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Journal of Colloid and Interface Science 337 (2009) 3238

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Journal of Colloid and Interface Science


Reactive Black dye adsorption/desorption onto different adsorbents:

Effect of salt, surface chemistry, pore size and surface area
A.W.M. Ip, J.P. Barford, G. McKay *
Department of Chemical and Biomolecular Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong

a r t i c l e i n f o a b s t r a c t

Article history: The adsorption of a large reactive dye, Reactive Black 5 dye, onto two bamboo based active carbons using
Received 26 March 2009 phosphoric acid in a two stage activation process and three conventional adsorbents, carbon F400, bone
Accepted 7 May 2009 char and peat, has been studied. The monolayer saturation adsorption capacities for Reactive Black 5
Available online 12 May 2009
were determined by the Langmuir isotherm analysis and are: 176, 157, 7, 447 and 545 mg dye/g adsor-
bent for active carbon F400, bone char, peat, bamboo carbon (2123 m2/g) and bamboo carbon (1400 m2/
Keywords: g), respectively. The equilibrium experiments were analysed using three isotherms, Langmuir, Freundlich
and RedlichPeterson and the based on the lowest SSE values, the RedlichPeterson was the best t cor-
Reactive dye
relation. The effect of adding salt, in the form of sodium phosphate, on the adsorption capacities has been
Bamboo activated carbon studied and was found to increase the adsorption capacities of both bamboo carbons to over 900 mg/g.
Bone char 2009 Elsevier Inc. All rights reserved.
Ionic strength

1. Introduction ation. Several different adsorbent source materials have already

shown the potential for dye adsorption [6], and there is a need to
Synthetics dyes have been widely used in textile, paper, food, search for adsorbents that have the potential to bind with reactive
cosmetics and pharmaceutical industries. The world total annual dyes.
dyes production is more than 7  105 tonnes [1] and about 2% of Bamboo cane, indigenous to Hong Kong and China, is available
dyes produced annually are discharged in efuent from manufac- as scaffolding waste from Hong Kong construction projects. A two
turing operations [2]. There was commonly about 1015% of un- step process has been used for production of bamboo derived acti-
used dyestuff entering the wastewater directly in the dyeing vated carbon. The rst step is a low temperature impregnation at
process but the loss of some reactive dyes in the dyeing process 150 C using phosphoric acid and the second step is the carboniza-
can be as high as 50% [2]. The discharge of highly colored efuent tion at high temperatures, namely, 600 C. The bamboo activated
is currently one of the worlds major environmental problems as carbons have been used successfully for the removal of acid dyes
some of the dyes and their metabolites are either toxic or muta- [79]. Bone char is produced by the calcination of cattle bones at
genic and carcinogenic and pose a potential health hazard to all 1000 C in the absence of oxygen and has shown a good adsorption
forms of life [3,4]. The use of reactive dyes has grown rapidly re- capacity for inorganic contaminants such as uoride [10] and me-
cently due to the increasing use of cellulosic bers and the techni- tal ions such as cadmium, copper and zinc [11,12], and has found
cal and economic limitations of other dyes used for these bers [5]. applications in the sugar and water purication [13]. Although,
However, reactive dyes have rather low rates of xation, and a high bone char has shown comparable dye removal capacity as acti-
concentration of reactive dyes is discharged into the efuent. They vated carbon, its use as an adsorbent for color removal is still lim-
are soluble in water and not easily biodegradable and thus the ited [14]. Peat, which is a low-grade and relatively inexpensive
reactive dyes may still remain in the efuent even after extensive carbonaceous fuel, is known to have excellent ion-exchange prop-
treatment [5]. The conventional treatments such as coagulation, erties and has received attention in wastewater treatment over the
occulation, and biological treatment are no longer able to achieve past 30 years. Commercial activated carbon, Filtrasorb 400 (F400),
high quality treated water. Adsorption is growing extensively in which was produced by steam activation of bituminous coal, has
use for wastewater treatment due to its ability to remove different been extensively studied for the adsorption of different kinds of
types of dye, produce high quality treated water and ease of oper- dyes and it will be used as model to compare with other
* Corresponding author. Fax: +852 2358 0054. Large amounts of salts have been utilized in the dyeing process
E-mail address: kemckayg@ust.hk (G. McKay). and it has been found that dissolved salts in aqueous phase affect

