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Materials Today: Proceedings 13 (2019) 812–821 www.materialstoday.com/proceedings

ICMES2018

Adsorption of Methylene Blue on industrial softwood waste "Cedar"

and hardwood waste "Mahogany": comparative study
M. El Hajama, b*, N. Idrissi Kandrib, A. Harracha, A. El khomsia, b and A. Zeroualea
a
LCMC, Chemistry Department, Faculty of Sciences and Techniques, University of Sidi Mohammed Ben Abdellah, Road Imouzzer, BP2202 Atlas,
FEZ -Morocco
b
LCA, Chemistry Department, Faculty of Sciences and Techniques, University of Sidi Mohammed Ben Abdellah , Road Imouzzer, BP 2202 Atlas,
FEZ –Morocco

Abstract

In this study, a new approach to treating textile effluents is to exploit industrial wood waste (Cedar and Mahogany) as a clean, a
biodegradable and an inexpensive biosorbents in the adsorption of methylene blue.
The adsorption potential of an aqueous solution of Methylene Blue (MB) on these sawdusts was evaluated by studying the
influence of various experimental parameters governing this adsorption.
Adsorption rates of 98% on Cedar sawdust and 96% on that of Mahogany were reached at pH=4 in room temperature. The
kinetic study showed that the adsorption process follows a pseudo-second order model for the two sawdusts; also, the equilibrium
isothermal model is a Langmuir type. The adsorption capacity of Langmuir model is 217.39 mg per one gram for Cedar with a
regression R² = 0.9509 and 149.25 mg per one gram for Mahogany with R² = 0.9541.
This study revealed that these sawdust used are very effective for the removal of Methylene Blue and can therefore be tested for
other types of industrial dyes.
© 2019 Elsevier Ltd. All rights reserved.
Peer-review under responsibility of the scientific committee of the International Conference on Materials and Environmental
Science, ICMES 2018.

Keywords: Adsorption, Methylene Blue, Cedar, Mahogany, wood waste, valorisation, environment;

*Corresponding author. Tel: +212-674719732

E-mail address: maryam.elhajam@usmba.ac.ma

2214-7853 © 2019 Elsevier Ltd. All rights reserved.

Peer-review under responsibility of the scientific committee of the International Conference on Materials and Environmental Science, ICMES
2018.
 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821 813

1. Introduction

In Morocco, the wood processing industry (sawmills) produces a huge quantities of waste in the form of sawdust
[1], these are sent directly to the areas for energy uses, which generates an environmental pollution due to the
release of toxic gases (CO2, CO, SO2 ..).
Nowadays, several studies have really interested on the environmental and sustainable aspects of sawmill waste,
through the valorization of all kinds of waste from the wood processing industry. The adsorption of synthetic dyes is
one of the widely used methods for the valorization of these sawdusts. Indeed these synthetic dyes are used in
several industrial levels such as, textile, leather, paper ... etc., and their discharges into the environment present a
source of worrying nuisance.
The objective of this work is to study the adsorption of a cationic dye (MB) using the industrial waste of Cedar
and Mahogany woods. The samples of these sawdusts were previously collected, pre-treated and characterized.

2. Materials and Methods

2.1. Materials

2.1.1. Adsorbents

The sawdusts used are collected from a local industrial unit of Fez-Morocco, washed with distilled water, dried at
100 °C and then crushed and sieved at different diameters (1mm, 800μm, 500μm and 100μm).

2.1.2. Adsorbate

The Methylene Blue is a powder synthesized by the "Pierron" company. It is a cationic dye of chemical formula
C6H12ClN3S, with a molar mass of 319.85 g per mole and having a purity higher than 85%. This adsorbate is used in
the form of aqueous solutions at different concentrations.

2.2. Methods

2.2.1. Adsorption procedure

The adsorption experiments have been carried out in glass flasks by stirring the colored solutions in the presence
of each of the two lignocellulosic substrates (sawdust). After each adsorption experiment, the adsorbent is removed
by centrifugation. The filtrate obtained is then analyzed by UV spectrophotometry using an UV2300II
spectrophotometer at the wavelength maxnm.
The amounts of the adsorbed dye were calculated from the concentrations of the solutions before and after
adsorption by the equation 1:

c0  ce
qe  V
m 1
( )

Where:
qe: amount of MB adsorbed at equilibrium (mg / g), and C0, Ce: initial and equilibrium dye concentrations (mg / l).
m: mass of adsorbent (g) and V: volume of the colored solution (l).

