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Article history:
Received 9 October 2013
Received in revised form 7 February 2014
Accepted 7 February 2014
Available online 26 February 2014
Keywords:
Fly ash
Hydrothermal synthesis
Heavy metal
Dye
Cationic surfactant
a b s t r a c t
Fly ash resulted from coal burning is a waste that can be used in wastewater treatment for removal of
dyes and heavy metals by adsorption.
Class F y ash (FA), collected from the Central Heat and Power (CHP) Plant Brasov (Romania), with
oxides composition SiO2 /Al2 O3 over 2.4 was used for obtaining a new substrate with good adsorption
capacity for dyes and heavy metals from wastewater. A new material was obtained from modied y ash
with NaOH and hexadecyltrimethylammonium bromide (HTAB) a cationic surfactant. Contact time, optimum amount of substrate and the pH corresponding to 50 mL solution of pollutants were the parameters
optimized for obtaining the maximum efciency in the adsorption process. The optimized adsorption
parameters were further used in thermodynamic and kinetic studies of the adsorption processes.
The adsorption kinetic mechanisms, and the substrate capacities are further discussed correlated with
the surface structure (XRD), composition (EDS, FTIR), and morphology (SEM, AFM).
The results indicate that the novel nano-substrate composite with y ash modied can be used as an
efcient and low cost adsorbent for simultaneous removal of dyes and heavy metals, the resulted water
respects the discharge regulations.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Textile industry is among the most polluting industries
regarding the fact that it uses a large amount of water during the
dyeing process [1] and because of this the discharged efuents are
loaded with numerous pollutants like dyes, toxic metals, suspended
solids, microbial pathogens and parasites, biodegradable, volatile
and recalcitrant organic compounds [2,3]. The efuents from textile
industry change the biological life of rivers and lakes [4,5].
Wastewaters with a load like this cause damages to the environment by creating problems to the groundwater resources [6]. These
wastewaters are highly colored, have a uctuating pH, high temperature and chemical oxygen demand, large amounts of suspended
oils. The main problem related to the dyes (which are stable to light
and are not biodegradable [2]) in wastewater is the color which
decreases the light permeability thus causing a negative effect on
photosynthesis [7]. Decreasing permeability of light, the amount
of oxygen decomposed lead to extinction of some living beings
and to restriction of the reuse of water. The heavy metals from the
15
The pollutant systems were synthetically prepared using bidistilled water and CdCl2 2.5H2 O (Scharlau Chemie S.A., c < 98%),
CuCl2 2H2 O (Scharlau Chemie S.A., c < 98%) and MB (C16 H18 N3 S)
(Fluka AG, reagent grade). The experiments were done using heavy
metal solutions in the concentration range of cCd = 0, . . ., 515 mg/L
and cCu = 0, . . ., 350 mg/L, respectively; methylene blue (MB) initial
concentrations were: cMB = 0.0625 mmol/L.
The behavior of the new adsorbents materials (FAA-CS24)
respectively (FAA-CS48) were tested to decide which one is the
most efcient adsorbent for the next adsorption processes.
Two series of experimental tests of adsorption were done using
the bicomponent pollutant systems:
(a) Adsorption on FAA-CS24 substrate in solutions containing two
pollutants:
- Cd2+ and MB, under mechanical stirring;
- Cu2+ and MB, under mechanical stirring;
(b) Adsorption on FAA-CS48 substrate in solutions containing two
pollutants:
- Cd2+ and MB, under mechanical stirring;
- Cu2+ and MB, under mechanical stirring.
The solutions were used at their natural pH; the initial pH of
the solutions containing dyes and heavy metals in contact with
FAA-CS24 substrate was 8.22, respectively 9.57 with FAA-CS48 substrate, which are higher than the new material point of zero charge
(PZC = 7.44).
Preliminary experiments proved that heavy metals and dyes
losses due to adsorption to the container walls are negligible.