0021-9797/$ - see front matter 2009 Elsevier Inc. All rights reserved.
A.W.M. Ip et al. / Journal of Colloid and Interface Science 337 (2009) 3238 33

the adsorption capacity of many organics in activated carbon. The 2.2. Chemical and physical characterization of the adsorbents
salts can alternate the surface charge of adsorbent and change the
ionic nature, hydrophobicity, size and solubility of the adsorbate The surface acidic and basic function groups were determined
[15,16]. Theoretically, when the electrostatic interaction between by Boehm titration method [26]. For the measurement of surface
the dye molecules and the adsorbent surface is attractive, addition acidity, 0.2 g of adsorbents were contacted with 50 ml of 0.05 N
of salts will decrease the adsorption capacities [1719], whereas, standard NaOH and shaken for 2 days. The mixture was ltered
when the electrostatic interaction between the dye molecules and then back-titrated with 0.05 N standard HCl. For the measure-
and the adsorbent surface is repulsive, addition of salts will in- ment of surface basicity, 0.2 g of adsorbents were contacted with
crease the adsorption capacity of the system [2023]. As the posi- 50 ml of 0.05 N standard HCl and shaken for 2 days. The mixture
tive and negative ions in the salts can neutralize the surface charge was ltered and then back-titrated with 0.05 N standard NaOH.
of the carbon and charged dye molecules, and reduce the electro- Mass titrations were employed to determine the point of zero
static interactions between the dye molecules and the adsorbent charge of the adsorbents. Different masses of adsorbent materials
surface [24]. For nonpolar hydrophobic chemicals, the presence within the concentration range 5100 g/L were put into contact
of salts can compete with the adsorbate for the active sites, which with a 0.01 M of KCl solution and shaken for 24 h until equilibrium
leads to the decrease of adsorption capacities [25]. pH was reached. The pHpzc is the pH at which a plateau is achieved
In present study, various adsorbents from different sources when plotting equilibrium pH versus adsorbent mass.
including bamboo derived activated carbons, bone char and peat The textural properties of the adsorbents were performed by
were chosen. They were tested for their adsorption capacity on a determining the nitrogen adsorption/desorption isotherm at
dye, Reactive Black 5 (RB 5) and compared with a commercial acti- 196 C using a Quantachrome Autsorb 1. The specic surface area
vated carbon (F400). In order to have a better understanding on the was calculated using the BET equation (SBET). The total pore volume
adsorption mechanisms of reactive dyes, desorption of reactive dye (Vp) was estimated from the amount of nitrogen adsorbed at a rel-
and the effect of salt on the adsorption of reactive dye, Reactive ative pressure of P/P0 = 0.97 and the average pore diameter was
Black 5, has been investigated. calculated from Dp = 4Vp/SBET. The micropores and mesopores vol-
ume were calculated using alpha-s method [27] and BJH method
2. Materials and methods [28], respectively.

2.1. Materials 2.3. Adsorption studies

Synthetic carbons, activated with phosphoric acid, have been Equilibrium adsorption studies were conducted by contacting
described and discussed in previous work [9]. Briey, the crushed 50 ml of dye solution of different initial concentration with
bamboo was impregnated with 85% phosphoric acid to a desired 0.05 g of adsorbent in glass bottles. The bottles were shaken until
impregnation ratio at 150 C for 2 h and carbonized at 600 C for equilibrium is reached. Upon equilibration, solutions were ltered
4 h in a ow of nitrogen. After carbonization, the carbon was through a 0.22 lm syringe lter, and analyzed by UVvis spectro-
cooled and washed with hot deionized water until the pH of wash photometer (Ultrospec 4300 pro) at its maximum absorbance
water became 5.5. Two bamboo activated carbons with impregna- (kmax = 599 nm) to determine the residual equilibrium liquid-phase
tion ratio 2 (BACX2) and 6 (BACX6), peat (sphagnum peat), bone dye concentration. The equilibrium adsorption capacity, qe (mg/g),
char (Brimac) and F400 (Calgon) were used for the adsorption at different dye concentrations was determined by a mass balance
studies. The particle size of peat, bone char and F400 used for the on the dye:
studies ranged from 500 to 710 lm and powdered activated car-
VC 0  C e
bon (<180 lm) was used for bamboo activated carbon. qe
In order to investigate the carbon produced for dye adsorption,
Reactive Black 5 (Chemical formula = C26H21N5Na4O19S6, MW = where C0 (mg/L) is the initial concentration, Ce (mg/L) is the equilib-
991.82 g/mol, and kmax = 599 nm), which is widely used in the dye- rium concentration in the liquid phase, V is the volume of liquid
ing industries is selected and its structure is produced by Chem- phase (L), and m is the mass of the adsorbent (g).
Draw and shown in Fig. 1. The dye was supplied by International The effect of salts on the adsorption of the dyes was investi-
Laboratory (USA). gated according to the same procedure. 0.05 g of adsorbent was

Fig. 1. Molecular structure of the Reactive Black 5.

