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Article history: In the present work, the adsorption ability of sugarcane bagasse to remove oil by-products from aqueous
Received 22 March 2009 solution was evaluated. The objective was treating the contaminated wastewater while enriching the
Received in revised form 16 October 2009 bagasse for its later use as fuel in boilers. Adsorption experiments were carried out in an agitated reactor
Accepted 16 October 2009
at room temperature to obtain kinetic curves and adsorption isotherms of gasoline and n-heptane on
Available online 24 October 2009
sugarcane bagasse. The results showed the great potential of bagasse as an adsorbent, since it was able to
adsorb up to 99% of gasoline and 90% of n-heptane in solutions containing about 5% of these contaminants.
Keywords:
In the adsorption kinetics of gasoline, the equilibrium was reached after just 5 min. This result shows that
Adsorption isotherm
Petroleum Hydrocarbons removal
the adsorption is very favorable. Langmuir, Freundlich, Temkin and D-R models did not describe well the
Bioadsorbents adsorption behavior obtained for these systems.
Sugarcane bagasse © 2009 Elsevier B.V. All rights reserved.
0304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.10.060
P.C. Brandão et al. / Journal of Hazardous Materials 175 (2010) 1106–1112 1107
Table 2
Nomenclature Commercial Brazilian gasoline composition.
qmax maximum capacity of adsorption (mL/g) Values reported by Ré-Poppi et al. [19].
b Henry’s constant (g/mL)
K dimensionless parameter of Freundlich isotherm
A parameter of Temkin isotherm (mL/g) a number 2, Buchner funnel, sealed. The two phases were split
B parameter of Temkin isotherm (mL/g) through decantation and the volumes were measured in a num-
ε Dubinin potential (mol/kJ)2 ber two test tube. The results showed a difference of 2% between
n parameter related to the solid heterogeneity in Fre- the initial and final volumes of gasoline. The difference is proba-
undlich isotherm bly due to evaporation, which is a very reasonable experimental
Np number of experimental points error.
The adsorption isotherms were obtained using a glass agi-
tated reactor at room temperature. 250 mL of water and 10 g of
sugarcane bagasse were placed in 600 mL beakers. After this, a
analyzer (Quantsorb Jr – QuantaChrome). In order to improve the certain amount of contaminant was added to each beaker. The
characterization, FTIR analysis was performed too. The sugarcane beakers were sealed and then, subjected to agitation. Two adsor-
bagasse, with diameter less then 0.297 mm, was mixed with KBr bate/adsorbent ratios were used to obtain the kinetic curves
powder and compressed to form a pellet. The FTIR spectra have of gasoline adsorption on sugarcane bagasse: 3.75 mL/g and
been recorded using a Bruker Equinox 55 with a spectral range 5.00 mL/g. For each of these ratios, the concentration of pollu-
from 4000 cm−1 to 400 cm−1 . An MIR, GLOBAR generator cooled tant in the water solution was measured after contact times of:
with air was used. The detection was carried out with a DLATGS 5 min, 15 min, 30 min, 45 min, 60 min and 90 min. In the end of
detector with a KBr window. The spectral resolution was about each experiment, the samples were filtered under vacuum using
4 cm−1 . a number 2, Buchner funnel, sealed. In some amounts of contam-
inant added, the filtrate presented two phases. In these cases, the
2.2. Kinetic curves and adsorption isotherms phases were split through decantation and the contaminant was
quantified through direct determination of volume in a number
To simulate the wastewater contaminated by oil by-products, two test tube. With this procedure, it was possible to deter-
commercial gasoline with 25% of ethanol was dispersed in water. mine by difference the amount of contaminant adsorbed on the
The adsorbent dose (10 g) and the stirring speed (400 rpm), were bagasse.
chosen using the results obtained during preliminary tests. Each The equilibrium is considered achieved when the adsorbed
experimental point was measured at least three times or until amount does not change with time of agitation. In this work,
the difference on the measured concentration was less than 10%. the equilibrium was achieved for all ratios of pollutant/adsorbent
Although the pH of the solution is an important variable in adsorp- within 60 min. The ratios used in this study are presented in
tion of ions, it is not so important in the adsorption of species Tables 3 and 4, for gasoline/bagasse and n-heptane/bagasse, respec-
such as the hydrocarbons used in this work. Therefore, pH, was tively.
