OXIDATION OF PROPYLENE BY MEANS OF SNO2-MOO3 CATALYSTS .2. HYDROGEN-DEUTERIUM EXCHANGE BETWEEN PROPYLENE AND WATER

被引:32
作者
BUITEN, J
机构
关键词
D O I
10.1016/0021-9517(69)90446-1
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
It has been found that in the presence of SnO2 covered with MoO3 and at a temperature of 360 °C, propylene and D2O rapidly exchange hydrogen against deuterium. The distribution of the deuterium over the propylene molecules proved to be approximately binomial. One of the hydrogen atoms in the propylene molecule participated only slightly in the exchange; this must have been the atom bonded to the central carbon atom. Infrared absorption measurements revealed that deuterium appears preferably in the methylene group (as was confirmed by a proton magnetic resonance measurement), and for the greater part in the cis position with respect to the methyl group. An explanation of the exchange which accounts for the availability of five hydrogen atoms in the propylene molecule for the exchange while being compatible with the abovementioned preference, is represented by a reversible reaction between propylene and acid surface hydroxyl groups yielding surfacebonded isopropyl groups (or isopropoxy groups, if the surface oxygen atoms are considered to be included). In our view, these groups also constitute the intermediate species in the oxidation of propylene to acetone and acetic acid. MoO3 gave a low exchange rate, while SnO2 proved to hold an intermediate position between MoO3 and SnO2 MoO3. The same applies to the rate of oxidation of propylene. With SnO2 MoO3, isopropyl alcohol was very rapidly dehydrated to propylene at 370 °C; also during oxidation of propylene over this catalyst, the off gas showed the low equilibrium concentration of isopropyl alcohol-even at a very high space velocity. In the dehydration of isopropyl alcohol, MoO3 showed a fairly high activity. The catalytic action of SnO2 on isopropyl alcohol, however, was directed almost exclusively towards the oxidative dehydrogenation to acetone. This is one of the arguments to be raised against the view that the above-mentioned isopropyl (isopropoxy) group is also an intermediate in the dehydration of isopropyl alcohol. All experiments were done in the presence of air and water vapor. © 1969.
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页码:373 / &
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