34 A.W.M. Ip et al. / Journal of Colloid and Interface Science 337 (2009) 3238

added to 50 ml of 400 mg/L or 1000 mg/L of dye with 0.1 M sodium Table 2
phosphate (adjusted to pH 7 using 0.5 M HCl) or 0.1 M sodium Acidity, basicity and point of zero charge (pHpzc) of the ve adsorbents.

chloride and shaken until equilibrium was reached. After the Adsorbent Total acidic groups (mmol/g) Total basic groups (mmol/g) pHpzc
equilibrium reached, the solution phase dye concentration was F400 0.396 0.420 7.33
determined. Bone char 0.13 3.067 9.83
Peat 2.26 0.923 4.39
2.4. Desorption study BACX2 2.52 0.045 1.84
BACX6 2.50 0.150 1.93

Adsorbents were contacted at a high dye concentration of

2000 mg/L until equilibrium was achieved. The adsorbents were
then ltered and dried in the vacuum oven at 40 C. The dye con- the adsorbate. The acidity/basicity and pHpzc are important chem-
centration in the liquid phase is measured in order to calculate the ical characteristics of adsorbents as it determines the net charge of
dye adsorbed onto the adsorbents. The adsorbents were then al- the adsorbent surface in the solution. Table 2 summarizes the
lowed to contact with 50 ml of deionized water at different pH chemical characteristics of the adsorbents. The results showed that
and 0.1 M sodium phosphate (pH 7) for the predetermined equilib- F400 contains both acidic and basic properties. F400 has more ba-
rium time of adsorption. The amount of dye desorbed was calcu- sic properties and has a relatively low density of surface functional
lated from the concentration of desorbed dye in the liquid phase. group. The combined effect of all functional groups determines the
The percentage of the dye desorbed from the adsorbents is pHpzc which is slightly alkaline for F400. In contrast, bamboo acti-
calculated: vated carbon has more acidic properties and has a relatively high
density of surface functional group as phosphate-containing carbo-
Mass of dye desorbed naceous structures like acid phosphates and polyphosphates are
Desorption%  100%
Mass of dye adsorbed present on the surface of synthetic phosphoric acid-activated car-
bons [30]. This result implied that the pHpzc is the lowest in all
3. Results and discussion adsorbents. Bone char also showed more basic properties, and
the basic and acidic sites are formed by the protonation and depro-
3.1. Physical characterization of adsorbents tonation of the hydroxyapatite surface hydroxyl groups [10]. Peat
surface is essentially acidic due to the extensive presence of car-
The adsorption of organic compounds is mainly controlled by boxylic groups of humic acid and fulvic groups. The basic groups
the physical interactions and chemical interactions between the may be attributed to the small number of phenolic hydroxides
adsorbates and the adsorbents. The physical characteristics of the on the peat.
adsorbent control the access of molecules to the ner pore inside
the carbon. The accessible adsorbent surface is especially impor- 3.3. Equilibrium isotherms for reactive dye adsorption on activated
tant for the adsorption of large molecules such as synthetic organic carbon
chemicals and naturally occurring organic materials. The physical
textures of the adsorbents were summarized in Table 1, indicating The equilibrium liquid phase concentration (Ce) for different
that the adsorbents have quite large differences in surface area, adsorbents was measured and their adsorption capacity (qe) was
pore volume and average pore diameter. Pores of adsorbents can calculated and the results which are expressed as plots of solid-
be divided into micropores (pore size <2 nm) and mesopores (pore phase dye concentration against liquid-phase dye concentration
size ranged between 2 and 50 nm). F400 has a typical high surface are shown in Fig. 2. It was found that, both bamboo activated car-
area for commercial activated carbons [29]. It has a larger volume bons have a much higher adsorption capacity than other adsor-
of micropore than mesopore and the smallest average pore diam- bents. It is because both bamboo activated carbons have a much
eter, indicating that the carbon has a higher microporosity. Both higher surface area and pore volume than other adsorbents.
bamboo activated carbons have a much higher surface area and Although, BACX2 has a higher surface area than that of BACX6,
pore volume compared with other adsorbents and BACX2 gives the adsorption capacity of BACX6 is higher. It is because BACX6
the highest surface area and micropore volume, whereas, BACX6 has a much higher mesopore volume than BACX2 and the meso-
has the highest mesopore volume. Bone char has a relatively low pore volume is important for adsorbing large molecules
surface area as it lacks microporosity which contributes most for [20,31,32]. The adsorption of dye molecules is restricted by nar-
surface area. Peat only has a very low surface area and pore vol-
ume, therefore, its sorption characteristic is mainly due to the
chemical interactions between the sorbate and its surface func-
tional groups.
F400 Bone Char Peat BACX2 BACX6
3.2. Chemical characterization of adsorbents
The chemical characteristics of the adsorbents affect the attrac- 500
qe (mg/g)

