Abstract
Cyclohexane oxidation was studied using the GifIV, the GoAggII, the GoAggIII and the GoChAgg systems. The GifIV system gives a conversion of cyclohexane of 40%, with a concentration of one + ol of 0.120 M, but shows low selectivity and needs large quantities of metallic zinc. The GoAggII system produces a 0.143 M solution of one + ol with 100% selectivity but is too slow for any industrial use. The GoAggIII system allows accumulation of the oxidation products. A 0.370 M solution of one + ol can be produced in 180 min of reaction time, but large quantities of catalyst are needed and the selectivity of one + ol is only 80%. Addition of HCl during the accumulations allows obtaining a 0.267 M solution of one + ol with 100% selectivity in 60 min of reaction time, compared to a 0.3 M solution of one + ol with only 80% selectivity in 40 min in the industrial oxidation process. On the other hand, the catalyst forms iron (hydr)oxide particles during the reaction and the pyridine has to be substituted by a cheaper and a less toxic solvent. The GoChAgg system is less active and deactivates rapidly during the accumulations. The best result obtained so far is a 0.120 M solution of one + ol with 100% selectivity in 120 min of reaction time. Substituition of pyridine by tert-butanol reduces the activity of the GoAggIII and the GoChAgg systems. Precipitation of the catalyst and rapid deactivation are observed. Up to now we could only prepare a 0.040 M solution of one + ol. Even so, we hope to find a solvent/buffer system which avoids the deactivation of the catalyst while maintaining the high activity and selectivity of the process.
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Schuchardt, U., Carvalho, W.A., Pereira, R., Spinacé, E.V. (1993). Cyclohexane Oxidation: Can Gif Chemistry Substitute for the Classical Process ?. In: Barton, D.H.R., Martell, A.E., Sawyer, D.T. (eds) The Activation of Dioxygen and Homogeneous Catalytic Oxidation. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3000-8_18
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