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T III LC iY
ELSEVIER Bioresource Technology 68 (1999) 95-100
Abstract
The effects of temperature, pH and ionic strength on adsorption of Cd(II) and Pb(II) onto carboxymethylated lignin from
sugar cane bagasse have been studied. Adsorption equilibrium data obtained using the batch technique were fitted to the
Langmuir model. A factorial design showed that the most important variables are temperature and ionic strength for the Pb(II)
adsorption in single and binary system respectively. For both metals, maximum binding capacity decreased with the ionic strength
increase. Increasing pH the Pb(II) adsorption is enhanced. Carboxymethylated lignin adsorbed Pb(II) selectively at pH 6.0, 30°C
and 0.1 mol dm -3 of ionic strength. © 1998 Published by Elsevier Science Ltd. All rights reserved.
(Kumar and Dara, 1981; Asai et al., 1986), palm kernel IY 0.2-
husk (Omgbu and Iweanya, 1990), peanut skin
0.1
(Randall et al., 1975), modified cellulosic materials
(Shukla and Sakhardande, 1990; Okeimen et al., 1985), 0.0
0.o lo 20 3.0 40 slo
pinus bark (Freer et al., 1989), corn cobs (Hawthorne-
Costa et al., 1995) etc., have received attention in these Ce ( mmol.dm -3 )
Fig. 1. Adsorption isotherms of Pb(lI) and Cd(lI) onto CLSCB at
30°C, pH 6.0 and 0.1 mol dm -3 of ionic strength. Symbols are experi-
*Corresponding author. mental data and solid lines are Langmuir fits.
0960-8524/99/$ - - see front matter © 1998 Published by Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 0 - 8 5 2 4 ( 9 8 ) 0 0 0 8 3 - 2
96 W.S. Peternele et aL/Bioresource Technology 68 (1999) 95-100
(Consolin Filho et al., 1996). The objective of this acid and precipitated with cold water, washed with hot
study was to contribute in the search for less expensive water and dried overnight at 50°C,
adsorbents and utilization possibilities for some
agricultural byproducts, which are in many cases also 2.2. Lignin reticulation
pollution sources.
Formic lignin (0.4 g) was dissolved in 10 c m 3 formal-
dehyde (38%) and 5.0cm 3 HCI, then refluxed for
2. Methods 30min. After reflux, lignin was precipitated with
diluted NaOH solution, filtered, washed with water
2.1. Lignin extraction until neutral pH, and dried at 50°C.
Sugar cane bagasse was extracted sequentially with 2.3. Reaction with chloroacetic acid
n-hexane, ethanol and water in a soxhlet system. The
sample obtained was then air dried. Formic acid To a dispersion of reticulated lignin (2.5g
(115 c m 3, 88%) was added to pre-extracted sugar cane lignin+20cm 3 of a 10% NaOH aqueous solution),
bagasse (10 g) and heated until reflux, when HCI was 5 cm 3 of a 36% aqueous chloroacetic acid solution was
added to obtain a 1% solution. After 3 h in reflux, the added under cooling with tap water. The resulting
sample was filtered and washed with concentrated solution was kept at 45°C and maintained under
formic acid. The solution was concentrated at reduced stirring during 4h. After acidification to p H 2 by
pressure until a viscous liquid was formed. This liquid diluted sulfuric acid addition, the solid precipitated was
was poured on cooled water and precipitated lignin filtered, and washed with water until neutral pH.
was obtained. This lignin was dissolved in hot formic
2.4. Methodology of adsorption experiments
Table 1
Langmuir parameters on Pb(II) and Cd(II) adsorptions onto CLSCB in different conditions (ionic strength: 0.1 mol dm -3)
initial concentration. A digital Micronal B 375 pH equilibrium constant and Ce is metal ion concentration
meter was used for pH measurements and buffer dissolved at the equilibrium) was utilized for estimating
solutions of acetic acid/sodium acetate 0.1 mol dm -3 qm and KL. Single saturation was not observed in some
was used in pH controlled adsorption experiments. isotherms. In these cases, the first saturation step was
considered for qm determination. In general, Pb(II)
adsorption was higher than Cd(II) adsorption. For
3. Results and discussion Cd(II), adsorption was always higher in the single
system compared with the binary system. This behavior
Adsorption of Cd(II) and Pb(II) from chloride salts is expected, considering that in the last case both metal
in aqueous solutions, onto carboxymethylated lignin ions will compete for the disposable binding sites at the
from sugar cane bagasse (CLSCB) was studied in adsorbent surface. However, Pb(II) is more adsorbed
single component and binary systems. Three experi- in the binary than in the single system, which support a
mental parameters were varied: temperature; pH; and synergistic effect. These way, adsorption of Pb(II) is
ionic strength. selective in relation to a binary system (with Cd(II)).
The results obtained at 30°C and at pH 5.0 and 6.0 Adsorption capacity (qm) is enhanced with increasing
are presented as adsorption isotherms in Figs 1 and 2. temperature in all the systems studied here (Table 1).
Saturation of Pb(II) and Cd(II) in both systems and The KL constant shows variable tendencies with
pH isotherms are shown, and could be fitted to a temperature variation. On the other hand, a tendency
Langmuir isotherm (Adamson, 1990). is observed for Pb(II) adsorption: KL at pH 6.0 is
The Langmuir equation, q/qm=KLCJ(I+KLCe) higher for the binary system and KL at pH 5.0 is higher
(where q is the amount of metal ion adsorbed, qm is the for the single system at the three temperatures. In
maximum adsorption capacity, KL is the Langmuir general, adsorption increases when pH is increased.