tive or repulsive interactions between the adsorbent surface and

Table 1 300
Specic surface area (SBET), micropore volume (Vmicro), mesopore volume (Vmeso) and
the average diameters (Dp) of the ve adsorbents. 200

Adsorbent 2
SBET (m /g) 3
Vmicro (cm /g) 3
Vmeso (cm /g) Dp (nm) 100
F400 793 0.363 0.123 2.44 0
Bone char 107 0 0.255 9.43 0 50 100 150 200 250 300 350 400 450 500 550 600
Peat 0.7 0 0.001 5.52
BACX2 2123 0.494 0.943 2.79
Ce (mg/L)
BACX6 1400 0.209 2.008 5.32
Fig. 2. Experimental adsorption capacities of the ve adsorbents.
A.W.M. Ip et al. / Journal of Colloid and Interface Science 337 (2009) 3238 35

rower pores and the presence of high total surface area and wider Table 3
pores always exhibited high dye adsorption capacities [33]. This Isotherm constants for RB 5 using different models.

showed that the pore structure of the adsorbents is an important Adsorbents F400 Bone char Peat BACX2 BACX6
factor that determines the adsorption capacity of reactive dyes. Langmuir isotherm
The surface chemistry of the adsorbents is another important KL 8.30 23.28 0.016 46.50 141.55
factor that controls the adsorption of adsorbate. The adsorbents aL 0.05 0.15 0.002 0.10 0.26
have a net negative charge on the surface when the equilibrium qe (mg/g) 175.81 156.51 7.003 446.98 545.22
SSE 867.54 1966.40 0.157 5051.04 19941.80
pH of the solution is higher than the pHpzc of the adsorbents,
whereas, the adsorbents have a net positive charge when the equi- Freundlich isotherm
aF 46.65 66.09 0.081 118.80 173.42
librium pH in the solution is smaller than the pHpzc of the adsor- bF 0.22 0.15 0.614 0.23 0.22
bents. Both F400 and bone char have an overall positive charge SSE 943.39 253.57 0.051 16882.89 21252.38
as the nal equilibrium pH is ranged from 6 to 6.8 for F400 and RedlichPeterson isotherm
7.5 to 9 for bone char. This is lower than the pHpzc of the two adsor- KR 27.10 479.03 0.237 68.36 291.20
bents and electrostatic attraction, which favored the adsorption aR 0.37 6.45 2.564 0.25 0.99
between the positively charged surface and the negatively charged bR 0.85 0.87 0.402 0.91 0.88
SSE 551.63 126.94 0.051 1088.92 1355.71
dye molecules. Peat, BACX2 and BACX6 have a net negative charge
on the surface as the nal equilibrium ranged from 5.2 to 5.3 for
peat and 3.4 to 3.5 for BACX2 and BACX6 which is higher than
the pHpzc of the adsorbents. Therefore, the negative surface re-
pulsed the negatively charged reactive dyes. This can help to ex- F400 Bone char Peat BACX2 BACX6
plain that peat only showed a small adsorption capacity for
Reactive Black 5 but always showed a high adsorption capacity 600
for basic dyes which are cationic dyes [34]. The extensive carbox- 500

qe (mg/g)
ylic groups of the humic and fulvic groups readily chemisorb the
cationic basic dye colored ion. However, Reactive Black 5 is an an-
ionic dye and will even experience repulsion with the negative sur- 300
face charge on the peat. 200
Reactive dyes and the surface of the bamboo activated carbon
are also negatively charged and the reactive dyes are still inten- 100
sively adsorbed. It suggested that the effect of Van der Waals 0
attraction and pp interactions should not be neglected and these 0 50 100 150 200 250 300 350 400 450 500 550 600
forces seem to be dominant and control the adsorption as the bam- Ce (mg/L)
boo activated carbon has a much higher surface area than other
adsorbents. Radovic et al. [35] and Michailof et al. [36] also sug- Fig. 3. Adsorption isotherm of Reactive Black 5 by different adsorbents (points:
gested that pp dispersion interactions dominate the adsorption experimental data; lines: Langmuir model).

