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Cumune Hydroperoxide Process for Phenol and Acetone

The oxidation of Cumune is the most widely used method for acetone
production as mentioned before. By the Cumune oxidation reaction, Cumune
Hydroperoxide is obtained;

Production of Cumune Hydroperoxide uses an uncatalyzed liquid phase

oxidation process operated at about 105115 C and 67 bars where the conversion is
limited to about 25%. [1] More recently, higher reactor temperatures around 140 C
are achieved with a conversion of 30 % for Hock process. [2]
The elementary reaction steps have been proposed by Bhattacharya [3] such
By applying steady state assumption for the radicals, following rate equations are
obtained for the Cumune process,
Table 1.1 Arrhenius parameters for the rate constants [3]

Another study on reaction rate was done by Hattori et al. [4], for which the
effective rate constant K is,

Dehydrogenation of Isopropyl Alcohol

The reaction mechanism for dehydrogenation of Isopropyl Alcohol is given
by R.M. Rioux and M.A. Vannice over copper catalysts as [5],

The final rate expression was found as;

Another study was made again by R.M. Rioux and M.A. Vannice with
carbon-supported Pt catalyst for the process [6]. The reaction kinetics for that
mechanism is summarized as;
where is an active site and Ki represents an adsorption equilibrium constant. The
site balances and substitutions are made, results in;

1. Guerra M.K., Process Economic Program Report No. 22C Phenol

Supplement, SRI International, California, March 1991.
2. Suresh A.K., Sharma M.M., Shridhar T., Engineering aspects of industrial
liquid-phase air oxidation of hydrocarbons, Ind. Eng. Chem. Res. 39, 3958
3997, 2000.
3. Bhattacharya A., Kinetic modeling of liquid phase autoxidation of Cumune.
Chemical Engineering Journal 137, 308319, 2008.
4. Hattori K., Tanaka Y., Suzuki H., Ikawa T., Kubota H., Kinetics of liquid
Phase oxidation of Cumune in bubble column, J. Chem. Eng. Japan 3, 7278,
5. Rioux R.M., Vannice M.A., Hydrogenation/dehydrogenation reactions:
isopropanol dehydrogenation over copper catalysts. Journal of Catalysis 216,
362376, 2003.
6. Rioux R.M., Vannice M.A., Dehydrogenation of isopropyl alcohol on carbon-
supported Pt and CuPt catalysts. Journal of Catalysis 233, 147165, 2005.