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A process for preparing 1,6-hexanediol from an aqueous carboxylic acid mixture comprising adipic acid, 6-hydroxy-caproic acid and small amounts of 1,4-cyclohexanediols, which aqueous carboxylic acid mixture is obtained as a by-product in the oxidation of cyclohexane to cyclohexanone/cyclohexanol using oxygen or oxygen-containing gases followed by water extraction, which process comprises esterifying the aqueous carboxylic acid mixture followed by catalytic hydrogenation,