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Chemosphere
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Chemical Engineering Department, Aristotle University of Thessaloniki, Un. Box 455, 54124 Thessaloniki, Greece
Department of Chemistry, University of Ioannina, GR-45110 Epirus, Greece
a r t i c l e
i n f o
Article history:
Received 11 February 2010
Received in revised form 2 June 2010
Accepted 9 June 2010
Available online 3 July 2010
Keywords:
Activated carbons
Biomass
Agricultural residues
Bromopropylate
Pesticides
Adsorption kinetics
a b s t r a c t
Activated carbons (ACs) can be used not only for liquid but also for vapour phase applications, such as
water treatment, deodorisation, gas purication and air treatment. In the present study, activated carbons produced from agricultural residues (olive kernel, corn cobs, rapeseed stalks and soya stalks) via
physical steam activation were tested for the removal of Bromopropylate (BP) from water. For the characterization of the activated carbons ICP, SEM, FTIR and XRD analyses were performed. Adsorption kinetics and equilibrium isotherms were investigated for all biomass activated carbons in aqueous solutions.
Experimental data of BP adsorption have tted best to the pseudo 2nd-order kinetic model and Langmuir
isotherm. The study resulted that corn cobs showed better adsorption capacity than the other biomass
ACs. Comparison among ACs from biomass and commercial ones (F400 and Norit GL50) revealed that
the rst can be equally effective for the removal of BP from water with the latter.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Leaching of chemical fertilizers and pesticides, applied to agricultural and forest land, is one of the main reasons for organic pollution in several water streams. Pesticides are greatly used in
Europe. Particularly in Greece their use in crops is higher than
the European average value. The pesticides are applied to the foliage of the crops, thus a considerable amount of the product results
in soil. The removal of the pesticides by conventional biological
treatments has proven to be ineffective, while activated carbons
could be more effective. Thus, activated carbons are applicable to
a wide range of processes for the removal of organic compounds
in water (Li et al., 2002; Moreno-Castilla, 2004; Gupta et al.,
2006; Dias et al., 2007).
ACs are adsorbents that are extremely porous and thus have a
very large surface area available for adsorption or chemical reactions. Adsorption, like ion exchange and chromatography, is a sorption process in which certain adsorbents are selectively transferred
from the uid phase to the surface of insoluble, rigid particles suspended in a vessel or packed in a column. Carbon adsorption has
numerous applications in removing pollutants from air or water
streams both in the eld and in industrial processes such as spill
cleanup, groundwater remediation, drinking water ltration, air
purication, volatile organic compounds removal, gasoline dispensing operations, and other processes. The adsorption process
is generally classied as physisorption (characterized by weak
van der Waals forces) or chemisorption (characterized by covalent
bonding).
Lignocellulosic biomass, widely recognized as a potential lowcost source for the production of high added value materials, has
been proved to be good precursors for the production of ACs. More
specically, ACs made from biomass are very effective for the removal of metal ions (Kadirvelu et al., 2003; Ho and Ofomaja,
2005; Giraldo and Moreno, 2008), phenols, phenolic compounds
(Dabrowski et al., 2005; Dursun et al., 2005), heavy metals and
dyes (Ricordel et al., 2001; Chuah et al., 2005) from aqueous solutions. Furthermore, they can adsorb arsenic (As) (Manju et al.,
1998) and trace metals (Ahmedna et al., 2004) from drinking
water, but also be used as support for noble metals or as catalysts
per se in liquid phase reactions (Besson et al., 2005). Activated carbons are also very efcient in the adsorption of nitrate and pesticides from surface waters (Kouras et al., 1995; Murayama et al.,
2003; Ayranci and Hoda, 2005; Aslan and Turkman, 2005).
Bromopropylate (isopropyl-4-40 -dibromobenzilate) is a bridged
diphenyl acaricide (miticide) effective against all stages of mites
such as eriophyidae (eriphyid mites), tenuipalpidae (false spider
mites) and tetranychidae (spider mites) (Vial et al., 1971). It kills
mites in all postembryonal stages, whether they are susceptible
or resistant to chlorinated hydrocarbons and/or organic phosphate
compounds (Westigard and Barry, 1970). Bromopropylate was rst
1329
1330
Table 1
Characteristics of ACs.
Sample name
CC
OK
SS
RS
NORIT GL 50
F400
Ultimate analysis
C%
H%
N%
76.3
0.92
4.19
54.73
1.05
0.46
58.26
0.8
0.43
59.5
0.97
0.47
n.a.
n.a.
n.a.
