5-Trioxane is industrially produced from aqueous formaldehyde solutions through reaction distillation catalyzed by sulfuric acid. Optimizing industrial process of the synthesis and developing new catalysts have attracted extensive attention. It is necessary to establish a vapor-liquid equilibrium model of the reaction system and reveal the multiple functions that the catalyst may play in the synthesis of 1
3
5-trioxane. For this reason
experimental data for the vapor-liquid equilibrium of (formaldehyde + 1
3
5-trioxane + H
2
SO
4
+ water) system are measured. The extended UNIFAC model is used for correlating the vapor-liquid equilibrium data
and the model parameters are determined
whereby systematic calculation is made. The results show that the sulfuric acid c
atalyst has triple functions in the reaction distillation process. The above results are of great significance for optimizing the production process of 1
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