In the process of CO2 hydrogenation, the major reaction is the
methanol formation, while reverse water-gas-shift reaction
composes of the side reactions [23]:
Methanol formation
CO2 þ3H2 ¼ CH3OH þ H2O; DH298 K¼ 90:70 kJ=mol
Reverse water-gas-shift reaction
CO2 þH2 ¼ CO þ H2O; DH298 K ¼ 41:19 kJ=mol
The methanol formation is an exothermal reaction with
reduction of reaction molecule number. Thus, the decrease of
temperature and the rise of pressure should favor for the reaction
from thermodynamical analysis. However, considering the reaction
rate and the chemically inert nature of CO2, the enhancement
of reaction temperature (>513 K) facilitates CO2 activation and
then the methanol formation. The reverse water-gas shift reaction
causes extra consumption of hydrogen and a reduction of
methanol formation. Meanwhile, the large amount of water form
as a by-product, from both methanol synthesis and the reverse
water-gas shift side reaction, also had an inhibitory effect on the
active metal during the reaction [24,25], leading to the deactivation
of the catalyst. Besides, other hydrogenated products such as
higher alcohols and hydrocarbons are usually associated with
methanol formation. Therefore, methanol synthesis from CO2
hydrogenation requires a more selective catalyst to avoid the
formation of undesired by-products.