The adsorption percentage of Methylene Blue is calculated by the equation 2:

814 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821

c0  ce
% Ads   100 (2)
c0
Where:
C0 and Ce are respectively the initial and the equilibrium dye concentrations (mg / l).

2.3. Study of adsorption kinetics

2.3.1. Pseudo-first-order model

The pseudo-first-order model is expressed by the equation 3 [2]:

Ln(q e  qt )  Ln(q e )  K1t 3

( )

Where:
qe, qt: amounts of MB adsorbed at equilibrium and at time t (mg / g).
K1: rate constant of the first order adsorption reaction of MB on sawdust (min-1), t: contact time (min).
The plot of Ln(q e  qt ) versus time (t) allows to describe the phenomena occurring during the first minutes of
the adsorption process [3].

2.3.2. Pseudo-second-order model

The pseudo-second-order model is expressed by the following equation 4 [4]:

t 1 t
 2

qt K 2 qe qe 

Where:
qe, qt: amounts of MB adsorbed at equilibrium and at time t (mg / g).
k2: rate constant of the second order adsorption reaction of MB on sawdust (g / mg / min), t: contact time (min).
The plot of (t/ qt) versus time (t) allows the determination of the parameters k2 and qe. The pseudo-second order
model is applicable in a wider time interval (usually the whole process of adsorption) [5].

2.4. Study of adsorption isotherms

2.4.1. Langmuir model

The Langmuir model is given by the following equation 5 [6]:

ce c 1
 e  (5)
qe qmax qmax K1

Where:
Ce: Equilibrium dye concentration (mg / l).
qe: amount of MB adsorbed at equilibrium (mg / g), qmax: maximum theoretical adsorption capacity (mg / g).
Kl: constant of thermodynamic equilibrium of adsorption (1 / mg).
The plot of (1/qe) versus (1/ce) allows to determine qmax from the slope (1/qmax) and K1 from the ordinate at the
origin (1/ (qmax K).
 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821 815

2.4.2. Freundlich model

The Freundlich model is given by the following equation 6 [7]:

1
Log(q e )  Log(K f )  Log(ce ) (6)
nf
Where:
qe: amount of MB adsorbed at equilibrium (mg / g), Ce: Equilibrium dye concentration (mg / l).
Kf: Freundlich constant, this is an indication of the adsorption capacity of the adsorbent.
nf: indicates the type of adsorption:
If nf <1 the adsorption is chemical, if nf = 1 the adsorption is linear and if nf> 1 adsorption is physical.
The parameters Kf and nf are determined from the plot of Log(q e ) versus Log(c e ) .

3. Results and discussion

3.1. Effect of sawdust mesh size

The influence of sawdust mesh size on the adsorption rate of Methylene Blue was studied using 1 g of each type
of adsorbent.
The histograms of the different results obtained (fig. 1) indicate the existence of a direct relationship between the
size of the particles adsorbent and the percentage of the adsorption of methylene blue, in fact the percentage of
adsorption is inversely proportional to the mesh size of the sawdusts used which have a direct relationship with the
specific surface area of these latest [8]. We note that more the grain is small; more the transfer to the center is fast
and therefore more the adsorption rate is important, this deduction has been reported by Ghosh et al. [9].
The adsorption percentage obtained increases from about 92% for the mesh size greater than 1000 μm to 98% for
mesh size smaller than 100 μm. Similarly, it is noted that this percentage of adsorption changes slightly (about 2%)
between the two types of sawdust used.

100
Cedar Mahogany
% of MB adsorption

96

92

88
<100µm 100µm-500µm 500µm-800µm 800µm-1000µm >1000µm
ᴓ (µm)

Fig. 1. Effect of mesh size on the MB adsorption, ([MB] = 60ppm, t=1h30min, room T, pH=6 and m=1 g).

3.2. Effect of sawdust mass

In order to estimate the optimum sawdust amount to be added to the colored solution, the experiments were
conducted using different quantities of raw sawdust (0.2-2 g).
816 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821

The results obtained (fig. 2) show an increase in the adsorption rate of MB with the increase of the mass of
sawdust added to the reaction medium, up to a maximum value of 0.8 g for Cedar and 1.2 g for Mahogany.
The increase in the dye reduction rate with the increase in the adsorbents mass is due to the availability of a large
active surface area in sites [10]. This deduction has been reported also by Deng et al. [11].

