Phosphoric acid used for the production of phosphate fertilizers is synthesized by the reaction of phosphate rock and sulfuric acid. As the reaction is exothermic, yield of phosphoric acid is poor at elevated temperature. Therefore, enhancement in its yield requires the process temperature be maintained by releasing the vapor (80°C) containing HF and SiF4 through a vacuum cooler. However, these valuable resources; F and Si, which can be utilized for the manufacture of refrigerant and polysilicon, respectively, are being wasted in the treatment process. We performed lab-scale experiments to estimate the amount of recoverable H2SiF6, a by-product of phosphoric acid manufacturing process. The experimental results showed a decrease of fluorine concentration by 0.12wt% in the liquid phase. Preliminary estimation showed a possible recovery of 5,509 ton/yr of fluorine considering the scale of the fertilizer manufacturing plant. Furthermore, field-scale experiment showed that H2SiF6 could be enriched in liquid phase from 0.35wt% to 7.33wt% and the vapor flow-rate from vacuum cooler was estimated at 51,000 m 3 /hr. Anew, the efficiency of fluorine recovery in the pilot-scale experiment was found to be 76.74% and the production of H2SiF6 was estimated at 5,340 ton/yr.