Escolar Documentos
Profissional Documentos
Cultura Documentos
com
Abstract
In this paper, the ability of coconut bunch waste (CBW), an agricultural waste available in large quantity in Malaysia, to remove basic dye
(methylene blue) from aqueous solution by adsorption was studied. Batch mode experiments were conducted at 30 C to study the effects of pH
and initial concentration of methylene blue (MB). Equilibrium adsorption isotherms and kinetics were investigated. The experimental data were
analyzed by the Langmuir, Freundlich and Temkin models of adsorption. The adsorption isotherm data were fitted well to Langmuir isotherm
and the monolayer adsorption capacity was found to be 70.92 mg/g at 30 C. The kinetic data obtained at different concentrations have been
analyzed using a pseudo-first-order, pseudo-second-order equation and intraparticle diffusion equation. The experimental data fitted very well the
pseudo-second-order kinetic model.
2008 Elsevier B.V. All rights reserved.
Keywords: Coconut bunch waste; Methylene blue; Adsorption isotherm; Equilibrium; Kinetics
0304-3894/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2008.01.034
66 B.H. Hameed et al. / Journal of Hazardous Materials 158 (2008) 6572
Fig. 2. Scanning electron microscope of (a) fresh CBW and (b) dye adsorbed 3.3. Effect of solution pH on dye adsorption
CBW.
Effect of pH on adsorption was studied using 100 mg/L dye
disappeared (1734.82 cm1 (C O stretch); 1507.98 cm1 (NH concentration, pH 212 at 30 C as given in Fig. 4. The dye
deformation) and 1383.98 cm1 (COH bend)) and new peaks adsorption was significantly changed over the pH value of 210.
(2346.73 cm1 , 2276.45 cm1 (NH stretch); 1166.96 cm1 The dye adsorption was constant at pH 1012. The lowest dye
(CN stretch) and 526.12 cm1 (CS stretch)) are also detected. adsorption was recorded at pH 2 (13 mg/g). The equilibrium
These changes observed in the spectrum indicated the possible adsorption (qe ) was found to increase with increasing pH. The qe
involvement of those functional groups on the surface of the increases from 13 to 85 mg/g for an increase in pH from 2 to 12.
CBW in sorption process. Wang et al. [29] reported that MB adsorption usually increases
Fig. 2 shows the SEM micrographs of CBW samples before as the pH is increased. Lower adsorption of MB at acidic pH is
after dye adsorption. The CBW exhibits a caves-like, uneven and probably due to the presence of excess H+ ions competing with
rough surface morphology. The surface of dye-loaded adsorbent, the cation groups on the dye for adsorption sites. At higher pH,
however, shows that the surface of CBW is covered with dye the surface of CBW particles may get negatively charged, which
molecules. enhances the positively charged dye cations through electrostatic
Table 1
Langmuir, Freundlich and Temkin isotherm model constants and correlation
coefficients for adsorption of MB onto CBW
Isotherm Parameters
Langmuir
Q0 (mg/g) 70.92
b (L/mg) 0.029
R2 0.999
Freundlich
KF 13.45
n 3.66
R2 0.953
Table 2
Comparison of adsorption capacities of various adsorbents for MB
Adsorbents Q0 (mg/g) T ( C) Reference
Table 3
Comparison of the pseudo-first-order, pseudo-second-order adsorption rate constants and calculated and experimental qe values obtained at different initial MB
concentrations
Initial conc. (mg/L) qe,exp (mg/g) Pseudo-first-order kinetic model Pseudo-second-order kinetic model
Fig. 10. The variation of the initial rate of adsorption with the initial MB con- Fig. 11. Plots for evaluating intraparticle diffusion rate constant for sorption of
centration. MB onto CBW.