87
0.3
0.5
Proximate analysis
Ash%
Moisture%
FC%
VM%
9.88
6.97
80.72
2.43
17.35
12.94
63.38
6.33
40.60
5.93
46.40
7.07
26.17
8.68
56.21
8.95
8.95
3.92
76.13
10.99
6.46
6.03
73.46
14.05
258
137
342
85
41
12
4.45
1.13
0
4160
5000
2130
1000
760
438
37
12
4.2
10 400
3720
4830
4600
940
500
132
17
4.8
6400
3360
490
860
121
45.5
4.5
7.8
0
600
0.30
0.30
570
0.31
0.29
490
0.28
0.21
650
n.a.
0.33
(Prasertmanukitch et al., 2004)
827
0.52
0.23
(Diamantopoulou et al., 2010)
removal %
C 0 C e
100
C0
qe
C 0 C e V
m
Corn Cob
1331
Olive kernel
Rapeseed
stalks
Soya stalks
Fig. 1. Characterization of ACs: (a) isotherms of ACs, and (b) FTIR spectra.
F error
s
Rpi qical qi exp =qi exp 2
where qical is the amount of substance, mg gr1 AC that was calculated; qiexp is the amount of substance, mg gr1 AC that was estimated experimentally; p the number of experiments.
2.3.3. ECD analyses
The gas chromatograph used for the analyses was a Shimadzu
14B, which had an ECD detector (63Ni electron capture) that works
at 300 oC and the column was an ADB-1 (J&W Scientic, Folsom,
RRF
C A AREAIS
AREAA C IS
1332
Table 2
General characteristics of Bromopropylate (BP).
Structure
3 10
Endpoint LD50 [Symyx
Toxicity database]
Pesticide type
Chemical group
Chemical
Formula
M.W.
Solubility in
water (mg L1)
Solubility in
organic
solvents (at 20 C)
Acaricide/
insecticide
Benzilate
C17H16Br2O3
428.13
0.1
High
Aquatic NEC
(kg m3)
1.7 107
Water DT50w
(D)
3
Mouse (oral)
Quail (oral)
Rat (oral)
Rat (skin)
>2
>4
Rabbit
(skin)
10 200
3.2. Specic results on ACs surface area, porosity and pore size
distribution
The surface area, total pore volume (Vptot) and micropore volume (Vmicro CO2), from CO2 adsorption, are presented in Table 1.
As observed, CC was the most microporous material giving the
highest BET surface area (630 m2 g1) and the highest micropore
volume (0.34 cm3 g1 C) of the four samples. On the contrary, RS
gave the lowest (490 m2 g1) BET area and the lowest micropore
volume (0.21 cm3 g1 C). The surface area and the microporous
area, calculated from CO2 adsorption, had similar trend. OK and
SS showed similar surface characteristics and porosity. Generally,
it was shown that activated carbons generated from biomass have
comparable characteristics with commercial ones.
The above conclusions were also veried by the isotherms. All
isotherms (Fig. 1a) at very low relative pressures (P/P0 < 0.3) presented an increase typical of adsorption taking place by lling of
micropores classied, as type I (microporous materials). The isotherms exhibited a continuous adsorption increase up to P/P0 near
unity, due to multiplayer coverage at pores greater than 4 nm. Isotherms of CC and OK can be classied as type I of the JUPAC classication for low conversion samples resembling microporous
structured materials with slit-shaped pores and extensive development of pore sizes. Isotherms of SS and RS can be classied as type
I, but also approach type IV of the JUPAC classication, with weak
hysteresis loop, characteristic of microporous materials with some
degree of mesoporosity.
Pore size distribution, besides surface chemistry, is the most
important characteristic of AC in the adsorption of organic compounds. The accessibility of the organic molecules to the microporosity depends on their size. Pores are classied according to their
size into micropores (<2 nm), mesopores (250 nm) and macrop-
1333
and RS) gives brous like structure in nature with long ridges,
resembling a series of parallel lines (Fig. 2a). Woody materials
are composed mostly of lignin, thus their morphology resemble
the morphology and structure of lignin. On the contrary softer
woody materials, straws, which are composed mostly of cellulose,
resemble the morphology of cellulose.
