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Multistage Treatment System for Textile Wastewater Combining

Electrocoagulation, Solar Photo-Fenton and Biological Oxidation


Processes
1,2

Uv8

D.R. Manenti , P.A. Soares , A.N. Mdenes , R. Bergamasco , S.M. Palcio , V.J.P. Vilar . (1) Programa de PsGraduao em Engenharia Qumica da Universidade Estadual de Maring, Av. Colombo 5790, Maring-PR, Brasil,
diegomanenti@hotmail.com. (2) LSRE Laboratory of Separation and Reaction Engineering Associate Laboratory
LSRE/LCM, Faculdade de Engenharia, Universidade do Porto (FEUP), R. Dr. Roberto Frias, Porto, Portugal. (3)
Programa de Ps-Graduao em Engenharia Qumica da Universidade Estadual do Oeste do Paran, R. da Faculdade
645, Toledo-PR, Brasil.

A multistage treatment system was designed for the treatment of a


real textile wastewater combining: a) a electrocoagulation (EC)
process, promoting a partial reduction of some organic
compounds, nitrogen and inorganic salts, avoiding the formation
of iron-dyes and iron-inorganic complexes, which reduces
significantly the photo-Fenton reaction rate; b) with a solar photoFenton oxidation process, enhancing the EC-treated effluent
biodegradability, mainly through dyes degradation into more
simple and biodegradable compounds; c) and an activated sludge
biological oxidation process, under aerobic conditions, in order to
achieve a final effluent in agreement with the discharge limits
imposed by the Portuguese regulations (COD < 150 mg O2/L).
Introduction
Textile industry generates large quantities of
highly colored effluents resulting from the fabrics
dyeing/printing
process.
Generally,
these
wastewaters present different recalcitrant dyes, with
a complex organic structure, high alkalinity,
detergents and high inorganic salts concentration.
Considering the complexity of the textile
wastewaters, the treatment strategy relies on the
adoption of a multistage treatment process, such
as, coagulation/flocculation, electrocoagulation,
advanced oxidation processes (AOPs), biological
processes, etc. to achieve a final wastewater with
quality enough to be discharged into receiving
water bodies, at comfortable costs, without the
generation of further wastes
Among the solar driven AOPs, the solar photoFenton oxidation process has been considered an
effective process to improve the biodegradability of
textile wastewater [1]. However, the iron-dyes and
iron-inorganic salts complexes, or even the iron
precipitation with phosphates, reduces significantly
the reaction rate [2]. In this context, the EC process
can be applied for partial reduction of organic
compounds, nitrogen and inorganic salts as a pretreatment of textile wastewater [3]. Thus, this work
proposes a multistage treatment system for real
textile wastewater, combining electrocoagulation,
solar photo-Fenton and aerated biological oxidation
processes.
Materials and Methods
The wastewater was collected before undergoing
any type of treatment, at an industrial textile plant
located in Vizela, north of Portugal.
The electrocoagulation lab-scale prototype
consists of a cylindrical glass container (1.5 L), a
magnetic stirrer and a pair of iron electrodes with
eight plates (5 cm x 11 cm x 0.15 cm) with 0.5 cm
gap between them. With a current density of 149 A
m-2, the initial solution pH of 7 and during 5 min of
electrolysis time [4], the electrodes were dipped into

the cylindrical glass containing 900 mL of the raw


textile wastewater. The active electrode surface
area was 0.035 m2. The electrodes were operated
in a mono polar mode and were connected to
terminals of directed current power supply
(Velleman, model DIG PS3020) that provided the
stabilized currents and voltages ranging from 0 to
20 A, and from 0 to 30 V, respectively. After 5 min
of electrolysis, the floating and precipitated
materials were withdrawn, the clarified effluent
sample was collected for the analytical
determinations, and the pre-treated textile
wastewater was submitted to the photocatalytic
system.
Initially, the effect of different photo-Fenton
variables, such as dissolved iron concentration (40,
60 and 100 mg Fe2+ L-1); pH (2.8, 3.6 and 4.5);
temperature (10, 30 and 50 C) and UV radiation
intensity (22, 44 and 68 W UV m-2); were evaluated in
a lab-scale photoreactor consisting of: i) a solar
radiation simulator (ATLAS, model SUNTEST
XLS+) with a 1700 Watt air-cooled xenon arc lamp,
a daylight filter and quartz filter with IR coating; ii) a
CPC with 0.023 m2 of illuminated area with
electropolished anodized aluminum reflectors and a
borosilicate tube; iii) one glass vessel (capacity of
1.5 L) with a cooling jacketed coupled to a
refrigerated thermostatic bath to ensure a constant
temperature during the experiment; iv) a magnetic
stirrer to ensure complete homogenization of the
solution inside the glass vessel; v) one peristaltic
pump (flow rate of 0.63 L min-1) to recirculate the
water between the CPC and the glass vessel. The
glass vessel was filled with 1 L (Vi = 270 mL; Vi/Vt =
0.27; ti = 0.43 min; tdark = 1.16 min; ACPC = 0.023 m2)
of electro-treated effluent and pumped to the CPC
unit and, homogenized by recirculation in the closed
system. The hydrogen peroxide (50% (w/v), 1.10 g
cm-3, Quimitcnica, S.A.) concentration was
maintained between 100-500 mg H2O2 L-1, during
the entire runs, through the addition of small
amounts to compensate the consumption, as

