Investigation of the mechanism of n-butane oxidation on vanadium phosphorus oxide catalysts: evidence from isotopic labeling studies.

The selective oxidation of n-butane to maleic acid catalyzed by vanadium phosphates (VPO) is one of the most complex partial oxidation reactions used in industry today. Numerous reaction mechanisms have been proposed in the literature, many of which have butenes, butadiene, and furan as reaction intermediates. We have developed an experimental protocol to study the mechanism of this reaction in which (13)C-isotopically labeled n-butane is flowed over a catalyst bed and the reaction products are analyzed using (13)C NMR spectroscopy. This protocol approximates the conditions found in an industrial reactor without requiring an exorbitant amount of isotopically labeled material. When [1,4-(13)C]n-butane reacted on VPO catalysts to produce maleic acid and butadiene, the isotopic labels were observed in both the 1,4 and 2,3 positions of butadiene and maleic acid. The ratio of label scrambling was typically 1:20 for the 2,3:1,4 positions in maleic acid. For butadiene, the ratio of label scrambling was consistently much higher, at 2:3 for the 2,3:1,4 positions. Because of the discrepancy in the amount of label scrambling between maleic acid and butadiene, butadiene is unlikely to be the primary reaction intermediate for the conversion of n-butane to maleic anhydride under typical industrial conditions. Ethylene was always observed as a side product for n-butane oxidation on VPO catalysts. Fully (13)C-labeled butane produced about 5-13 times as much isotopically labeled ethylene as did [1,4-(13)C]butane, indicating that ethylene was produced mainly from the two methylene carbons of n-butane. When the reaction was run under conditions which minimize total oxidation products such as CO and CO(2), the amounts of ethylene and carbon oxides produced from fully (13)C-labeled butane were almost equal. This strongly suggests that the total oxidation of n-butane on VPO catalysts involves the oxidation and abstraction of the two methyl groups of n-butane, and the two methylene groups of n-butane form ethylene. An organometallic mechanism is proposed to explain these results.