not controlled. For all tests it did not varied significantly from
the initial value (pH 4.5). In order to verify if there was consider- 2.3. Correlation of experimental results
able hydrocarbons evaporation or sorption on the glassware during
the adsorption experiments, three “blank” runs were conducted. The experimental results obtained were used in the thermody-
In these tests, 250 mL of solution with different concentrations of namic modeling of the adsorption process. A non-linear regression
gasoline in water were placed in 600 mL beakers. The beakers were of the results was carried out using the software program STATIS-
sealed and then, subjected to agitation for 60 min. In the end of TICA. Version 5.1. The weighted least squares method was used as
each experiment, the samples were filtered under vacuum using a minimization criterion. For all of the models, the relative mean
Table 1
Literature references about use of sugarcane bagasse as an adsorbent.
Table 3
Gasoline/bagasse ratios used in adsorption experiments.
Table 4
n-Heptano/bagasse ratios used in adsorption experiments.
deviation (DMR) (%) was calculated, according to Eq. (1): 2.4. Evaluation of superior calorific value
n
qcal − qe /qe In order to verify if the hydrocarbon remained in the bagasse
i=1 i i i
DMR = (1) after the adsorption process, experiments tests to evaluate the
Np
superior calorific value were performed before adsorption and 1
where qcal and qe are amounts adsorbed in the equilibrium calcu- week after adsorption. The sugarcane bagasse containing gaso-
lated by the model and measured experimentally respectively, and line was retrieved after an adsorption experiment conducted with
Np is the number of experimental points used. 250 mL of water, 50 mL of gasoline and 10 g of bagasse. The tests
The models tested were Langmuir (Eq. (2)), Freundlich (Eq. were conducted according Brazilian rules (ABNT NBR 8633/84).
(3)), Temkin (Eq. (4)) and Dubinin–Radushkevich (D-R, Eq. (5))
isotherms since they are the models most often mentioned in the 3. Results and discussion
literature to describe adsorption processes in liquid phase. In Eqs.
(2)–(5) Ceq is the concentration of adsorbate in equilibrium (mL/mL) The characterization of “in-nature” sugarcane bagasse is pre-
and qeq is the adsorbed amount per gram of adsorbent (mL/g) in the sented in Table 5. The values of moisture content and ash content
equilibrium. are in agreement with that reported in literature [15], as well as,
the values found for volatile matter and fixed carbon, reported
qmax bCeq
qeq = (2) by Brazilian Industry of Ethanol. However, the value of surface
1 + bCeq
area is different from those reported in the literature [15–17].
1/n This is probably due to the fact that the sugarcane bagasse used
qeq = KCeq (3) in this work was “in-nature” rather than pretreated or activated
materials which, of course, presented higher values for the surface
qeq = A + B ln(Ceq ) (4)
area.
Fig. 1 shows the FTIR spectrum from untreated sugar cane
qeq = qmax exp(−kε) (5)
bagasse. The result is in agreement with that reported in the lit-
In the Langmuir isotherm (Eq. (2)), qmax is a parameter related to
the maximum capacity of adsorption and b is the Henry’s constant, Table 5
parameter related to the force between adsorbate and adsorbent. Physical and chemical characterization of the
The parameter K of the Freundlich isotherm (Eq. (3)) is associated adsorbent.
to the adsorption capacity and the parameter n is related to the Contents Results
solid heterogeneity. The Temkin isotherm (Eq. (4)) assumes that
Moisture (%) 8.1 ± 0.1
the fall in the heat of adsorption is linear rather than logarithmic,
Ashes (%) 1.3 ± 0.1
as implied in the Freundlich equation. A and B are Temkin constants. Volatile matter (%) 88.6 ± 1.7
In Eq. (5), D-R isotherm, ε(RT ln(1 + 1/Ceq )) is the Polanyi potential, Fixed carbona (%) 1.9
qmax (mL/g) is the adsorption capacity, and k (mol2 /kJ2 ) is a constant Surface area 40 m2 /g
related to the adsorption energy when it is transferred to the surface a
Fixed carbon (%) = 100 − moisture (%) −
of the solid from infinity in the solution. volatile matter (%) − ashes (%).
