The present invention provides a process for preparing 1,6-hexanediol from
a carboxylic acid mixture which comprises adipic acid, 6-hydroxycaproic
acid and small amounts of 1,4-cyclohexanediols and is obtained as a
by-product in the oxidation of cyclohexane to cyclohexanone/cyclohexanol
with oxygen or oxygen-containing gases and by water extraction of the
reaction mixture, by esterification of the acids and hydrogenation, in
which a) the mono- and dicarboxylic acids present in the aqueous
dicarboxylic acid mixture are reacted with a low molecular weight alcohol
to give the corresponding carboxylic esters, b) the resulting
esterification mixture is freed of excess alcohol and low boilers in a
first distillation stage, c) a separation of the bottom product is
carried out in a second distillation stage into an ester fraction
substantially free of 1,4-cyclohexanediols and a fraction comprising at
least the majority of the 1,4-cyclohexanediols, d) the ester fraction
substantially free of 1,4-cyclohexanediols is catalytically hydrogenated
and e) 1,6-hexanediol is obtained in a purifying distillation stage from
the hydrogenation effluent while removing an alcohol-low boiler mixture
in a manner known per se, wherein alcohol is removed by a membrane system
from the mixtures, obtained after the esterification in stage b) and/or
after the hydrogenation in stage e), of alcohols and low boilers and
recycled into the esterification.