - THE IMPACT OF REACTION CONDITIONS ON THE EFFECTIVE ROLE OF THE PROMOTOR/, Catalysis letters, 48(3-4), 1997, pp. 151-157
This paper reports on the first study that the authors know of of the
effect of alkali promotion of Pt on methanation. Methanation was inves
tigated on a 4.5 wt% Pt/SiO2 catalyst promoted with different amounts
of K+ (K+/Pt = 0, 0.1, and 0.2) for two different temperature ranges (
503-552 K and 573-665 K). The methanation rate was 10-70% lower on the
promoted catalysts for reaction temperatures of 573 to 665 K. In this
temperature range, the relative decrease in rate upon promotion was a
function of K+ loading and did not vary with temperature, p(H2), p(CO
), or time-on-stream. In addition, there was no significant effect of
K+-promotion on activation energy (ca. 29 kcal/mol) or methanation rea
ction orders with respect to CO and H-2 (-0.1-0.0 and 0.4-0.6, respect
ively). However, there was a decrease in the number of methane-destine
d surface intermediates upon promotion as determined by steady-state i
sotopic transient kinetic analysis (SSITKA). All these observations le
ad to the conclusion that, in this higher reaction temperature range,
K+ acts mainly as a site-blocking agent for methanation on Pt and does
not change the reaction rate of the limiting step, probably hydrogena
tion. Between 503 and 552 K, the activation energy and reaction orders
with respect to (H)2 and CO were also not affected by K+. However, th
e catalyst with a K+/Pt ratio of 0.1 showed the highest methanation ac
tivity. In this lower temperature range and for all the catalysts, the
apparent activation energies were also found to be lower, 18 vs. 29 k
cal/mol, compared to those at higher temperatures. The reaction order
with respect to CO was higher (0.2-0.3) in comparison with what was ob
served in the higher temperature range(ca. -0.1-0.0). These results su
ggest, that, in the low temperature range and for low loadings of K+,
K+ affects the rate-determining step resulting in a rate increase grea
ter than the decrease due to the blockage effect. Thus, K+ serves as a
rate promoter at low reaction temperatures while its only effective f
unction is site blockage at higher temperatures.