Separation of Azeotropic Dimethylcarbonate/Methanol Mixtures by Pervaporation: Sorption and Diffusion Behaviors in the Pure and Nano Silica Filled PDMS Membranes

Abstract

In this article, polydimethylsiloxane and hydrophobic nano-silica filled polydimethylsiloxane membranes were prepared and employed in dimethylcarbonate (DMC) removal from the DMC/methanol mixture via pervaporation. The sorption and diffusion behavior of the binary molecule were discussed separately to provide qualitative estimation of the PV performance in both membranes. Compared with the polydimethylsiloxane membrane, hydrophobic nano-silica filled polydimethylsiloxane membranes had a little lower sorption selectivity but higher diffusion selectivity. In both membranes, the sorption value was obtained by both experimentation and model prediction. The Flory-Huggins model was performed to predict the solvent uptakes and the sorption concentrations based on the experimental results. The sorption behavior of DMC was predictable, while the methanol solubility was a little higher than the experimental results. Moreover, the diffusion behavior was studied by Fick's law, the calculated diffusion coefficients of the permeates demonstrated a diffusion-coupling phenomenon, especially in hydrophobic nano-silica filled polydimethylsiloxane membranes. Methanol molecules diffused faster than DMC, suggesting the low diffusion selectivity. The PV performance was affected by both sorption and diffusion. Sorption was demonstrated to be a decisive factor in this pervaporation process.

Keywords:

• dimethylcarbonate/methanol separation
• pervaporation
• polydimethylsiloxane
• sorption diffusion

ACKNOWLEDGEMENTS

The authors greatly appreciate the financial support of the Major State Basic Research Program of China (2009CB623404), National Natural Science Foundation of China (20736003, 20906056), National High Technology Research and Development Program of China (2007AA06Z317, 2008EG111021), Foundation of the Ministry of Education of China (20070003130), Foundation of the State Key Laboratory of Chemical Engineering (SKL-ChE-08A01), and Postdoctor Science Foundation of China (023201073, 023201069).