9

th
Green Chemistry Conference. AN INTERNATIONAL EVENT Alcal de Henares - Spain, 2011

Removal of 1,4-dioxane by advanced oxidation processes
Daphne Hermosilla, Luis Cortijo, Noem Merayo, Carlos Negro and ngeles Blanco
Cellulose and Paper Research Group, Department of Chemical Engineering, Complutense University of Madrid, 28040, Madrid,
Spain - dhermosilla@quim.ucm.es
Keywords: 1,4-dioxane, Fenton process, ozonation.


Introduction
1,4-dioxane is an important water contaminant
classified as a toxic, hazardous and priority
pollutant, within the Class 2B by the US
Environmental Protection Agency and the Inter-
national Agency for Research on Cancer. It is
widely used as a degreasing agent, as a component
of paint and varnish removers, and as wetting and
dispersion agent in the textile industry; and it is also
a by-product of many industrial processes
1-3
.
1,4-dioxane is resistant to biodegradation and
difficult to remove by conventional water treatment
methods. Distillation is considered the most
effective physical technology to remove this
chemical, whereas carbon adsorption and air
stripping have been reported as inadequate
2
.
Moreover, oxidation with chlorine or permanganate
is ineffective.
Advanced oxidation processes (AOPs) are water
treatment processes based in the formation of
hydroxyl radicals in sufficient quantity to effect
chemical transformation of contaminants
4
, and they
have shown success treating some bio-recalcitrant
compounds
5,6
. Therefore, AOPs may represent a
good alternative treatment for these compounds;
although limited research has been reported to date
regarding this possibility.
As a consequence, this research aimed to study
the viability and the optimization of the 1,4-dioxane
oxidation treatment by both Fenton and ozonation
methods. Optimization was carried out to achieve
the highest reduction of the chemical oxygen
demand (COD) and biodegradability enhancement
in synthetic and industrial wastewater.
Material and methods
Synthetic water was prepared adding 247.8mgL
-1

of 1,4-dioxane trying to simulate real concentration
in industrial wastewater. 1,4-dioxane was supplied
by Sigma-Aldrich (Highland, USA); and solutions
were prepared in ultrapure water and kept in the
dark. Industrial wastewater was supplied by a
factory after its biological treatment plant.
Fenton oxidation experiments were carried out in
batch mode inside 500mL-beakers containing
250mL of wastewater. Temperature was set at 25C.
An appropriate amount of FeSO
4
was dissolved in
the solution, and the required amount of H
2
O
2
was
subsequently added to start the Fenton reaction. The
experiments were carried out until the total
consumption of the added H
2
O
2
was achieved. pH
(2.8-7.2), and the addition of H
2
O
2
([H
2
O
2
]/DQO=
1.0625-4.250) and FeSO
4
([H
2
O
2
]/[Fe
2+
]=1-10) were
optimized.
Ozonation experiments were conducted in a
glass jacketed cylindrical bubble reactor (height=1
m, diameter=5 cm) fed with a continuous flow of
ozone gas (4.0 Lmin
1
) produced from ordinary
grade air passed through polycarbonate filters, and
subsequently enriched with oxygen. The system
consisted of an ozone generator (Model 6020,
Rilize, Gijn, Spain), a flow controller (Model F-
201AV, Bronkhorst, Ruurlo, The Netherlands),
and an ozone on-line analyzer (Model 964C, BMT
Messtechnik GMBH, Berlin, Germany). The reactor
was fed with 1000 mL wastewater containing the
1,4-dioxane solution. pH and ozone consumption
were optimized. Additional experiments were
carried out adding H
2
O
2
.
Results
COD was reduced up to 60% and 80% by Fenton
and ozonation treatments, respectively, under
optimized reaction conditions. Moreover, the
presence of this compound was totally removed,
being oxidized to more biodegradable compounds,
such as ethylene glycol and volatile fatty acids. As
consequence, the biodegradability of the wastewater
was significantly improved.
Fenton process was mainly affected by the
concentration of H
2
O
2
and pH (Figure 1), although
the effect of pH was not as relevant as it has resulted
in the Fenton treatment of other compounds
7-8
. In
fact, COD removal decreased only a 10% when the
process was performed at pH=7.2 instead than at the
optimized value of pH=2.8 (Figure 1). The modif-
ication of ion ferrous concentration resulted in less
than an 8% COD reduction.
The optimum pH value resulted above 9 in the
ozone process, achieving a COD removal higher
Hermosilla et al.

than 80% (Figure 2). Other authors have not
reported optimized pH conditions, which may have
induced to reject the ozonation alternative as a
viable treatment
1-9-10
. The addition of H
2
O
2
in the
ozone process improved the kinetics of COD
removal along the whole tested pH range.

%
C
O
D
r
e
m
o
v
a
l
[H
2
O
2
]/COD
pH
%
C
O
D
r
e
m
o
v
a
l
[H
2
O
2
]/COD
pH

Fig. 1 Response surface for optimizing Fenton treatment.

O
3,
gL
-1
0.0 0.5 1.0 1.5 2.0 2.5
%

C
O
D

r
e
m
o
v
a
l
0
25
50
75
100
pH 7
pH 8.5
pH 9
pH 9.5
pH 10

Fig. 2 COD removal in the treatment of ozone of synthetic
wastewater containing 1,4 dioxane.
Ozone experiments with industrial wastewater
were carried out at pH=9. Furthermore this
wastewater contained carbonates that buffered the
pH value, so pH control was not needed. There was
no reduction of efficiency associated to the presence
of carbonate. Under these conditions, a COD
removal of 85% was achieved in a wastewater
containing 1,4-dioxane and several other inorganic
compounds. The ozone process combined with H
2
O
2

achieved an even higher reduction of the COD
(97%).
The Fenton process applied to industrial
wastewater samples containing 1,4-dioxane
achieved a 63% COD reduction at the following
reaction conditions: [H
2
O
2
]/COD=4.25, [Fe
2+
]=1.5,
and pH=2.8.



Conclusions
Fenton process and ozonation showed good
enough results to be considered an alternative for
removing 1,4-dioxane from either synthetic, or real
industrial wastewaters.
Fenton process allowed achieving a 60%
reduction of the COD; even an acceptable COD
removal close to 50% may result at low Fe
2+

concentration (10) and neutral pH value.
Ozonation was able to reduce the COD up to
85% at pH=9; but its application is not acceptable at
pH<7.
The addition of H
2
O
2
improved significantly the
ozonation treatment (12-15% COD removal) of
industrial wastewater containing 1,4 dioxane.
Acknowledgements
This research was carried out in the framework
of the projects AGUA Y ENERGA (CTM2008-
06886-C02-01), funded by the Ministry of Science
& Innovation of Spain; AQUAFIT4USE
(211534), funded by the EU; and PROLIPAPEL
(P2009/AMB-1480) funded by Community of
Madrid.
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