PURPOSE: To recover the subject substances in the form of a valuable components such as phenol and to achieve the resource-saving effect, by carrying out vapor-phase catalytic reaction of phenol with methanol in the presence of a metal oxide to obtain the subject compounds, purifying the compounds and thermally decomposing the discharged high-boiling substance at a specific temperature.

CONSTITUTION: Phenol and methanol are subjected to vapor-phase catalytic reaction at 250-600°C in the presence of a metal oxide. The gaseous by-products, unreacted methanol, unreacted phenol, produced water and o-cresol and/or 2,6-xylenol are separated from the obtained reaction product. The high-boiling substances separated in the above separation process are decomposed by heating at ≥300°C, preferably about 320-350°C to recover phenol, o-cresol and 2,6-xylenol. The heat source for the above heating method is especially preferably an organic thermal medium and the thermal decomposition is carried out usually for 2-4hr.