B.H. Hameed et al. / Journal of Hazardous Materials 158 (2008) 6572 71
Fig. 13. Adsorbent mass (W) against volume of effluent (V) treated for different
3.7. Design of batch sorption from isotherm data percentages of MB removal (C0 = 50 mg/L).
A schematic diagram of a batch sorption process is shown 3.8. Cost-estimation of coconut bunch waste sorbent
in Fig. 12 where the effluent contains V (L) of water and an
initial MB concentration C0 , which is to be reduced to C1 in The coconut bunch waste accumulates in the agro-industrial
the adsorption process. In the treatment stage W (g) CBW (dye- yards, has no significant industrial and commercial uses, but
free) is added to solution and the dye concentration on the solid becomes an issue and contributes to serious environmental prob-
changes from q0 = 0 (initially) to q1 . The mass balance for the lems. Hence, the utilization of such agriculture solid waste for
dye in the single-stage is given by wastewater treatment is most desirable. The cost of this waste
as a dye sorbent is only associated with the transport and pro-
V (C0 C1 ) = W(q0 q1 ) (14) cess expenses which are approximately US$ 50/ton whereas
Under equilibrium conditions, the average price of activated carbon used in Malaysia is US$
10001100/ton. Thus the proposed CBW sorbent is more than
C1 Ce and q1 qe 20 times cheaper than activated carbon. Although the adsorp-
tion capacity of CBW may be lower than commercial activated
VC0 + Wq0 = VCe + Wqe (15) carbons, the adsorbent is renewable material, abundantly avail-
able and, therefore, low-cost adsorbent. The CBW would be an
For the adsorption of MB on CBW, the Langmuir isotherm gives economical alternative for the commercially available activated
the best fit to experimental data. Consequently equation can be carbon in removal of basic dye from aqueous solutions.
best substituted for q1 in the rearranged form of Eq. (15) giving
adsorbent/solution ratios for this particular system, 4. Conclusions
W (C0 C1 ) C0 C e
= = (16) In this work, the ability of CBW sorbent to remove MB from
V qe Q0 bCe /(1 + bCe )
aqueous solution was investigated. Experimental results show
Fig. 13 shows a series of plots (50, 60, 70, 80 and 90% dye CBW was effective for the removal of MB from aqueous solu-
removal at different solution volumes, i.e., 1, 2, 3, 4, 5, 6, 7 and tion. Since CBW used in this work is freely, abundantly and
8 L) derived from Eq. (16) for the adsorption of MB on CBW at locally available, the resulting sorbent is expected to be econom-
initial concentration of 50 mg/L. The amount of CBW required ically viable for removal of basic dye from aqueous solution.
for the 90% removal of MB solution of concentration 50 mg/L Results obtained were modeled using three isotherm models:
was 5.1, 10.3, 15.4 and 20.6 g for dye solution volumes of 1, 2, Langmuir, Freundlich and Temkin. Equilibrium isotherms were
3 and 4 L, respectively. well described by the Langmuir equation, giving maximum
adsorption capacity of 70.92 mg/g at 30 C. The adsorption
Table 4 kinetics can be well described by the pseudo-second-order
Intraparticle diffusion constants for different initial MB concentrations at 30 C model equation. The coconut bunch waste appeared to be suit-
Initial conc. (mg/L) qe,cal (mg/g) ki (mg/g h1/2 ) C R2 able for the removal of MB from aqueous solutions.
50 31.814 9.05 10.97 0.977
100 40.309 12.83 11.19 0.972 Acknowledgment
200 60.076 13.69 28.26 0.952
300 61.913 12.42 33.52 0.985 The authors acknowledge the research grant provided by the
400 66.718 15.91 30.61 0.973
Universiti Sains Malaysia under the Research University (RU)
500 64.731 14.36 34.81 0.991
Scheme (Project No: 1001/PJKIMIA/814005).
72 B.H. Hameed et al. / Journal of Hazardous Materials 158 (2008) 6572
References [24] F.D. Ardejani, Kh. Badii, N.Y. Limaee, S.Z. Shafaei, A.R. Mirhabibi,
Adsorption of Direct Red 80 dye from aqueous solution onto almond shells:
[1] N. Sapari, Treatment and reuse of textile wastewater by overland flow, Effect of pH, initial concentration and shell type, J. Hazard. Mater. 151
Desalination 106 (1996) 179182. (2008) 730737.
[2] E.A. Clarke, R. Anliker, Organic dyes and pigments, in: Handbook of envi- [25] D. Ozer, G. Dursun, A. Ozer, Methylene blue adsorption from aqueous
ronmental chemistry, anthropogenic compounds, vol. 3, part A, New York, solution by dehydrated peanut hull, J. Hazard. Mater. 144 (2007) 171
SpringerVerlag, 1980, pp. 181215. 179.