The kinetic and thermodynamic adsorption parameters of the
heavy metals and MB from bi-pollutant systems were evaluated
from batch experiments; in each experiment, 0.1 g of FAA-CS24 or
0.1 g of FAA-CS48 substrate was stirred (200 rpm) at room temperature (2023 C), with 50 mL solution, at initial concentrations
(CiCd = 515 mg/L, CiCu = 350 mg/L) set according to the experimental
study; for the kinetic studies, aliquots were taken each at 15, 30,
60, 90, 120, 150, 180, 240, 300 min, when stirring was briey interrupted and the substrate was removed by centrifugation (GL-20G,
Shanghai).
The supernatant was further analyzed by AAS (Analytic Jena,
ZEEnit 700), at: Cd = 228.8 nm and Cu = 324.75 nm and UVvis
absorbance measurements (PerkinElmer UVVIS spectrophotometer, Lambada-950) were done at the maximum absorption
wavelength (665 nm) for MB.
3. Results and discussion
3.1. Characterization of the substrates
The siliconalumininous composition in the y ash is conrmed by XRD spectra, Fig. 1. The major crystalline components
of washed y ash are: SiO2 (quartz), mullite (3Al2 O3 2SiO5 ),
16
The XRD data show that the new substrates, FAA-CS24 and FAACS48, have well embedded the new phase of alumino-silicates with
area picks more high. The crystallite sizes were calculated using the
Scherrer equation. (1) [20].
=
Fig. 1. XRD data of (1) FAw, (2) FAA-CS48 and (3) FAA-CS24.
K
cos
(1)
Fig. 2. AFM images for (a) FAw; (b) FAA-CS24; (c) FAA-CS48.
17
Table 1
Surface composition, in atomic %, of the FAA-CS surface before and after adsorption the (Cd2+ + MB) solution.
Element
FAA-CS24
N
O
Na
K
Al
Si
S
Ca
Ti
Br
Cd
FAA-CS48
Before adsorption
After adsorption
Before adsorption
After adsorption
16.40
39.50
2.53
1.58
1.22
10.08
28.53
1.92
1.49
7.68
27.00
39.48
4.64
9.09
72.23
1.71
5.56
8.93
0.19
0.17
0.16
0.00
1.96
3.16
5.45
1.67
0.12
3.23
8.93
0.19
0.17
2( SiO ) + M
2+
( Si O)2 M
(2)
(3)
Fig. 4. XRD of FAA-CS24 (1) before and (2) after adsorption the (Cu2+ + MB) solution.
18
Fig. 6. EDS spectra of FAA-CS24. Intensity of Si, Al, Cd on surface scanned after contact with the (Cd2+ + MB) solution.
Fig. 7. EDS spectra of FAA-CS48. Intensity of Si, Al, Cd on surface scanned after contact with the (Cd2+ + MB) solution.
19
Table 2
Characteristics of IR bands associated with zeolites (common for all zeolites).
Type of IR band vibrational
Frequency [cm1 ]
Internal tetrahedral
Pore opening vibrations
T O bending vibration
Symmetric stretch of T O bond
300420
420500
660
External tetrahedral
Double ring vibration
Symmetric stretch
Asymmetric stretch of TO bond
Asymmetric stretch
500670
750820
9501500
10501150
T = Si or Al.
The SEM and AFM images, Fig. 8(a) and (b), shows modied surfaces due to adsorption processes of the MB and the Cd2+ , Cu2+ ions,
conrmed by roughness modication.
These AFM images were used to characterize the surface morphology: the uniformity, grain size and pore size distribution [23]
of the samples Fig. 9.
Supplementary information was obtained using the FTIR spectra. The y-ash based substrate has a composition close to a zeolite
(SiO2 /Al2 O3 over 2.4); therefore the frequency regions corresponding to different types of vibrations in zeolites, presented in Table 2
were considered as reference [24] in investigating the experimental
results.
T = SiorAl
Fig. 10 Illustrates the FTIR spectra of the substrates before and
after adsorption. The asymmetric stretching modes of Si O Si or
Si Al O in all samples analysis was suggested by the absorption band at 954.21 cm1 for all with sharp peaks, indicating the
links between the framework units in the structure of FAA-CS.