process when most of the surface is unavailable for the adsorption

of co-ionic species. In addition, under a highly acidic environment, K LCe
both reactive dyes and the surface of bamboo activated are not qe
1 aL C e
fully ionized, which can reduce the repulsion of the dye molecules
where qe is the solid phase concentration of adsorbed species at
and the carbons surface and enhance the adsorption.
equilibrium (mg/g), Ce is the equilibrium concentration of the
adsorbate in the solution at equilibrium (mg/L), aL is the Langmuir
3.4. Isotherm models
isotherm constant (L/g) and KL is Langmuir isotherm constant (L/g).
This equation obeys the Henrys Law at low concentration and is
The equilibrium isotherms describe how the adsorbent inter-
acts with the adsorbate. The correlation of experimental results applicable to homogenous sorption where the sorption of each sor-
to adsorption model can help to understand the mechanisms of bate molecule on the surface has equal sorption activation energy.
adsorption and the heterogeneity of the adsorbent surface, and it The KL/aL gives the theoretical monolayer saturation capacity, q0
is also of importance in the practical design and operation of (mg/g). The isotherm constants, aL, KL, q0 and SSE are presented in
Table 3. The monolayer capacity of F400, bone char, peat, BACX2
adsorption. Three commonly used isotherm models, namely, Lang-
muir, Freundlich, and RedlichPeterson were employed to describe
the adsorption of RB 5. A minimizing procedure was adopted to
F400 Bone char Peat BACX2 BACX6
solve the equation by minimizing the sum of the error square
(SSE) between the theoretical data for qe calculated from the equa-
tions and the experimental data. Table 3 summarizes the corre- 600
sponding constants for each system. The results which are 500
qe (mg/g)

expressed as plots of solid-phase dye concentration against li- 400

quid-phase dye concentration are shown in Figs. 3 and 4.
3.4.1. The Langmuir isotherm 200
Langmuir [37] suggested a theory to describe the monolayer 100
coverage of adsorbate over a homogenous adsorbent surface. The 0
adsorption isotherm is based on the assumption that sorption 0 50 100 150 200 250 300 350 400 450 500 550 600
takes place at specic homogenous sites within the adsorbent.
Ce (mg/L)
Once an adsorbate molecule occupies a site, no further adsorption
can take place at that site. Thus, an equilibrium value can be Fig. 4. Adsorption isotherm of Reactive Black 5 by different adsorbents (points:
reached and the saturated monolayer curve can be expressed as: experimental data; lines: RedlichPeterson model).
36 A.W.M. Ip et al. / Journal of Colloid and Interface Science 337 (2009) 3238

and BACX6 is 175.8, 156.5, 7.0, 447.0 and 545.2 mg/g, respectively. Table 4
The adsorption isotherm data of Reactive Black 5 onto various The effect of salts on dye adsorption.

adsorbents were tted with the Langmuir model and shown in F400 Bone char BACX2 BACX6 Peat
Fig. 3. Adsorption capacities (mg/g) with C0 = 400 ppm
Normal 165.80 156.20 338.23 380.24 3.16
3.4.2. Freundlich isotherm NaCl 274.75 160.64 398.73a 398.73a 24.28
In 1906, Freundlich [38] suggested a model to describe the Na2PO4 231.78 157.23 401.22a 401.22a 51.45

