Abstract: A process for preparing trioxane from methanol includes: step 1: subjecting a mixture of methanol and methylal to a reaction to obtain formaldehyde, and absorbing the formaldehyde with water to obtain a concentrated formaldehyde aqueous solution; step 2: subjecting the concentrated formaldehyde aqueous solution to cyclization to obtain a mixture containing trioxane, and passing the mixture through a trioxane concentration tower to obtain a crude trioxane product; step 3: converting a by-product and unreacted formaldehyde in the crude trioxane product into methanol, conducting dehydration through a membrane dehydration process, and subjecting a retentate to dealcoholization to obtain purified trioxane; and step 4: subjecting the remaining streams to reactive distillation to obtain a mixture of methanol and methylal at a top-and water at a bottom of the reactive distillation tower; returning the mixture of methanol and methylal to step 1; and returning or discharging the water.