Glycerol Conversion to Lactic Acid with Unsupported Copper Salts and Bulk Cupric Oxide in Aqueous Alkali Media.

Glycerol conversion to lactic acid (LA) was investigated in aqueous alkali over eight unsupported copper compounds (CuBr2, CuBr, CuCl2, CuCl, CuF2, Cu(NO3)2,CuO, and Cu2O) for studying the effects of anion and valence. Powder X-ray diffraction and scanning electron microscopy measurements indicated that these copper compounds were reduced to metallic copper with different morphologies. Divalent copper compounds exhibited much better performances than the corresponding univalent species, ascribed to their greater reduction heat and higher local reaction temperature. Divalent copper species activity, ionic radius, and the reported reduction potential decreased in the same order: bromide > chloride > floride ≫ nitrate. With increasing reaction temperature, catalyst amount, NaOH concentration and reaction time, glycerol conversion, and LA selectivity increased (due to by-product conversions to LA). Kinetic studies indicated that glycerol disappearance rate was first-order with respect to its concentration. CuBr2 had greater activation energy and therefore exhibited better performance than CuO when reaction temperature was greater than 155 °C. At 185 °C, CuBr2 reached 95.7% lactic acid yield and 98.65% glycerol conversion.