Abstract
Abstract The isomerization of butenes has been studied over four kinds of ThO2 catalysts which differ in starting materials or preparative procedures. The selective ThO2 catalysts for the formation of 1-olefin in the dehydration of 2-alkanol, which were prepared from nitrate and oxalate, were active and gave high cis/trans ratios in the isomerization of 1-butene, whereas the non-selective ThO2 catalyst, which was prepared from chloride, was completely inactive. The isomerization reaction was poisoned by both CO2 and NH3. The activity was enhanced by the treatment with hydrogen, but was reduced by the treatment with oxygen, the selectivity being unchanged with both treatments. The coisomerization of cis-2-butene and cis-2-butene-d8 showed that the isomerization involved an intramolecular hydrogen transfer, and a large isotope effect, 6.0, for the formation of 1-butene and a small isotope effect, 1.5, for the formation of trans-2-butene were observed. With these results, the nature of active sites on thorium oxide, and the reaction mechanism were discussed.
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