Professional Documents
Culture Documents
Textile Dye Beech Wood
Textile Dye Beech Wood
Textile Dye Beech Wood
a r t i c l e i n f o a b s t r a c t
Article history: The purpose of this paper is to establish the experimental conditions for removal of several textile dyes
Received 13 December 2007 from aqueous solutions by sorption on beech wood sawdust, an industrial waste lignocellulosic product.
Received in revised form 31 March 2008 From the six dyes tested, the sorbent shows preference for three dyes: Direct Brown, Direct Brown 2
Accepted 12 June 2008
and Basic Blue 86. Sorption of dyes on the beech wood sawdust is dependent on the nature of dye, pH,
Available online 21 June 2008
dyes concentration, contact time, and amount of sorbent. By comparative kinetic studies, the rate of
sorption was found to conform with good correlation to pseudo-second-order kinetics. The parameters
Keywords:
that characterize the sorption were determined on the basis of Langmuir isotherms. The preference of
Sorption
Dyes
beech sawdust for dyes increases as follows: Basic Blue 86 < Direct Brown 2 < Direct Brown. The maximum
Beech wood sawdust capacity of sorption of the commercial dye (of ∼60% purity) was found to be 526.3 mg g−1 for Direct Brown.
Equilibrium isotherms © 2008 Elsevier B.V. All rights reserved.
Kinetics
0304-3894/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2008.06.046
1458 V. Dulman, S.M. Cucu-Man / Journal of Hazardous Materials 162 (2009) 1457–1464
maximum retention value of adsorption of 333.3 mg g−1 was isotherms. The experimental data were also analysed using the first
reached for the commercial dye Direct Orange 8 of ∼52% purity and second order kinetic models.
[11].
Batch and column kinetics of some basic dyes on untreated 2. Materials and methods
or treated beech sawdust was investigated in order to explore its
potential use as a low-cost adsorbent for textile wastewaters. The 2.1. Sorbent
obtained results indicated that treatment with CaCl2 [7] or pre-
hydrolysis [10] enhances the adsorption properties of the original The beech wood sawdust obtained from the local wood process-
material. Also an increase of initial pH from 8 to 11.5 increases the ing industry was milled and screened and then sieved. The particles
amount of methylene blue adsorbed [8]. under 0.16 mm were used in all experiments. All the results were
Beech sawdust and wheat straw was used for the preparation reported to mass of dry adsorbent (105 ◦ C).
of ion exchangers, which might be used for decolorization of tex-
tile wastewater [23]. A product with anion exchanger properties 2.2. Dyes
was obtained by chemical modification of beech wood sawdust by
quaternization and crosslinking [24]. Cr2 O7 2− ions are significantly There were used commercial dyes, without a preliminary purifi-
adsorbed on beech sawdust. The maximum sorption efficiency of cation. The dyes were purchased from the Faculty of Textiles and
100% has been obtained at pH 1 [25]. Leather, Iasi:
The aim of this work is to study the removal of some commercial
textile dyes: Direct Brown, Direct Brown 2 and Basic Blue 86 by • C.I. Direct Brown 2 with a content of ∼60% pure dye.
adsorption onto beech sawdust. • C.I. Direct Brown with a content of ∼60% pure dye.
The influence of some parameters such as: nature of dye, pH • C.I. Basic Blue 86 with a content of ∼40% pure dye.
of initial solutions, dyes concentration, contact time and adsor-
bent dosage has been studied. The parameters that characterize The molecular structure and some characteristics of dyes are
the adsorption were estimated using Langmuir and Freundlich reported in Table 1. Aqueous solutions of 1000 mg L−1 textile dye
Table 1
Selection of dyes (pHi –pH of the initial dye solution)
were prepared using double distilled water and they were subse-
quently diluted when necessary.
Fig. 2. Effect of agitation time and dye concentration on removal of dyes by beech
wood sawdust.
For all three dyes the sorption is very fast initially. It was
observed that depending on concentration approximately 90%
Direct Brown, 72–52% Direct Brown 2 and 92–57% Basic Blue 86
is retained after 15 min time of contact with the sorbent.
The rate constant for the adsorption of dyes on beech wood saw-
dust was obtained using the equations of pseudo-first-order system
(Lagergren) and pseudo-second-order system (Ho). The intraparti-
cle diffusion was also considered. A detailed approach of these
models for acid and basic dyes is given in many papers and among
them could be mentioned those of Ho and McKay [27], Ho and
Chiang [28] and Shiau and Pan [29]. Fig. 3. Lagergreen plots for the sorption of dyes by beech wood sawdust.