determined
by
analyses
throughout
the
experiments.
A new experiment, considering the optimum
photo-Fenton variables values, was carried out in a
pilot plant installed at FEUP, Portugal. The solar
collector consists of a CPC unit (illuminated volume
(Vi) = 5.1 L; Vi/Vt = 0.34; illuminated time (ti) = 0.25
min; dark time (tdark) = 0.50 min; ACPC = 0.455 m2) of
four borosilicate tubes (SchottDuran type 3.3,
Germany, cut-off at 280 nm, internal diameter 50
mm, length 1500 mm and width 1.8 mm) connected
in series by polypropylene junctions, with their CPC
mirrors in electropolished anodized aluminum,
supported by a aluminum structure, oriented to
south and tilted 41 (local latitude). A volume of 15
L of electro-treated textile wastewater was added to
the recirculation tank of the CPC units and
homogenized by turbulent recirculation. The pH
was adjusted (2.8) with sulfuric acid, and iron
sulfate salt (100 mg Fe2+ L-1) was added. In the
kinetic experiment the first dose of H2O2 added was
500 mg L-1 and during the reaction the
concentration was maintained between 100 and
500 mg L-1 by the addition of small amounts of H2O2
as consumed, measuring the concentration of H2O2
in small time intervals. For biodegradability tests, a
new photo-Fenton experiment was performed
maintaining all parameters, with exception for H2O2
dose. In this case, a small amount of H2O2 was
added to photoreactor, and after H2O2 total
consumption, a sample was taken for bioassays
and a new dose of H2O2 was added. The intensity
of solar UV radiation is measured by a global UV
radiometer (ACADUS 85-PLS), which provides data
in terms of incident W UV m-2. A final experiment,
considering the consumption of H2O2, amount of UV
radiation (integrated by the UV radiometer) or
partial mineralization, was carried until reached the
biodegradability set point. At this moment the
reaction stopped, and the pre-treated textile
wastewater was neutralized with NaOH to a pH
around 7, leading to iron precipitation, followed by a
period of three hours for sedimentation of iron
sludge. After that, the electro-photo-treated was
submitted to the biological aerated reactor.
The lab-scale biological oxidation reactor is
composed by a cylindrical glass container (1 L),
equipped with a magnetic stirrer and a compressor
to supply air. pH, temperature and dissolved
oxygen were monitored by a multiparameter Hanna
(model HI 9829). The biological reactor was firstly
colonized using activated sludge from a
conventional municipal wastewater treatment plant,
and small amounts of electro-photo-treated textile
wastewater was added during three days in order to
adapt the biomass. After this preliminary adaptation
period, the electro-photo-treated (1 L) was added
into the biological reactor, after settling the biomass
present inside. The biological reactor was operated
under aerobic conditions, to promote nitrogen
removal and also to remove biodegradable organic
compounds. pH was controlled between 7.5 and
8.5, and oxygen concentration was maintained
between 0.5 and 2 mg O2 L-1.

Results and Discussions


The textile wastewater presents a dark-blue color,
resulting from the mixture of different reactive dyes,
originating a maximum absorbance peak at 641 nm.
The effluent present an alkaline pH (11.3), a
moderate total dissolved nitrogen (45.5 mg N L-1),
and organic load (COD = 1239 mg O2 L-1 and DOC
= 408 mg C L-1), exceeding the discharge limits into
receiving waters imposed by the Portuguese
legislation (Decree law no236/98). The effluent
presents also a high concentration of chlorides (5.5
g Cl- L-1), sodium (4.1 g Na+ L-1), sulfate (118 mg
SO42- L-1) and potassium (180 mg K L-1) ions.
Preliminary tests showed that the addition of 100
mg Fe2+ L-1 to the textile wastewater at pH 2.8 lead
to 50% and 80% reduction of DOC and
dissolved iron concentration, respectively (data not
showed). This may be attributed to the precipitation
of the iron-organic complexes, which was visually
observed by the formation of high amounts of
suspended solids. After the beginning of the photoFenton reaction, the DOC remained almost
constant even for high amounts of energy, meaning
that the iron-pollutants complexes avoid the
formation of hydroxyl radicals necessary for the
organic compounds mineralization. However, after
5 min electrolysis time, partial decolorization of the
textile wastewater was observed, leading to 44 and
47% DOC and COD removal, respectively. After the
electro-treatment, the iron dose added for the
photo-Fenton reaction resulted in a proportional
dissolved iron concentration, meaning that no ironorganic complexes were formed, and consequently
high photo-Fenton reaction rates will be obtained.
Afterwards, using the electro-treated wastewater,
the influence of the main solar-photo-Fenton
reaction variables was evaluated under controlled
conditions in a lab-scale photoreactor with a
sunlight simulator. After the EC, the solar photoFenton process contributed to complete textile
wastewater decolorization and an effective
mineralization,
with
an
optimum
catalyst
concentration of 100 mg Fe2+ L-1, leading to 80%
mineralization at pH 2.8, requiring a UV energy
dose of 16.6 kJUV L-1 and consuming 54 mM of H2O2
(data not showed).
A Zahn-Wellens test was carried out to evaluate
the wastewater biodegradability at different
treatment stages, using the best variable conditions
of electro-photo-Fenton treatment (EC - pH 7, 149
A m-2 and 5 min; photo-Fenton - pH 2.8, 100 mg
Fe2+ L-1) in a CPC pilot plant (Figure 1). The DOC
and COD concentration decreased 80% and 83%,
respectively, showing a strong oxidation of the
organics. This is well correlated with the carbon
oxidation state (COS) parameter as it increased
from -0.7, indicating the presence of some reduced
organic compounds, to 3.2 after 21.7 mM of H2O2
consumed, representing strong mineralization and
generation of highly oxidized intermediates, thus
improving the biodegradability. Similar behavior
was observed for the average oxidation state
(AOS). Figure 1 shows also a fast increase on the
DOC corresponding to low-molecular-weight

