Cu/ZnO-based catalysts are widely used for methanol production from CO/CO2/
H-2. In recent years there has been growing interest in methanol synthesis
from CO2/H-2. Cu/ ZnO catalysts are less active for methanol production in
CO2-rich feed gas, but the activity appears to be promoted by the addition
of Pd to the catalyst. This paper presents a brief chronological overview o
f kinetic results in these catalyst systems including the work done by the
author. Experiments at controlled levels of conversion, including microreac
tor studies, have provided an insight into the role of products in the kine
tics of methanol synthesis. In particular, it has been shown that the produ
ct water inhibits CO2 hydrogenation to methanol. Under these conditions, Pd
appears to promote the activity, but in fact it plays a role in counteract
ing the inhibition by water. This could possibly be explained by hydrogen s
pillover which moderates the [Cu(metal) + H2O=Cu-O(ads) + H-2] redox. The p
aper goes on to discuss the mechanistic effect of water on Cu/ZnO-catalyst
systems under CO2-rich and CO-rich atmospheres.