Eighteen binary metal oxides consisting of TiO2–MmOn, ZnO–MmOn and Al2O3–MmOn (MmOn: metal oxide) were prepared by the usual co-precipitation method, their acid amounts and strengths being determined by n-butylamine titration using various acid-base indicators. The acid strengths of fourteen of the tested binary oxides of molar ratio 1 : 1 were found to be remarkably higher than those of the component single oxides. High acid strengths were as follows: H0≤−8.2 for TiO2–SiO2, H0≤−5.6 for TiO2–Al2O3 and Al2O3–ZrO2 and H0≤−3 for TiO2–CdO, TiO2–SnO2 and ZnO–SiO2. The acid amounts of sixteen binary oxides were larger than those of the component oxides. The effect of the composition of binary oxides on acidity was examined for TiO2–Al2O3, ZnO–Al2O3 and Al2O3–ZrO2. The acidity maxima appearing for TiO2–Al2O3 and ZnO–Al2O3 were found to be of molar ratio\simeq9:1 and for Al2O3–ZrO2\simeq3:2. A fairly good correlation has been demonstrated between the observed highest acid strengths and the average electronegativities of metal ions of binary oxides.
The catalytic activity and the sintering property of iron oxide catalysts with and without potassium additives have been studied. The potassium oxide acts as a promoter and is effective under given conditions in increasing the activity of the catalyst from four to ten times. The effects of the promoter can be classified thus: (1) Structural promoter: The increase in the apparent bulk density and the shrinkage of the catalyst tablet upon calcination during the preparation of the catalyst are prevented by potassium additives. The differences in the specific surface area and in the pore volume of the catalyst between with and without potassium promoter are slight. These effects on iron oxide appear to be caused largely by the formation of K2Fe22O34. (2) Synergetic promoter: The potassium promoter changes the apparent energy of activation of the dehydrogenation reaction from 28 to 43 kcal/mol. The increase in the catalytic activity is due to the increase in the pre-exponential factor. The increase in the factor can be explained in terms of the higher concentration of the active center produced by the interaction of the potassium promoter with iron oxide. (3) Selectivity promoter: The formation of benzene by a side reaction is retarded by potassium additives.
The exchange reactions of oxygen atoms between oxygen and carbon dioxide on metal oxides were studied by the static batch method in the temperature range from
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