Biodiesel was synthesized by industrial palmitic acid and methanol, using solid acid Zr(SO4)2/TiO2 as catalyst. Effects of mass fraction of Zr (SO4)2 in the catalyst, calcination temperature and time of catalyst, mass ratio of methanol to industrial palmitic acid, catalyst dosage and reaction time on the esterification rate were investigated. The catalyst and ester product were analysed by GC-MS, FTIR and DTG/DTA methods. Assessment experiments show that the catalytic activity of the supported Zr(SO4)2/TiO2 catalyst was higher than the unsupported Zr(SO4)2 catalyst. The esterification rate can reach at 98.9% under the following conditions: calcination temperature of catalyst 400 ℃, loading amount of Zr(SO4)2(based on total mass of catalyst) 65%, mass ratio of methanol to industrial palmitic acid 12/25, mass fraction of Zr (SO4)2/SiO2 in palmitic acid 8.0% and reaction time 5 h. Analysis result of GC-MS showed that the ester product were mainly hexadecanoic acid methyl ester and 10-octadecenoic acid methyl ester.