[3] H. Zollinger, Azo Dyes and Pigments. Colour Chemistry-Synthesis, Prop- [26] Y. Bulut, N. Gozubenli, H. Aydn, Equilibrium and kinetics for adsorption
erties and Applications of Organic Dyes and Pigments, VCH, New York, of direct blue 71 from aqueous solution by wheat shells, J. Hazard. Mater.
1987. 144 (2007) 300306.
[4] K.G. Bhattacharyya, A. Sharma, Kinetics and thermodynamics of methy- [27] A. Upadhyay, K. Jayadev, R. Manimekalai, V.A. Parthasarathy, Genetic
lene blue adsorption on Neem (Azadirachta indica) leaf powder, Dyes relationship in Indian coconut accessions based on RAPD markers, Sci.
Pigments 65 (2005) 5159. Hort. 99 (2004) 353362.
[5] E. Forgacsa, T. Cserhatia, G. Oros, Removal of synthetic dyes from wastew- [28] MAO (Ministry of Agriculture), Hectareage of industrial crops by types,
aters: a review, Environ. Int. 30 (2004) 953971. Malaysia, available from World Wide Web: http://www.doa.gov.my, 2006
[6] G. Crini, Non-conventional low-cost adsorbents for dye removal: a review, (accessed online 25 April 2007).
Bioresour. Technol. 97 (2006) 10611085. [29] S. Wang, L. Li, H. Wu, Z.H. Zhu, Unburned carbon as a low-cost adsorbent
[7] B.H. Hameed, A.T.M. Din, A.L. Ahmad, Adsorption of methylene blue for treatment of methylene blue-containing wastewater, J. Colloid Interface
onto bamboo-based activated carbon: kinetics and equilibrium studies, J. Sci. 292 (2005) 336343.
Hazard. Mater. 141 (2007) 819825. [30] J. Eastoe, J.S. Dalton, Dynamic surface tension and adsorption mechanisms
[8] I.A.W. Tan, B.H. Hameed, A.L. Ahmad, Equilibrium and kinetic studies of surfactants at the air water interface, Adv. J. Colloid Interface Sci. 85
on basic dye adsorption by oil palm fibre activated carbon, Chem. Eng. J. (2000) 103 144.
127 (2007) 111119. [31] K.R. Hall, L.C. Eagleton, A. Acrivos, T. Vermeulen, Pore-and
[9] B.H. Hameed, A.L. Ahmad, K.N.A. Latiff, Adsorption of basic dye (methy- solid-diffusion kinetics in fixed-bed adsorption under constant-pattern con-
lene blue) onto activated carbon prepared from rattan sawdust, Dyes ditions, I&EC Fundam. 5 (1966) 212223.
Pigments 75 (2007) 143149. [32] H. Freundlich, Uber die adsorption in losungen (adsorption in solution), Z.
[10] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Optimization of preparation con- Phys. Chem. 57 (1906) 384470.
ditions for activated carbons from coconut husk using response surface [33] R.E. Treybal, Mass Transfer Operations, 2nd ed., McGraw Hill, New York,
methodology, Chem. Eng. J. 137 (2008) 462470. 1968.
[11] D. Kavitha, C. Namasivayam, Experimental and kinetic studies on methy- [34] V.J.P. Poots, G. McKay, J.J. Healy, Removal of basic dye from effluent
lene blue adsorption by coir pith carbon, Bioresour. Technol. 98 (2007) using wood as an adsorbent, J. Water Pollut. Contr. Fed. 50 (1978) 926
1421. 935.
[12] Z. Aksu, Application of biosorption for the removal of organic pollutants: [35] Y.S. Ho, G. McKay, Sorption of dye from aqueous solution by peat, Chem.
a Review, Process Biochem. 40 (2005) 9971026. Eng. J. 70 (1998) 115124.
[13] A.A. Ahmad, B.H. Hameed, N. Aziz, Adsorption of direct dye on palm ash: [36] M.J. Temkin, V. Pyzhev, Recent modifications to Langmuir isotherms, Acta
kinetic and equilibrium modeling, J. Hazard. Mater. 141 (2007) 7076. Physiochim., URSS 12 (1940) 217 222.
[14] B.H. Hameed, A.A. Ahmad, N. Aziz, Isotherms, kinetics and thermody- [37] A.E. Ofomaja, Sorption dynamics and isotherm studies of methylene blue
namics of acid dye adsorption on activated palm ash, Chem. Eng. J. 133 uptake on to palm kernel fibre, Chem. Eng. J. 126 (2007) 3543.
