This work aims to shed light on the use of two biochars, obtained from the pyrolysis at 550 °C of heavy-metal-contaminated Jatropha curcas L. roots, as heterogeneous catalysts for glycerol esterification using residual glycerine. To do this, glycerine from biodiesel production was purified. In a first step, H3PO4 or H2SO4 was used to remove non-glycerol organic matter. The glycerol-rich phase was then extracted with ethanol or propanol, which increased the glycerol content from 43.2% to up to 100%. Subsequently, the esterification of both purified glycerine and commercial USP glycerine was assayed with acetic acid (AA) or with acetic anhydride (AH) at 9:1 molar ratio to glycerol using Amberlyst-15 as catalyst. Different reaction times (from 1.5 to 3 h) and temperatures (100–115 °C when using AA and 80–135 °C when using AH) were assessed. Results revealed that the most suitable conditions were 80 °C and 1.5 h reaction time using AH, achieving 100% yield and selectivity towards triacetylglycerol (TAG) almost with both glycerines. Finally, the performance and reuse of the two heterogeneous biocatalysts was assessed. Under these conditions, one of the biocatalysts also achieved 100% TAG yield.