Cedar Mahogany
100
% of MB adsorption

85

70

55
0 0.5 1 1.5 2
Mass of sawdusts (g)

Fig. 2. Effect of the adsorbents mass on MB adsorption, ([MB] = 60ppm, t = 1h30min, room temperature, pH = 6 and 100μm <Φ <500μm).

3.3. Effect of contact time

The effect of the contact time on the adsorption rate of MB on the two sawdusts was studied during 3 hours (from
5 to 240 min with a pitch of 5 min).
The results obtained (fig. 3) show that the adsorption of methylene blue on the various sawdusts passes through
two stages: one fast and the other slow and decisive. The adsorption rate reaches its maximum in the first of 60
minutes and remains stable along the adsorption. This is due to the availability of a large number of vacant
adsorption sites on the surface of sawdust at the initial stage of adsorption [12].

Cedar Mahogany
99
% of MB adsorption

96

93

90
0 20 40 60 80 100
time (min)

Fig. 3. Effect of contact time on MB adsorption, ([MB] = 60 ppm, 100 μm <Φ <500 μm, room temperature, pH = 6, m = 1 g of sawdust).
 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821 817

3.4. Effect of initial dye concentration

The monitoring of the methylene blue adsorption was carried out at different concentrations ranging from 0.2 to
600 ppm rate.
The results obtained show that the adsorption percentage is practically nil for concentrations not exceeding 5 ppm
(fig. 4-b) and it increase with the concentration until is stabilize from the concentration [MB]=10 ppm.
Cedar reaches its maximum adsorption capacity of MB at an adsorbate concentration of 200 ppm, whereas for
Mahogany, the maximum percentage of adsorption is reached for a concentration not exceeding 100 ppm. Above
these concentrations (fig.4-a), the adsorption rates fall due to the saturation of the adsorption sites noted also by
Ozer et al.[13].

Cedar Mahogany
100

80
% of MB adsorption

60

40

20
a
0
0 100 200 300 400 500 600
Concentration (ppm)

Cedar Mahogany

100

80
% of MB adsorption

60

40

20
b
0
0 20 40 60 80 100
Concentration (ppm)

Fig. 4. Effect of initial dye concentration on MB adsorption, (m = 1 g , 100 μm <Φ <500 μm, room temperature, t = 1h30min and pH = 6).

a: Concentration range of [0.2-600 ppm], b: Concentration range of [0.2-100 ppm]

818 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821

3.5. Effect of pH on MB adsorption

The monitoring of the percentage of adsorption of MB on the two sawdusts as a function of the pH was studied
by varying the pH values from 1 to 10 using a solution of hydrochloric acid HCl (0.1N) or of sodium hydroxide
NaOH (0.1N).
The results obtained (fig. 5) show that the adsorption of BM in a very acidic medium (pH of 1 and 2) is low, but
it reaches the equilibrium at pH = 3 and it stabilizes in a basic medium up to a pH equal to 10. Beyond pH=10, the
medium takes a black color due to the dissolution of wood tannins and also the degradation of sawdust by the
saturated alkaline solution.
This can be explained by the fact that at low pH values 1 and 2, the surface of the adsorbent would be surrounded
by H+ ions which decreases the interaction of methylene blue ions (cationic pollutant) with the sites of the adsorbent.
On the other hand, at pH between 3 and 11, the concentration of H+ decreases, which generates a good interaction
between the dye ions and the surface sites [14]. A similar observation has previously been reported by Hamdaoui et
al. [15].

Cedar Mahogany
100

93
% of MB adsorption

86

79

72

65
1 2 3 4 5 6 7 8 9 10
pH

Fig. 5. Effect of pH on BM adsorption, ([MB] = 60ppm, t = 1h30min, 100μm <Φ <500μm, room temperature, m = 1 g of sawdust)

3.6. Kinetics of adsorption

From the results obtained (Fig. 6 and Table. 1), we observe that for the first order kinetic model the correlation
coefficients R2 are 0.9355 and 0.899 for sawdust of Cedar and Mahogany respectively. The adsorbed quantities at
equilibrium, determined experimentally are different from those calculated. On the other hand, the correlation
coefficient for the pseudo-second order kinetic model is 1 for both sawdust and the equilibrium adsorbed quantities
determined experimentally are closer to those calculated.
This observation suggests the applicability of the second-order kinetic model to the adsorption process in this
study. Similar results have been observed by Abdallah et al. [16].
 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821 819

