INTENSIFICATION OF THE CYCLOHEXANE LIQUID PHASE OXIDATION PROCESS

Abstract

Liquid-phase oxidation of cyclohexane to cyclohexanol and cyclohexanone was studied in the absence of solvents under an air pressure of 0.5-5 MPa, in the temperature range 115-150 °C, catalyzed by N-hydroxyphthalimide (N-HPI). It was established for the first time that the use of N-HPI as a catalyst in place of the conventionally used metal salts of variable valence allowed a 2-3-fold increase in the conversion of the initial hydrocarbon and selectivity from 70-75 to 90%. The combined use of N-HPI with cobalt(II) acetate results in an additional increase in the conversion of cyclohexane by 30-40%, the selectivity of cyclohexanol and cyclohexanone formation to 94-97%, which seems to be due to the synergistic effect between the two components of the catalyst. The mechanism of catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone is discussed. It has been suggested that N-HPI plays a dual role in the oxidation of cyclohexane: it catalyzes the conversion of cyclohexane to cyclohexanol and cyclohexanone and, on the other hand, promotes the conversion of cyclohexanol to cyclohexanone, thereby substantially reducing the formation of adipic acid and its esters, by-products of the reaction, and increases selectivity of oxidation. This also explains the unusually high (1.3-1.5 : 1) ketone: alcohol ratio in the oxidation products of cyclohexane in the presence of N-HPI. The high selectivity of the formation of the desired products, the conversion of cyclohexane, the moderate temperature, the available catalyst, suggest that this method of oxidizing cyclohexane to cyclohexanol and cyclohexanone may be of interest for further practical use.