Abstract
Further understanding of the reaction in
which 2,3-butanediol is dehydrated over thorium oxide to methyl vinyl carbinol
and butadiene has been gained by measuring the adsorption on thoria of water,
methyl ethyl ketone and the above-mentioned diol, carbinol, and diene, at
temperatures up to 200 �C. In some instances satisfactory isotherms could not
be obtained because sufficient chemisorption occurred, followed by
polymerization or dehydration reactions, to reduce seriously the area of thoria
surface available for adsorption. There was evidence to suggest that water,
alone of the vapours concerned, was taken up in greater amount than could be
accounted for by adsorption. The bearing of this on the dehydration and its
relation to the structure of the catalyst is briefly discussed. A suggestion in
a previous paper(1) that water is the product which retards the catalytic
dehydration is confirmed.
At temperatures little above 50 �C, methyl
vinyl carbinol is dehydrated by thoria to butadiene, while methyl ethyl ketone
at room temperature undergoes self-condensation on thoria to yield a methyl
heptenone. Also at quite low temperatures dimerization of butadiene brings
about appreciable reduction of available surface. Some loss of activity on this
account must therefore be expected when thoria is used to dehydrate
2,3-butanediol, even though butadiene is adsorbed only weakly.
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