All commercial catalysts for methanol synthesis and for the water–gas shift reaction in the low temperature region contain
zinc oxide in addition to the main active component, copper. The varied benefits of zinc oxide are analysed here. The formation
of zincian malachite and other copper/zinc hydroxy carbonates is essential in the production of small, stable copper crystallites
in the final catalyst. Further, the regular distribution of copper crystallites on the zinc oxide phase ensures long catalyst
life. Zinc oxide also increases catalyst life in the water–gas shift process by absorbing sulphur poisons but it is not effective
against chloride poisons. In methanol synthesis, zinc oxide (as a base) removes acidic sites on the alumina phase which would
otherwise convert methanol to dimethyl ether. Although bulk reduction of zinc oxide to metallic zinc does not take place,
reduction to copper–zinc alloy (brass) can occur, sometimes as a surface phase only. A new interpretation of conflicting measurements
of adsorbed oxygen on the copper surfaces of methanol synthesis catalysts is based on the formation of Cu–O–Zn sites, in addition
to oxygen adsorbed on copper alone. The possible role of zinc oxide as well as copper in the mechanisms of methanol synthesis
is still the subject of controversy. It is proposed that, only under conditions of deficiency of adsorbed hydrogen on the
copper phase, hydrogen dissociation on zinc oxide, followed by hydrogen spillover to copper, is significant.
zinc oxide - copper catalysts - methanol synthesis - water–gas shift reaction - malachite - aurichalcite - georgeite - sulphur poisoning - chloride poisoning - dimethyl ether - brass - hydrogen spillover
This revised version was published online in June 2006 with corrections to the Cover Date.