Mechanical pulps are bleached by treatment with oxygen gas and alkali
in the presence of borohydrides. The combined treatment gives brightne
ss gains of 15-20 points, comparable with those achieved using stabili
zed alkaline 4% hydrogen peroxide. By contrast the reaction of oxygen
and alkali alone darkens high-yield pulps; and treatment with borohydr
ide in the absence of added oxygen bleaches only partially, to give ab
out half the brightness gained if oxygen is added. Evidence is present
ed that the bleaching occurs via the conversion of oxygen molecules (O
-2) to hydroperoxide ions (HOO-) by reaction of the oxygen with ionize
d phenolic groups in the lignin. The hydroperoxide ions are thus gener
ated in situ in the lignin where they bleach by reacting with coloured
lignin quinone and coniferaldehyde chromophores. Without the addition
of borohydride the lignin phenolic groups are irreversibly oxidized b
y oxygen to coloured products. The primary role of the borohydride is
to regenerate the phenolic groups and maintain an oxygen --> hydropero
xide[(O-2) --> (HOO-)] cycle. In principle other reducing agents could
be used as alternatives but in practice only sodium borohydrides and
substituted borohydrides have been found to be sufficiently stable to
the reaction conditions. In a secondary role, the borohydride also con
tributes to the bleaching by reducing radicals, organic peroxides and
carbonyl compounds present in the pulps.