石油学会誌

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The catalytic activity of a Mo-X-As oxide system (X=Mg, Ca, Sr or Ba) in vapor phase oxidation of 1-butene has been investigated in connection with the composition and structure of the catalyst, and the reaction kinetics has also been studied. The reaction was made carried out 430-490°C with 12-22% 1-butene and 12-20% oxygen in nitrogen. X-ray and IR analyses were made for the purpose of identifying the structure of the catalyst.
The addition of As component to the Mo-X binary oxide system, which has a considerably high activity for the formation of butadiene, 2-butene and CO+CO₂, caused a decrease in yields of 2-butene and carbon oxides and An increase in butadiene selectivity. The highest activity for butadiene formation was obtained with the Mo-X-As oxide catalyst in which the atomic ratio of Mo:X:As was 1:1:1. A Mo-X-As oxide catalyst of larger atomic number of X, gave higher selectivity but lower yield in butadiene formation. The rate was of the first order in 1-butene and independent of oxygen, concerning all of the formations of butadiene, 2-butenes and carbon oxides.
It was clarified that the molybdate of alkaline earth metal X exists in both the binary and the ternary oxide catalysts, Mo-X and Mo-X-As, and have a high activity of isomerization and carbon oxide formation together with that of diene formation. However, the activity of isomerization and carbon oxide formation are suppressed by the coexistence of As component, in the cases of X=Ba and X=Mg, Ca, Sr respectively.

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A method of measuring heat of formation of 2-methylparaffin-urea adducts was investigated. It was made feasible in this study to measure heat of the adduct formation of nine different 2-methylparaffins ranging from C₁₃ to C₂₁ by using specially designed twin type conduction calorimeter under selected reaction conditions favourable for adduction. The heat of formation of 9 kinds of 2-methylparaffin-urea adducts obtained were in the range of 1.25 to 1.75kcal/mole urea and 13.1 to 27.3kcal/mole of 2-methylparaffin. The heat of formation per mole of 2-methylparaffin increased linearly with an increase of carbon number and the contribution of a methylene group to the heat of formation was found equal to that of n-paraffins. Relations between the heat of formation and the total carbon number of 2-methylparaffin and also between the heat of formation and the CH₂ number could be expressed by the following equation, respectively:
ΔH₂-MeP=-1.6₅n+7.9
ΔH₂-MeP=-1.6₅(m-1)
where n: total carbon number of 2-methylparaffins
m: CH₂ number of 2-methylparaffins

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