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Nowdays, biodiesel is a one of renewable bio fuel which being developed. By increasing biodiesel production, will increase the formation of glycerol as a by-product of the reaction. So it takes some effort to convert the glycerol into another product in order to increase the economic value of glycerol. One of these is by converting glycerol into triacetin which can be used as a bio additive in fuel through the acetylation process. The important thing to do before converting glycerol is removing the impurities from the crude glycerol. This study aims to determine the effect of concentration and type of acid used in the glycerol purification process. The purification process were done by acidification, adsorption, filtration, distillation and evaporation. The acidification processes use H3PO4 (85%), H2SO4 (98%), HCl (37%) and the acid percentage is 0.5%, 1%, 2.5%, 5%, 7.5%, 10% (v/v). The purified glycerol were analyzed using GC (Gas Chromatography) to determine glycerol content, water content, density and viscosity and is converted to triacetin by the esterification reaction using Ni / Zeolite as a catalyst. The esterification products were analyzed by titration to determine the reaction conversion. From this study it can be concluded that the highest glycerol concentration was achieved in the addition of H3PO4 with a concentration of 5% (v /v) with glycerol content of 79.59%, density 1.277 g / ml, viscosity 266.48 cP, moisture content 3.261% and glycerol conversion 82.39%. And its application as a bio additives can increase the Octane Number of commercial gasoline by 6.5%.