(2007) 195203. [38] F.A. Pavan, E.C. Lima, S.L.P. Dias, A.C. Mazzocato, Methylene blue
[15] M. Hasan, A.L. Ahmad, B.H. Hameed, Adsorption of reactive dye onto biosorption from aqueous solutions by yellow passion fruit waste, J. Haz-
cross-linked chitosan/oil palm ash composite beads, Chem. Eng. J. 136 ard. Mater. 150 (2008) 703712.
(2008) 164172. [39] R. Han, W. Zou, W. Yu, S. Cheng, Y. Wang, J. Shi, Biosorption of methylene
[16] B.H. Hameed, D.K. Mahmoud, A.L. Ahmad, Sorption of basic dye from blue from aqueous solution by fallen phoenix trees leaves, J. Hazard. Mater.
aqueous solution by pomelo (Citrus grandis) peel in a batch system., Col- 141 (2007) 156162.
loids Surf., A: Physicochem. Eng. Aspects 316 (2008) 7884. [40] Y. Bulut, H. Aydn, A kinetics and thermodynamics study of methy-
[17] F.A. Batzias, D.K. Sidiras, Simulation of methylene blue adsorption by lene blue adsorption on wheat shells, Desalination 194 (2006) 259
salts-treated beech sawdust in batch and fixed-bed systems, J. Hazard. 267.
Mater. 149 (2007) 817. [41] F. Banat, S. Al-Asheh, R. Al-Ahmad, F. Bni-Khalid, Bench-scale and
[18] A. Mittal, A. Malviya, D. Kaur, J. Mittal, L. Kurup, Studies on the adsorp- packed bed sorption of methylene blue using treated olive pomace and
tion kinetics and isotherms for the removal and recovery of methyl orange charcoal, Bioresour. Technol. 98 (2007) 30173025.
from wastewaters using waste materials, J. Hazard. Mater. 148 (2007) [42] F. Ferrero, Dye removal by low cost adsorbents: hazelnut shells in compar-
229240. ison with wood sawdust, J. Hazard. Mater. 142 (2007) 144152.
[19] H. Demir, A. Top, D. Balkse, S. lk, Dye adsorption behavior of Luffa [43] M.C. Ncibi, B. Mahjoub, M. Seffen, Kinetic and equilibrium studies of
cylindrica fibers, J. Hazard. Mater. 153 (2008) 389394. methylene blue biosorption by Posidonia oceanica (L.) fibres, J. Hazard.
[20] J.F. Osma, V. Saravia, J.L. Toca, Toca-Herrera, S. Rodrguez, Couto, sun- Mater. 139 (2007) 280285.
flower seed shells: a novel and effective low-cost adsorbent for the removal [44] S. Chakrabarti, B.K. Dutta, Note on the adsorption and diffusion of
of the diazo dye Reactive Black 5 from aqueous solutions, J. Hazard. Mater. methylene blue in glass fibers, J. Colloid Interface Sci. 286 (2005) 807
147 (2007) 900905. 811.
[21] V.J.P. Vilar, C.M.S. Botelho, R.A.R. Boaventura, Methylene blue adsorp- [45] S. Lagergren, Zur theorie der sogenannten adsorption geloester stoffe,
tion by algal biomass based materials: biosorbents characterization and Kungliga Svenska Vetenskapsakad, Handl. 24 (1898) 139.
process behaviour, J. Hazard. Mater. 147 (2007) 120132. [46] Y.S. Ho, G. McKay, The sorption of lead(II) ions on peat, Water Res. 33
[22] F. Cicek, D. zer, A. zer, A. zer, Low cost removal of reactive dyes (1999) 578584.
using wheat bran, J. Hazard. Mater. 146 (2007) 408416. [47] Y.S. Ho, G. McKay, The kinetics of sorption of divalent metal ions onto
[23] V. Ponnusami, S. Vikram, S.N. Srivastava, Guava (Psidium guajava) leaf sphagnum moss peat, Water Res. 34 (2000) 735742.
powder: novel adsorbent for removal of methylene blue from aqueous [48] W.J. Weber Jr., J.C. Morris, Kinetics of adsorption on carbon from solution,
solutions, J. Hazard. Mater. 152 (2008) 276286. J. Sanit. Eng. Div. Proceed. Am. Soc. Civil Eng. 89 (1963) 3159.