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Article history:
Received 18 April 2012
Received in revised form 8 November 2012
Accepted 8 November 2012
Available online 16 November 2012
Keywords:
Wastewater
Adsorption
Photocatalysis
Fenton-system
Fly ash
a b s t r a c t
Wastewaters resulting from the textile and dye nishing industries need complex treatment for efcient
removal of colour and other compounds existent in the dyeing and rising baths (heavy metals, surfactants, equalizers, etc.). Modied y ash (FA) mixed with TiO2 photocatalyst represent a viable option
for simultaneous removal of dyes and heavy metals, and the optimized conditions are discussed in this
paper for synthetic wastewaters containing methyl-orange (MO) and cadmium. For a cost-effective dye
removal process, further tests were done, replacing the photocatalyst with a (photo)Fenton system. The
optimized technological parameters (contact time, amount of y ash and amount of Fe2+ /H2 O2 ) allow
to reach removal efciencies up to 88% for the heavy metal and up to 70% for the dye. The adsorption
mechanisms and the process kinetic are discussed, also considering the possibility of in situ generation
of the Fenton system, due to the y ash composition.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Economic growth brings transformation, with a focus on
high-tech products and domestic goods, including the dyes manufacturing and the textile nishing industries; an immediate
consequence is the increase in water consumption and in wastewaters discharged into efuents. There are more than 10,000 dyes
currently used in the textile industry and over 280,000 tonnes of
the textile dyes are discharged every year worldwide [1]. Dyes
and heavy metals are hazardous pollutants which can modify the
physical and chemical properties of any ecosystem. Wastewaters
resulted in the dye nishing industry have high BOD to COD values
(>2000 mgO2 L1 ) while the discharge limits [2,3] are much lower
(BOD < 40 mgO2 L1 ; COD < 120 mgO2 L1 ), indicating the need for
wastewater treatment, because most of the dyes are slowly or nonbiodegradable.
Most of the wastewaters resulted in the dye nishing industry
are also containing additives (solubility and anti-foaming agents,
pH conditioners, whitening agents, etc.) and heavy metals, making the wastewater treatment complex and difcult. Toxicological
studies show that the most bio-toxic heavy metal is cadmium (also
774
Table 1
Fly ash composition.
Major oxides (wt.%)
SiO2
Al2 O3
Fe2 O3
CaO
MgO
K2 O
Na2 O
TiO2
MnO
LOIa
53.32
22.05
8.97
5.24
2.44
2.66
0.63
1.07
0.08
1.58
Cu
Zr
Sn
Pb
As
Ni
Zn
Ti
Cr
Co
700
60
100
35
100
55
160
6414
100
115
12
Loss of ignition.
Table 2
The surface characteristics of FA-M with TiO2 .
Component
Surface area
(m2 /g)
Total pore
volume (cm3 /g)
Average pore
diameter (nm)
FA-M
TiO2
11.33
50.02
0.06
0.25
20.33
30.08
775
Fig. 1. XRD of raw FA, washed with water (1) and of FA-M (2).
c0 ct
100
c0
(1)
where c0 represents the initial concentration and ct the concentration at moment t for the pollutant species (heavy metal or dye).
Preliminary experiments proved that heavy metal and MO
losses due to adsorption on the beakers walls and on the lter
paper were negligible. Blank tests done with the alkali conditioned
FA showed that during the experiments duration (up to 360 min) no
leaching occurred. Experiments also showed that there was no shift
in the absorption peak (in the initial solution and after the removing processes); supplementary interference with the Degussa P25
powder was investigated by analysing the spectra of ultra-pure
water and the supernatant resulted after ltering a Degussa P25
suspension in ultra-pure water and there were no differences.
3. Results and discussion
3.1. The substrates
The XRD spectra, Fig. 1, show that y ash contains crystalline compounds such as carbon (graphite), SiO2 (tetragonal
and orthorombic) combined with Al2 O3 as rhomb H, -Al2 O3 and
mullite (3Al2 O3 2SiO5 ), aluminosilicates with ions of Na+ or Ca2+ .
During the initial FA washing, the alkali and alkali-ferrous oxides
are likely to be removed; the further NaOH treatment can end up
in silica re-precipitating, as previously outlined [19,20].
The XRD data also show that FA contains small amounts of
crystalline titanium oxide (as brookite and as non-stoichiometric
Ti4 O7 ) thus indicating a possible photocatalyitic activity. Other
crystalline oxides are also part of y ash, as bixbyite (Mn2 O3 ) commonly found with hematite that can be responsible for in situ
oxidation/reduction systems of Fenton type. The unburned carbon,
as micro-sized crystallites is part of the FA and can explain the
776
Fig. 2. The AFM topography and average macro-pore size distribution in (a) FA-M before adsorption, (b) TiO2 before adsorption, (c) FA + TiO2 after MO interaction, and (d)
FA-M after MO adsorption.
2( AlO ) + M
2+
( Al O)2 M
(2)
Protolytic equilibria
Ti OH + H
Ti OH
Ti O + H
(4)
(5)
(7)
(8)
(9)
(10)
(11)
Ti OH2
(3)
(Ti O )2 M + 2H+
(6)
777
(12)
Fig. 4. Methyl-orange removal efciency on FA-M:TiO2 substrates from monocomponent pollutant systems in adsorption (A) and photocatalytic (F) experiments:
(a) inuence of H2 O2 addition and (b) inuence of the MO concentration
(C1 = 104 mol L1 and C2 = 5 105 mol L1 ).
Under UV irradiation, in the photo-Fenton system, supplementary amounts of HO are produced from the fast hydrogen peroxide
decomposition:
H2 O2 + UV HO + HO
(13)
(14)
Fe2+ + HO Fe3+ + HO
(15)
778
Parameter
1
5 104
0.358
27,228
0.952
CFe2+ (mol L )
qe (mg g1 )
k2 (g mg1 min1 )
R2
103
0.384
5319.2
0.998
2 103
0.708
19,261
0.964
3 103
0.617
4793.5
0.9795
Table 4
Kinetic parameters of the Cd2+ removal in photo-Fenton + adsorption processes.
Cd2+ (Cd2+ + MO)
Parameter
CFe2+ = 3 10
qe (mg g1 )
k2 (g mg1 min1 )
R2
initial c i
metal
qt =
mol L
UV
Visible
UV
Visible
632.981
1.5751
0.978
727.517
2.8378
0.973
538.331
0.0019
1
540.355
0.0093
1
Cd2+ /MO
concentrations of the
ct
Cd2+ /MO
ms
)V
(16)
and momentary c t
Cd2+ /MO
(Cd2+ ) and
(c i 2+
Cd /MO
(17)
Two low costs alternative processes were tested for the treatment of wastewaters containing dyes and heavy metals. The mixed
substrates of modied y ash and TiO2 proved to be highly efcient in cadmium adsorption, even after 30 min of contact, and
methyl-orange could be well removed, with efciencies above 75%
(after 300 min), when H2 O2 was added to systems with the dye
concentration of 0.05 mM.
Wastewaters containing mixed cadmiummethyl-orange can
be treated using modied y ash and photo-Fenton systems, under
UV irradiation. The results allow optimizing the Fe2+ amount for
reaching (after 90 min) methyl-orange removal efciencies close
to 70% while the cadmium adsorption was of 88%.
Acknowledgements
This paper is supported by the Sectoral Operational Programme
Human Resources Development (SOP HRD), nanced from the
European Social Fund and by the Romanian Government under the
contract number POSDRU ID 59323.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.
jhazmat.2012.11.013.
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