In this type of material, water molecules are associated with the
cations that are in some extent hydrogen bonded to the oxygen
ions of the framework, explaining the peak with less intensity,
recorded at 16351644 cm1 which is characteristic to the bended
mode in the water molecules. The absorption band observed
from 3200 to 3600 cm1 was attributed to the hydroxyl group
stretching/vibration in Si OH, Al OH Al, Si OH Al units [25]. I
R spectroscopic studies conducted by Rayalu et al. [26] showed
that there was good agreement between IR and the XRD analysis.
3.3. Adsorption
In aqueous solutions hydrated heavy metal cations can be
subject of (for) hydrolysis, according to reaction (4), written for
divalent heavy metals [14]:
M2+ (aq) + nH2 O M(OH)2n + nH+
(4)
i
e
(cHM/MB
cHM/MB
)
i
cHM/MB
100
(5)
Good removal efciencies are obtained after 120 min for heavy
metals and earlier for MB, Fig. 11(a) and (b). For further thermodynamic studies the contact time optimized used for Cd2+ and Cu2+
cations, when equilibrium adsorption process was reached.
Increased efciencies over 90% for MB, 60% for cadmium and
71% for copper in adsorption processes are mainly related to the
morphology of substrates Fig. 2.
The average roughness in case of FAA-CS24 (123.61 nm) is bigger
than the average roughness of FAA-CS48 (56.441 nm). The value of
surface roughness provides information about the effective surface
area of the material, increasing surface roughness value signies
the increasing defects in the surface area and a possible increase
in the number of active sites, that is why the removal efciency
of MB and Cd2+ in case of using FAA-CS24 as substrate is bigger
than in case of FAA-CS48, Fig. 12(b). Both substrates are effective
in removing the pollutants by adsorption process but considering
the consumption of energy in substrate preparation the substrate
notated FAA-CS24 can be recommended.
The dates from Fig. 11(a), Fig. 13, indicate removal of hydrated
copper cations and MB cations by the same mechanism.
These dates correlated with the elemental EDS analysis of substrates Figs. 6 and 7 indicate that both substrates are effective
in removing the pollutants by adsorption process but considering
the consumption of energy in substrate preparation the substrate
notated FAA-CS24 can be recommended.
The removal efciency of heavy metals from solution with two
pollutants (HM cations and MB) is much higher for all pollutants
(Cu2+ , Cd2+ cations and MB) Fig. 13, as result of increasing the substrate dosage implicit of the active sites.
20
(11)
Fig. 10. IR spectrum (1) FAA-CS48, (2) FAA-CS24, (3) FAA-CS48/MB + Cu2+ , (4) FAACS24/MB + Cu2+ after adsorption with the (Cu2+ + MB) solution.
The amount of FAA-CS24 in the removal processes was optimized considering the highest risk of cadmium and copper cations.
Based on the experimental results, this amount was set at 0.15 g
FAA-CS24 in 50 mL pollutant solution, Fig. 13.
The same rate of curve (for copper, cadmium cations and for MB)
Fig. 11, can indicate the next interactions:
The Cd2+ and Cu2+ cations can also be adsorbed by the silanol
group (Si OH) of the layers, (Eqs. (7) and (8)) and MB will be protonated by electrophilic attack giving in solution the new species
MBH+ , Fig. 14.
Si OH + Cu2+ (H2 O)n Si OCu+ (H2 O)nx + H+ (H2 O)x
(7)
(8)
The presence of electron donated NH2 groups and conjugated electrons in complex may enhance the electron density
on S atom developing stable complexes with the heavy metals,
conrmed by dates from Table 1.
3.4. Uptake kinetics of heavy metals on FATiO2
In all cases after a rapid adsorption of cadmium, copper cations
and methylene blue (Fig. 10), adsorption slowly reached equilibrium at 120 min.