carboxylate anions (LMCA/DOC ratio) after the


beginning of the photo-Fenton reaction, achieving
maximum values of 4.3% (considering the LMCA
analyzed) at 21.7 mM of H2O2 consumed (sample
7).
According to the Zahn-Wellens test the textile
wastewater presents a moderate biodegradability
(59%).
The
biodegradability
remained
approximately constant for the sample that suffered
the EC treatment, however, as expected, the
biodegradability was enhanced during the photoFenton treatment, achieving values of 62.3, 73.2
and 79.7%, corresponding to 4.5, 12.2 and 21.7
mM of H2O2 consumed (samples 5, 6 and 7),
respectively. Sample 6 can be considered the best
point to stop the pre-oxidation process, since
achieved a COD < 150 mg O2 L-1 (discharge limit
into receiving bodies imposed by the Portuguese
legislation Decree law no 236/98) after 28 days of
the Zahn-Wellens test.
A new experiment (Figure 2), considering the
optimum electro-photo-Fenton variables values,
was carried leading to DOCfinal = 113.5 mg C L-1 and
CODfinal = 276 mg O2 L-1. As above mentioned, after
pH neutralization of the electro-photo-treated textile
wastewater and iron sludge removal, the effluent
was further treated in a biological aerated reactor,
leading to a final wastewater with the following
characteristics: total decolorization, DOC = 38 mg C
L-1, COD = 139 mg O2 L-1, Total Nitrogen = 7.4 mg
N L-1, Ammonia = 4.0 mg N-NH4+ L-1 and Sulfate =
900 mg SO42- L-1, which are in agreement with the

discharge limits
legislation.

imposed

by

the

Portuguese

Figure 1. Evolution of DOC, COD, AOS, COS, LMCA/DOC


ratio (fraction of DOC related to low-molecular-weight
carboxylate anions) and Dt after 28 days during the electrophoto treatment. S1-S7 = 382.3; 170.8; 162.5; 136.6; 123.6;
103.4 and 76.2 mg C L-1, respectively.

Conclusions
Considering the combination of a EC, photoFenton reaction and a biological oxidation system,
in order to reach a final COD < 150 mg O2 L-1, the
energy dose required for the photo-Fenton reaction
is 6.9 kJUV L-1 (t30W = 60 min; T = 30 oC; pH = 2.8;
-2

UV G ,n = 35 W m ) consuming 12 mM of H2O2, and

leading to 74% mineralization (DOCfinal = 103.4 mg


C L-1).

Figure 2. Electrocoagulation/solar-photo-Fenton/biological treatment sequence of the real textile wastewater. I1, I2 and I3 =
intervals between each process (pH adjust, addition of iron and sludge).

Acknowledgements
Diego R. Manenti and Petrick A. Soares acknowledge their Ph.D. fellowships (BEX 9794/11-5 and 5512/10-7
processes) supported by CAPES. V. Vilars acknowledges Cincia 2008 Program.
References
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[2] C. H. Langford, J. H. Carey. Canadian Journal Chemistry, 53 (1975) 2430.
[3] F.R. Espinoza-Quiones, M.M.T. Fornari, A.N. Mdenes, S.M. Palcio, S.M. Silva, N. Symanski, A.D.
Krumov, D.E.G. Trigueros, Chemical Engineering Journal, 151 (2009), 59.
[4] S.M. Palcio, F.R. Espinoza-Quiones, A.N. Mdenes, C.C. Oliveira, F.H. Borba, F.G. Silva Jr., Journal
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