Q4
0.4-
0,4-
A j f J
03. j~rJ
/. /
0.3-
/
A
0.3-
~ 0.2-
E
E
E 0.2-
o"
01- I~'0.1 . Ionic Strength 1
Ior~c SUeagth
~i
//.m _~ ~ - ~ • •
• 0.1
A 0.5
• 1.0
0.1-
0.0
•
,L
•
0.1
0.5
1.0
GO i i / i B
0.0 1'.0 2.0 4,0 5.0 6.0
0 1 2 3 4 5
Ce( mmol / dm 3) Ce( mmol.dm-3)
"7,
0BiB /
.6
1 "7
0.8--
0.7-
0.6-
,---, 0.5-
O) O,4-
B +
This behavior must be related to the increase in the (three factors, each at two levels) was applied. The
ionization degree of the carboxylate groups present in standard experimental matrix for the factorial design
the modified lignin (Hawthorne-Costa et al., 1995, and the results of q , are shown in Table 2. A statistical
Consolin Filho et al., 1996). analysis was performed on these qm results, and the
NaC1 was added to give ionic strength of 0.5 and main effects and interaction effects for the different
1.0 mol dm -3 to evaluate the ionic strength influence variable combinations were calculated. The results
on the Pb(II) and Cd(II) adsorption experiments at (Table 2) show that temperature is the most important
30°C and at 50°C. Some of these isotherms obtained factor in the single system (Pb(II)), while ionic strength
are in Figs 3-6. The general tendency was adsorption is the most important variable for the binary system.
decreasing with increasing ionic strength. In many
cases, the addition of the neutral salt resulted in a
change of the shape of the isotherm. These changes
have been interpreted as being due to the presence of
4. Conclusions
more than one binding site present at the surface lignin Cheap materials such as lignin can be easily modified
particles (Wieber et al., 1988). in order to obtain new materials able to adsorb heavy
As observed with ionic strength 0.1 mol dm -3, Cd(II) metals ions. Carboxymethylated lignin from sugar cane
adsorption was always higher in the single than in the bagasse can adsorb Pb(II) and Cd(II) from aqueous
binary system (Figs 5 and 6). On the other hand, there solutions. In general, the Pb(II) adsorption process
is not a definite tendency with respect to pH in Cd(II) obeys Langmuir's model and Cd(II) presents adsorp-
adsorption. tion in multilayer, especially when the temperature is
Pb(II) adsorption showed better defined isotherms higher than 30°C. When ionic strength increases, the
(Figs 3 and 4). To qm data, a full 23 factorial design maximum adsorption capacity diminishes.
Iorac Slam~h e ~
• 0.1 . ~
0.2 A ~"g
.---. 0.2.
E
E ~ 0.1,
o"
01, E
. . c _
0.1 ~ • 0.1
- - A - - 0.5
00, - - u - - 1.0
c.(mm /dm3)
010
o.o . ,
1.o .
z0
, , ,
3.0 •
4~o slo 6.0
Ce( mmol.dm"3)
B
0.07
(~5-
°'~ 1 B
A (~D"
OD
Table 2
Adsorption capacity (qm) of CLSCB toward Pb(ll) in different conditions and factorial analysis
Variable qm (rnmol/g)
1 - - - 0.388 0.447
2 + - - 0.141 0.317
3 - + - 0.645 0.552
4 + + - 0.786 0.352
5 - - + 0.519 0.594
6 + - + 0.398 0.425
7 - + + 0.653 0.635
8 + + + 0.505 0.481
I 0.504 0.476
A -0.0936 -0.164
B 0.286 0.059
AB 0.090 0.014
C 0.029 0.117
AC - 0.04 1 0.002
BC - 0.165 - 0.011
ABC 0.104 0.021
CMLSCB can adsorb Pb(II) selectively rather than Asai, S., Konishi, Y., Tomisaki, H., 1986. Separation of mercury from
Cd(II) under special conditions (pH 6.0, 30°C and ionic aqueous mercury chloride Solutions by onion skins. Sep Sci and
Technol 21(8), 809-821.
strength of 0.1 mol dm-3), when both ions are present Consolin Filho, N., Winlder-Hechenleitner, A., G-6mez-Pineda, E.
in mixture. A., 1996. Copper(II) adsorption onto sugar cane bagasse. Intern J
Factorial analysis of Pb(II) adsorption suggests that Polymeric Mater 34, 211-218.
temperature is the most important factor in the single Freer, J., Baeza, J., Maturana, H., Palma, G., 1989. Removal and
system, adsorption increases with increasing tempera- recovery of uranium by modified Pinus radiata D don bark J Chem
Technol Biotechno146, 41-48.
ture. When Pb(II) and Cd(II) are present in a binary
Gabald6n, C., Marzal, P., Seco, A., 1996. Cadmium and zinc adsorp-
system, ionic strength is the most important factor. In tion onto activated carbon: influence of temperature, pH and
this case adsorption diminishes with increasing ionic metal/carbon ratio. J Chem Tech Biotechnol 66, 279-285.
strength. Hawthorne-Costa, E.T., Winkler Hechenleitner, A.A., G6mez-
Pineda, E.A., 1995. Removal of cupric ions from aqueous solutions
by contact with corn cobs. Sep Sci Technol 30(12), 2593-2602.
Acknowledgements Huang, C.P., Ostovic, F.B., 1978. Removal of cadmium(II) by
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Kumar, P., Dara, S.S., 1981. Binding heavy metal ions with polymer-
AAWH, EAGP, WSP acknowledge grants from ized onion skin. J Polym Sci, Polym Chem Ed 19, 397-402.
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