P.C. Brandão et al. / Journal of Hazardous Materials 175 (2010) 1106–1112 1109
Table 6
Superior calorific value of sugarcane bagasse. the sugarcane bagasse enough to improve its superior calorific
Type of bagasse Superior calorific value.
value (kJ/g) Fig. 2 shows the influence of contact times between the phases
“in-nature” 29.14 on the final amount of gasoline left in the liquid phase. Fig. 3
1 week after adsorption 33.98 presents the kinetic curves of adsorption expressed in terms of
adsorbed gasoline per gram of bagasse. The kinetic curves are
slightly changed by the initial ratio of gasoline/bagasse. For the
erature for sugarcane bagasse untreated [18]. The strong signal ratio P = 3.75 mL/g, the equilibrium was reached after 60 min and
at 3400 cm−1 is typical from cellulose and the reasonable defined 85% of the initial gasoline was adsorbed during the first 5 min.
shoulder at 3250 cm−1 is related to hemi-cellulose. The medium Therefore, there was a very small variation on the adsorbed
signal, between 1500 cm−1 and 1750 cm−1 , is due to the carboxylic volume between 5 min and 60 min, around 3 mL. For the ratio
groups, present in lignin and hemi-cellulose. This is consistent with P = 5 mL/g, an average value of 8.5 mL of gasoline was detected
the nature of Brazilian sugarcane bagasse that is composed by 49.1% in the solution between the times of 3 min and 60 min. This
of cellulose, 20.3% of lignin, 27.8% of hemi-cellulose and 1.6% of corresponds to an adsorption percentage of 83% and a capacity
ashes. of adsorption of 4.15 mL/g. Therefore, it can be concluded that
In order to verify if the hydrocarbons adsorbed remained in the adsorption kinetics of gasoline on sugarcane bagasse is very
the solid, measurements of superior calorific values of the sug- fast.
arcane bagasse were conducted before and 1 week after the Fig. 4 shows the percentage of pollutant adsorbed (Pads ) on
adsorption. The results are presented in Table 6. It can be notice sugarcane bagasse, at room temperature, versus the initial con-
that there was an improvement of the superior calorific value centration of pollutant in aqueous solution. It can be observed
of bagasse by the adsorption of gasoline. Therefore, even after that sugarcane bagasse is able to adsorb up to 99% of gasoline
a week following the adsorption, there was still gasoline left in and 90% of n-heptane in aqueous solutions containing around of
5% of these contaminants. For higher concentrations, that could
Fig. 2. Final volume of solute in water after the adsorption of gasoline on sugarcane Fig. 4. Percentage of pollutant adsorbed as a function of initial concentration of
bagasse at room temperature as a function of contact time. pollutant in aqueous solution.
1110 P.C. Brandão et al. / Journal of Hazardous Materials 175 (2010) 1106–1112
Table 7
Parameters of the isotherms tested in this work, with respective correlation coefficients (R2 ) and mean relative devia-
tions (MRD).
Isotherm System
Water/gasoline Water/heptane
K 14.9450 3.4663
1/n 0.3431 0.1250
Freundlich
R2 0.96176 0.51071
MRD (%) 12.6 20.3
[25] U. Garg, M.P. Kaur, G.K. Jawa, D. Suda, V.K. Garg, Removal of cadmium(II) from [27] U.K. Garg, M.P. Kaur, V.K. Garg, D. Sud, Removal of hexavalent chromium from
aqueous solutions by adsorption on agricultural waste biomass, Journal of Haz- aqueous solution by agricultural waste biomass, Journal of Hazardous Materials
ardous Materials 154 (2008) 1149–1157. 140 (2007) 60–68.
[26] U.K. Garg, M.P. Kaur, V.K. Garg, D. Sud, Removal of Nickel(II) from aqueous [28] L.H. Wartelle, W.E. Marshall, Chromate ion adsorption by agricultural by-
solution by adsorption on agricultural waste biomass using a response surface products modified with dimethyloldihydroxyethylene urea and choline
methodological approach, Bioresource Technology 99 (2008) 1325–1331. chloride, Water Research 39 (2005) 2869–2876.