Process intensification of heterogeneous dehydrochlorination of β-chlorohydrins by using n-propanol as co-extractant
The synthesis of terminal epoxides, which are vital components in pharmaceuticals and resins, often involves dehydrochlorination of β-chlorohydrins. Although intrinsic kinetics indicate that the dehydrochlorination reaction in the presence of sodium hydroxide could be very rapid, the practical implementation could always be hindered by long reaction time and low conversion rate. Extended contact between the product and the alkaline solution can lead to hydrolysis of the epoxy group, thus necessitating the process intensification to realize higher production efficiency and selectivity. Here, by characterizing thermodynamic equilibrium data and in-situ recording of the reaction that proceeded in a constant interphase reactor, the heterogeneous dehydrochlorination is demonstrated to occur primarily in the organic phase, and the overall reaction rate depends on the equilibrium concentration of sodium alkoxides. This finding, which is fundamentally different from the traditional view that chlorohydrin is first dissolved in the aqueous phase and then reacts with NaOH, leads us to use inert alcohols to assist in the extraction of NaOH. Based on this method, the reaction time can be reduced over 80 % both in batch and continuous reactors. Besides, the method is demonstrated to be effective in the dehydrochlorination of five different long-chain β-chlorohydrins.
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