V. Dulman, S.M. Cucu-Man / Journal of Hazardous Materials 162 (2009) 1457–1464 1461
Table 2
Kinetic parameters for the effect of initial concentration for the investigated dyes
Dye c0 (mg L−1 ) qe,experimental First order Second order Intraparticle diffusion
(mg g−1 )
qe,calculated k1 (min−1 ) R2 qe,calculated k2 (g mg−1 min−1 ) h (mg g−1 min−1 ) R2 ki (mg g−1 min−1/2 )
(mg g−1 ) (mg g−1 )
Brown 2 320 mg L−1 0.0268 min−1 and for Basic Blue 86 100 mg L−1
0.0522 min−1 . For all three dyes there is a great disagreement
between experimental and calculated values of concentration at
equilibrium.
h = k2 q2e (5)
qt = ki t 1/2 (6)
1 1 1
= + (8)
qe bqm ce qm
Table 3
Analysis of Langmuir isotherms
dyes decreases as follows: Direct Brown > Direct Brown 2 > Basic
Blue 86.
The maximum retention capacity is 526.3 mg g−1 for the textile
dye Direct Brown (with a content of ∼60% pure dye).
Together with other studies on the beech wood sawdust the
results of the present study encourage us to consider that this nat-
ural material, of low cost and available in large quantities, could be
a convenient sorbent for removal of dyes from textile wastewaters.
Acknowledgement
Financial support for the present work was obtained from 1469
CNCSIS Project.
References
Fig. 6. Langmuir plots for the sorption of dyes by beech wood sawdust.
[1] C. Hessel, C. Allegre, M. Maisseu, F. Charbit, P. Moulin, Guidelines and legislation
for dye house effluents, J. Environ. Manage. 83 (2007) 171–180.
librium or separation factor [13,31]: [2] S. Nawar, H. Doma, Removal of dyes from effluents using low-cost agricultural
by-products, Sci. Total Environ. 79 (1989) 271–279.
1 [3] G. Crini, Non-conventional low-cost adsorbents for dye removal: a review,
RL = (10) Bioresource Technol. 97 (2006) 1061–1085.
1 + bc0 [4] E. Forgacs, T. Cserháti, G. Oros, Removal of synthetic dyes from wastewaters: a
review, Environ. Int. 30 (2004) 953–971.
where c0 is the initial concentration of dye (mg L−1 ). [5] C.I. Pearce, J.R. Lloyd, J.T. Guthri, The removal of colour from textile wastewater
Values of RL between 0 and 1 (Table 3) show a favourable adsorp- using whole bacterial cells: a review, Dyes Pigments 58 (2003) 179–196.
tion. Batzias and Sidiras [9] found RL values to be close to zero for [6] A. Shukla, Y.H. Zhang, P. Dubey, J.L. Margrave, S. Shyam, The role of sawdust
in the removal of unwanted materials from water, J. Hazard. Mater. 95 (2002)
two basic dyes, methylene blue and basic blue, adsorbed on treated 137–152.
beech sawdust. For untreated sawdust the authors have obtained [7] F.A. Batzias, D.K. Sidiras, Dye adsorption by calcium chloride treated beech
higher values of RL . sawdust in batch and fixed-bed systems, J. Hazard. Mater. 114 (2004) 167–174.
[8] F.A. Batzias, D.K. Sidiras, Simulation of dye adsorption by beech sawdust as
The data for the adsorption of dyes on sawdust are presented in
affected by pH, J. Hazard. Mater. 141 (2007) 668–679.
Fig. 6. The constants obtained by regression analysis conform well [9] F.A. Batzias, D.K. Sidiras, Simulation of methylene blue adsorption by salts-
to Langmuir equation with good correlation coefficients varying treated beech sawdust in batch and fixed-bed systems, J. Hazard. Mater. 149
(2007) 8–17.
from 0.9913 to 0.9982 (Table 3). This good agreement shows the
[10] F.A. Batzias, D.K. Sidiras, Dye adsorption by prehydrolysed beech sawdust in
homogeneity of the adsorbent surface. batch and fixed-bed systems, Bioresource Technol. 98 (2007) 1208–1217.
The Langmuir analysis for comparing the adsorption of the three [11] V. Dulman, S. Cucu-Man, V.I. Popa, R. Mureşan, Adsorption properties of beech
investigated dyes on the same adsorbent shows the greatest mono- wood sawdust related to some textile dyes, Anal. Şt. Univ. “Al. I. Cuza” Iaşi VIII
(2000) 245–252.
layer capacity of 526.3 mg g−1 for Direct Brown and the following [12] V.K. Kumar, S. Sivanesan, Isotherms for Malachite Green onto rubber wood
order of preference: Direct Brown > Direct Brown 2 > Basic Blue 86. (Hevea brasiliensis) sawdust: comparison of linear and non-linear methods,
The comparison of Langmuir isotherm constants for similar dyes Dyes Pigments 72 (2007) 124–129.
[13] F. Ferrero, Dye removal by low cost adsorbents: hazelnut shells in comparison
indicates that beech wood sawdust is an effective adsorbent for the with wood sawdust, J. Hazard. Mater. 142 (2007) 144–152.
investigated dyes compared to other non-conventional sorbents [14] M. Özacar, I.A. Şengil, Adsorption of metal complex dyes from aqueous solutions
[32–35]. by pine sawdust, Bioresource Technol. 96 (2005) 791–795.
[15] M. Özacar, I.A. Şengil, A kinetic study of metal complex dye sorption onto pine
sawdust, Process Biochem. 40 (2005) 565–572.