The larger pores contained multiple smaller ones, also noticeable in the straight tubes, which were each with nearly uniform
dimensions. In all samples the external surfaces were found covered with smooth open pores of different sizes. Furthermore, due
to devolatilization, collisions of these compounds with pore walls
might bring about their cracking and carbon deposition (Kumar
and Gupta, 1995; Della Rocca et al., 1999; Bonelli et al., 2001),
causing the fragmentation and the irregular shapes which were observed. Activated carbons after adsorption showed the same
shapes, but more eroded and throttle surfaces than the ones before
adsorption.
Fig. 2. Characterization of ACs (a) SEM analysis of CC and RS ACs, and (b) XRD analysis of CC and SS ACs.
1334
Fig. 3. Kinetic study: (a) BP removal (%) versus time for all ACs, and (b) Legergrens
Pseudo 2nd-order kinetics for all ACs.
of BP on the ACs generated from agricultural residues are best tted by the pseudo-second-order kinetic model compared to pseudo-rst-order kinetic model. It is worth to mention that
commercial ACs did not have a better behaviour than the manufactured ACs. Bacaoui et al. (2002) who studied olive cake as a precursor for activated carbon production in herbicides removal has also
observed that AC with large macropores and micropores showed
better adsorption capacities and ability to adsorb herbicides than
commercial carbons. Besides, for pseudo-second-order kinetic
model the adsorbed amount, qe is almost equal to the qe estimated
Table 3
Adsorption kinetic results.
Sample-raw material
R2
75
135
135
135
75
75
0.0117
0.01995
0.01677
0.0225
0.01616
0.023
0.1403
0.142
0.1692
0.1383
0.13867
0.1247
0.0948
0.0866
0.078
0.0893
0.0897
0.0817
0.6222
0.8154
0.3441
0.949
0.0851
0.312
0.09408
0.0878
0.0849
0.0904
0.0906
0.08
0.0948
0.0866
0.078
0.0893
0.0897
0.0817
0.9972
0.9998
0.9543
0.9998
0.9523
0.9354
75
135
135
135
75
75
7.56
4.28
0.8465
4.85
3.39
2.41
1335
Langmuir
Ka
Corn cob
Olive kernel
Soya stalks
Rapeseed stalks
Norit GL 50
F400
26.64
16.88
59.44
106.29
16.73
38.38
Freundlich
qm
R
2
18.9 10
12.3 102
11.6 102
7.9 102
21.17 102
15.6 102
0.9952
0.9963
0.9913
0.9993
0.9991
0.9977
Fer
4
3.7 10
7.42 104
5.85 104
7.64 104
9.16 104
4.97 105
Kf
R2
Fer
0.77
0.622
2.095
0.659
2.556
0.538
1.63
1.46
0.996
1.878
0.854
2.779
0.9107
0.9285
0.9601
0.8886
0.8984
0.9793
9.71 103
1.53 103
3.82 103
1.43 103
1.33 102
2.34 103
that were pyrolysed were corn cob, olive kernels, soya stalks and
rapeseed stalks. Pyrolysis chars were subsequently activated with
steam. The produced ACs were analyzed by IR, SEM, XRD and from
the analyses some important characteristics of the four biomass
samples have been revealed. Furthermore, the ACs were tested
for the adsorption of an acaricide, Bromopropylate, from aqueous
solution. Kinetics and equilibrium studies were performed. For
the sake of comparison, two commercial ACs (F400 and NORIT
GL50) were also tested by the same procedure.
The kinetic analysis showed that pseudo 2nd-order model is
applicable to all samples, while the equilibrium study showed that
the Langmuir model is best tted the isotherms. The AC with the
higher adsorption capacity for Bromopropylate was proved to be
corn cob, then olive kernel and soya stalk, while rapeseed stalks
gave the lower results for the specic application. The BP removal
from water achieved in this study was 90100% for all ACs for an
equilibrium time in the range 75135 min.
The ACs from biomass residues proved to have similar or even
better Bromopropylate removal capacity than the commercial ones
(F400 and NORIT GL50).
Acknowledgments
The authors would like to thank the Department of Physics of
Aristotle University of Thessaloniki and especially Dr. Labrini
Papadopoulou for her assistance on the SEM analyses; the Laboratory of Inorganic Chemistry of Chemical Engineering Department,
Aristotle University of Thessaloniki for the FTIR analysis and Dimitrios Petrakis Assistant Prof. from the Department of Chemistry, of
University of Ioannina, for his assistance on the porosimetry
analyses.
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