First order (Cedar) pseudo- second-order (Cedar)

t (min) 50
0
0 50 100 40
-1
30

t/qt
Ln(qe-qt)

-2
20
-3 y = 0.1696x + 0.0761
10
R² = 1
-4 y = -0.0356x - 1.2685 0
R² = 0.9355 0 100 200 300
-5
t(min)

First order (Mahogany) pseudo- second-order (Mahogany)

t (min)
0 50
0 20 40 60 40
-1
30
Ln(qe-qt)

t/qt
-2
20
-3 y = 0.1714x - 0.0309
10 R² = 1
-4 y = -0.055x - 1.5352
0
R² = 0.899
-5 0 100 200 300
t (min)

Fig. 6. Graphical representation of the modeling of adsorption kinetics of MB on Cedar and Mahogany, first-order and pseudo-second-order
models

The parameters of the adsorption kinetics of MB on sawdust of Cedar and Mahogany are summarized in Table 1:

Table. 1. Parameters of adsorption kinetics of MB on Cedar and mahogany sawdusts (1st and 2nd order)

1st order 2nd order

R2 K1(min-1) qe (mg/g) R2 K2 (g/mg.min) qe (mg/g)
Cedar 0.9355 0.0356 0.2812 1 0.3779 5.8962

Mahogany 0.899 0.055 0.2154 1 1.0417 5.8343

3.7. Adsorption isotherms

The plotting of the experimental values for the adsorbate / adsorbent systems studied indicate that the adsorption
process of Methylene Blue on the two sawdusts (Fig. 7 and table. 2) is favorably described by the Langmuir
isotherm with excellent linear regression coefficients R2 which are close to the unit.
The maximum adsorption capacities of MB on the Cedar and Mahogany sawdust are approximately 217.39 mg
per gram and 149.25 mg per gram respectively.
820 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821

Langmuir model (Cedar) Freundlich model (Cedar)

0.4 2

0.3 1.5

Log qe
1/qe

0.2 1

0.1 0.5 y = 0.6291x + 0.7604

y = 0.1795x + 0.0046
R² = 0.8976
R² = 0.9509
0 0
0 1 2 -0.5 0 0.5 1 1.5
1/ce Log ce

Langmuir model (Mahogany) Freundlich model (Mahogany)

0.4 1.5
0.3
1
1/qe

Log qe
0.2

0.1 y = 0.3741x + 0.0067 0.5

y = 0.668x + 0.5373
R² = 0.9541
0 R² = 0.8992
0 0.5 1 0
1/ce 0 0.5 1 1.5
Log ce

Fig. 7. Linear modeling of the Langmuir and Freundlich adsorption isotherms of the MB on Cedar and Mahogany

The calculated parameters of Langmuir and Freundlich adsorption isotherms are collated in Table 2.

Table. 2. Parameters of Langmuir and Freundlich isotherms of BM adsorption on cedar and mahogany sawdusts

Methylene Blue
Isotherms Parameters Cedar Mahogany
Qmax (mg/g) 217.39 149.25
Kl 0.026 0.018
Langmuir R2 0.9509 0.9541
Kf 5.76 3.45
nf 1.59 1.49
Freundlich R 2
0.8976 0.8992
 M. El hajam et al. / Materials Today: Proceedings 13 (2019) 812–821 821

4. Conclusion

The present study involves the use of a new biosorbent from the sawdust of two types of wood (Cedar and
Mahogany) to demonstrate their low-cost adsorption potential for the removal of environmentally harmful dyes.
A maximum color suppression of 98% and 96% was achieved for a concentration range of 10 to 200 ppm for
Cedar and 10 to 100 ppm for Mahogany, at room temperature and at the initial pH of the solution during the first 60
minutes of adsorption. Increasing the temperature from 20 to 50 ° C has no effect on the adsorption rate.
In addition, the exploitation of the adsorption isotherms using different classical models has shown that the
equilibrium of the biosorption process follows the Langmuir model. The adsorption kinetics of Methylene Blue on
the both sawdusts is described by a pseudo-second-order model.
The results of the adsorption of Methylene Blue on the Cedar and Mahogany sawdust are very encouraging; this
could be an alternative to remove the rejects of textile. The Cedar can be tested to absorb the dyes with a very high
concentration range.

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