The adsorption capacity qt , in a V solution volume (50 mL), on
an ms amount of substrate (0.1 g), was evaluated using Eq. (9):
qt =
i
t
(cHM/MB
cHM/MB
)V
ms
(9)
KL
t,
2.303
(10)
(12)
(13)
where qmax (mg/g) represents the maximum monolayer adsorption capacity, a is a constant related to the adsorption free energy,
qeq is the amount of metal ions adsorbed from the solution with
the equilibrium concentration, Ceq .
- the Freundlich isotherm linearization:
ln qeq = ln kf +
1
ln ceq
n
(14)
21
Fig. 11. Removal efciency vs. contact time of (a) Cd2+ , (b) Cu2+ and MB from pollutant system in adsorption processes.
Fig. 12. The inuence of type of substrate in removing the Cd2+ , Cu2+ and MB from pollutant system by adsorption processes.
Table 3
Kinetic parameters of the heavy metal adsorption.
Substrate
KL (min1 )
R2
k2 (g/mg min)
Cu (Cu + MB)
FAA-CS24
FAA-CS48
0.005
0.014
0.953
0.992
0.013
MB(MB + Cu2+ )
FAA-CS24
FAA-CS48
MB(MB + Cd2+ )
FAA-CS24
FAA-CS48
2+
Interparticle diffusion
qe (mg/g)
R2
R2
0.446
0.231
119.058
138.889
0.969
0.996
5.754
5.330
0.888
0.696
0.097
0.055
156.25
126.582
0.995
0.993
2.989
0.017
0.987
0.312
21.754
0.089
1.7068
1.649
0.994
1
0.0861
0.2272
0.916
0.314
0.048
0.870
0.728
1.134
6.225
1.613
1.634
0.999
0.999
0.016
0.365
1.394
1.056
0.873
0.880
2+
11.554
42.240
101.0
0.939
0.951
0.929
0.613
Table 4
Adsorption isotherm parameters.
Solution system/substrate
2+
2+
Cu (Cu + MB)FAA-CS24
Cd2+ (Cd2+ + MB)FAA-CS24
MB (MB + Cu2+ ) FAA-CS24
MB (MB + Cd2+ ) FAA-CS24
Langmuir parameters
Freundlich parameters
2
qmax (mg/g)
a (L/mg)
KF
R2
56.497
87.719
0.3111
1.227
0.0016
0.0009
0.108
0.078
0.987
0.987
0.966
0.869
2.399
2.935
1.795
0.574
6.380
4.616E09
0.915
0.904
0.766
0.929
22
References
Fig. 13. Removal efciency of HM cations and MB vs. FAA-CS24 substrate dose in
adsorption process.
Supplementary, after adsorption and ltration the substrate loaded with pollutants was dried at 125 C and
subjected to desorption process. After 48 h, for ratio
mpFAA-CS/Cd+MB :Vbidistilled water = 0.3 g:100 mL there are no desorption of cadmium. Very small concentration of methylene blue was,
but not evaluated by spectrophotometer. These materials can be
reused for stufng in blocks of stone.
4. Conclusions
This results show that the y ash has potential to be used as
an alternative and cheap source of silica or alumino-silicates in the
production of adsorbents.
Micro-nano substrate was obtained in a hydrothermal process,
starting from y ash powder and HTAB cationic surfactant and was
tested for simultaneous removal of heavy metal cations and dyes,
in a single step process by adsorption.
The FAA-CS24 structural, morphology analysis and pore distribution showed that the substrate has a high crystallinity degree
and a surface with broad open pores, efcient in heavy metals (Cd2+
and/or Cu2+ ) removal from systems also containing methylene blue.
The kinetic and thermodynamic studies show that the substrate
has a good adsorption capacity mainly based on the electrostatic
attractions between the substrate and Cd2+ and/or Cu2+ cations.
Of the two substrates, FAA-CS24 substrate is effective in removing the pollutants by adsorption process and more economical in
terms of the process of obtaining, the energy consumption is lower.
Acknowledgment
This work was supported by the grant PNII-RU-TE-2012-30177/2013, nanced by Romanian National Authority for Scientic
Research, CNCS UEFISCDI.
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