The anaerobic digestion of glycerol derived from biodiesel manufacturing, in which COD was found to be 1010 g/kg, was studied in batch laboratory-scale reactors at mesophilic temperature using granular and non-granular sludge. Due to the high KOH concentration of this by-product, H(3)PO(4) was added to recover this alkaline catalyst as agricultural fertilizer (potassium phosphates). Although it would not be economically viable, a volume of glycerol was distilled and utilised as reference substrate. The anaerobic revalorisation of glycerol using granular sludge achieved a biodegradability of around 100%, while the methane yield coefficient was 0.306 m(3) CH(4)/kg acidified glycerol. Anaerobic digestion could be a good option for revalorising this available, impure and low priced by-product derived from the surplus of biodiesel companies. The organic loading rate studied was 0.21-0.38 g COD/g VSS d, although an inhibition phenomenon was observed at the highest load.