3.5.2. Freundlich isotherm [16] O. Hamdaoui, Batch study of liquid-phase adsorption of methylene blue using
Analyses of the experimental data set show that Freundlich cedar sawdust and crushed brick, J. Hazard. Mater. 135 (2006) 264–273.
[17] N. Yeddou, A. Bensmaili, Kinetic models for the sorption of dye from aqueous
model is not appropriate for the prediction of the isothermal pro- solution by clay–wood sawdust mixture, Desalination 185 (2005) 499–508.
files for the sorption of the investigated dyes on beech sawdust. [18] V.K. Garg, M. Amita, R. Kumar, R. Gupta, Basic dye (methylene blue) removal
from simulated wastewater by adsorption using Indian rosewood sawdust: a
timber industry waste, Dyes Pigments 63 (2004) 243–250.
4. Conclusions [19] S. Chakraborty, S. De, J.K. Basu, S. DasGupta, Treatment of a textile effluent:
application of a combination method involving adsorption and nanofiltration,
The beech wood sawdust can be considered an efficient non- Desalination 174 (2005) 73–85.
[20] I. Safarik, M. Safarikova, F. Weyda, E. Mosiniewicz-Szablewska, A. Slawska-
conventional adsorbent for removal of three commercial dyes: Waniewska, Ferrofluid-modified plant-based materials as adsorbents for batch
Direct Brown, Direct Brown 2 and Basic Blue 86, from six dyes separation of selected biologically active compounds and xenobiotics, J. Magn.
tested. Magn. Mater. 293 (2005) 371–376.
[21] V. Dulman, S. Cucu-Man, V.I. Popa, Sorption of some textile dyes by oak wood
The extent of dye removal decreases with the increasing of the sawdust, Cell. Chem. Technol. 36 (2002) 515–525.
solution pH for Direct Brown and Direct Brown 2. For these two [22] V.G. Petrovici, V.I. Popa, The Chemistry and the Chemical Processing of Wood,
dyes the optimum pH was of 3.0 and for the cationic dye Basic Blue vol. II, Lux Libris, Brasov, 1997 (in Romanian).
[23] Y.A. Laszlo, Removing acid dyes from textile wastewater using biomass for
86 of 4.43–7.07.
decolorization, Am. Dyest. Rep. 83 (1994) 17–20.
The kinetics of adsorption for the three commercial dyes on [24] I. Šimkovic, Preparation of anion exchangers from beech sawdust and wheat
beech sawdust follows the pseudo-second-order rate expression. straw, Ind. Crop. Prod. 10 (1999) 167–173.
[25] F.N. Acar, E. Malkoc, The removal of chromium(VI) from aqueous solutions by
It has been also concluded that the intraparticle diffusion is not the
Fagus orientalis L., Bioresource Technol. 94 (2004) 13–15.
only rate-controlling step. [26] C. Namasivayam, D. Prabha, M. Kumutha, Removal of direct red and acid brilliant
The experimental data were well correlated by the Langmuir blue by adsorption on to banana pith, Bioresource Technol. 64 (1998) 77–79.
adsorption isotherm. The parameters that characterize the sorption [27] Y.S. Ho, G. McKay, Sorption of dye from aqueous solution by peat, Chem. Eng. J.
70 (1998) 115–124.
were determined. The obtained values indicate favourable adsorp- [28] Y.S. Ho, C.C. Chiang, Sorption studies of acid dyes by mixed sorbents, Adsorption
tion for the tested dyes on beech wood sawdust. The preference for 7 (2001) 139–147.
1464 V. Dulman, S.M. Cucu-Man / Journal of Hazardous Materials 162 (2009) 1457–1464
[29] C.Y. Shiau, C.C. Pan, Adsorption of Basic Dyes from aqueous solution by various [33] M.M. Nassar, Y.H. Magdy, Removal of different basic dyes from aqueous solu-
adsorbents, Sep. Sci. Technol. 39 (2004) 1733–1750. tions by adsorption on palm-fruit bunch particles, Chem. Eng. J. 67 (1997)
[30] C. Namasivayam, N. Kanchana, Waste banana pith as adsorbent for color 223–226.
removal from wastewaters, Chemosphere 25 (1992) 1691–1705. [34] V. Vadivelan, V.K. Kumar, Equilibrium, kinetics, mechanism, and process design
[31] C. McKay, H.S. Blair, J.R. Gardner, Adsorption of dyes on chitin. I. Equilibrium for the sorption of methylene blue onto rice husk, J. Colloid Interf. Sci. 286
studies, J. Appl. Polym. Sci. 27 (1982) 3043–3057. (2005) 90–100.
[32] N. Kannan, M.M. Sundaram, Kinetics and mechanism of removal of methylene [35] G. McKay, G. Ramprasad, P. Mowli, Desorption and regeneration of dye colours
blue by adsorption on various carbons—a comparative study, Dyes Pigments 51 from low-cost materials, Water Res. 21 (1987) 375–377.
(2001) 25–40.