The production of solketal fuel additive was studied from the reaction of glycerol and acetone in the presence of pressurized CO 2 as switchable catalyst. A design of experiments (DoE) was used to study the significance of temperature, initial pressure of CO 2 , glycerol/acetone molar ratio, and reaction time. The response variable was the glycerol conversion that was analyzed by GC-MS. Temperature, reaction time and initial pressure of CO 2 were statistically significant whereas the molar ratio of glycerol/acetone was not. The maximum conversion at the optimal conditions (118 • C, 42 bar and 5 h) was 61%. Reactions with glycerol doped with common contaminants present in the glycerin of biodiesel production was also carried out. Water has a drastic effect on the conversion, as well as the concomitant addition of water and NaCl. Reactions with a glycerin of biodiesel production, using NaOH or Ba(OH) 2 as catalyst of transesterification, gave 6 and 20% conversion, respectively.
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