Semibatch wet air oxidation (WAO) experiments were conducted on aqueous sol
utions of linear alkylbenzene sulfonates (LAS) at various pH's, to determin
e whether acidic and/or. basic pH affects the rate and extent of the degrad
ation and desulfonation of LAS and its refractory sulfonated intermediates.
It was found that acidic pH increases the removal of TOC, COD, and LAS, as
well as increasing desulfonation. Acid catalysis of the desulfonation and
aromatic ring cleavage reactions is thought to be responsible. Conversely,
the WAO of LAS and its intermediates was less effective at high pH. It is h
ypothesised that this is due to radical scavengers and the dominance of the
superoxide radical in the alkaline environment. Desulfonation might also b
e autocatalyzed in unmodified LAS WAO reactions by reaction products, as ac
id is a product of LAS WAO reactions. Experiments were conducted at 240 deg
reesC at neutral (unmodified) and alkaline pH's to compare WAO in the prese
nce and "absence" of this acid. Desulfonation occurred to the same extent a
t both pH's, indicating that it was not significantly autocatalyzed by the
acid generated during WAO.