properties of heterogeneous systems. This model has been widely Adsorption capacities (mg/g) with C0 = 1000 ppm
applied in heterogeneous adsorption systems especially for organic Normal 173.21 171.16 469.94 602.71 5.44
NaCl 319.24 168.29 843.26 803.22 29.82
compounds and high interactive species on activated carbon. The
Na2PO4 398.14 173.22 963.15 929.16 55.27
studies from Freundlich showed that the ratio of the amount of sol-
ute adsorbed onto a given mass of adsorbent to the concentration The dye was totally removed and hence the adsorption capacity is equal to the
initial concentration of the dye.
of the solute in the solution was not a constant at different solution
concentrations. He proposed this multi-site adsorption isotherm
by using NaCl and Na2PO4, however, the change in adsorption
for heterogeneous surfaces and expressed it as
capacities is less obvious for using NaCl for the electrolyte as pH
qe aF C be F is one of the most important parameters affecting the adsorption
process. It was found that NaCl did not affect the initial pH and
where qe is the solid phase concentration of adsorbed species at the nal pH of the system. However, Na2PO4 would bring the initial
equilibrium (mg/g), Ce is the equilibrium concentration of the pH and the nal pH of the system to pH 7. The order of adsorption
adsorbate in the solution at equilibrium (mg/L), aF is the Freundlich capacities per unit weight was: BACX2 > BACX6 > F400 > bone
constant (L/g) and bF is the Freundlich exponent. char > peat. It follows the same sequence as the surface area of
From the SSE values shown in Table 3, the Freundlich model the adsorbents. Newcombe and his co-workers [20] also found that
only showed a better correlation of experimental data than the the adsorption capacities are proportional to the secondary
Langmuir equation for the dye adsorption onto bone char and peat. micropores and mesopores of activated carbon. The adsorption
Other adsorbents do not t the Freundlich equation well. The aF va- mechanisms in the absence of strong electrostatic interaction are
lue is the relative indicator of adsorption capacity. The extent of hydrophobic and/or pp interactions which would be the same/
adsorption is the highest for BACX6 and the lowest for peat, and or similar for carbon which have in common is graphite like carbon
is characterized by the value of aF which is 0.081 and 173.2 for peat on their surface. Bone char also comprises 1015% active carbon.
and BACX6, respectively. As discussed in Section 3.2, the electrostatic interaction be-
tween the dye molecules and F400 and bone char surface is attrac-
3.4.3. RedlichPeterson isotherm (RP isotherm) tive. In contrast, the electrostatic interaction between the dye
Redlich and Peterson [39] incorporated three parameters into molecules and bamboo activated carbons and peat is repulsive.
an empirical isotherm. This isotherm combines the features from Theoretically, the adsorption capacities will increase for bamboo
both Langmuir and Freundlich isotherms into a single equation activated carbons and peat, and decrease for F400 and bone char.
and the mechanism of adsorption is hybrid and does not follow However, not all the experimental results in this study follow the
ideal monolayer adsorption. theory. The salts can neutralize the negative charged dye mole-
K RCe cules and the negatively charged surface of bamboo activated car-
qe bon and peat, enabling them to adsorb more dye molecules. On the
1 aR C be R
other hand, the salts can also neutralize the positive surface and
where qe is the solid phase concentration of adsorbed species at weaken the attractive force between dye molecules and bone char
equilibrium (mg/g), Ce is the equilibrium concentration of the and F400, however, the adsorption capacities did not decrease. It
adsorbate in the solution at equilibrium (mg/L), KR is RP isotherm means that other interactions besides the interaction between
constant (L/g), aR is RP isotherm constant (L/mg) and bR is the the dye molecules and the adsorbent surface may affect the
exponent which lies between 0 and 1. When bR = 1, it becomes a adsorption process. Lateral repulsion between the adsorbed mole-
Langmuir equation; when bR = 0, it becomes Henrys Law. cules and the repulsion between the adsorbed molecules and the
The RP isotherm constant, KR, aR and bR and the SSE for the RP non-adsorbed molecules in the solution oppose the adsorption
isotherm are listed in Table 3. The correlation of the dye adsorption and more important when the surface concentration is high
data with RP isotherm model was high. It provides the lowest SSE [20,40]. The salts can also interact with the adsorbate and screen
values for all the adsorbents, with SSE values of 552, 127, 1089, the repulsive force between the dye molecules and the carbon sur-
1356 and 0.051 for F400, bone char, BAC 2, BAC 6 and peat, respec- face between the adsorbed species. This effect does not inuence
tively. The adsorption isotherms with the RP model are presented the adsorption capacity of bone char as the surface is essentially
in Fig. 4 which indicates that the RP isotherm model describes the saturated and there is no possibility of further adsorption. Al-Degs
adsorption of Reactive Black 5 extremely well. It is expected that et al. [41] has investigated the effect of ionic strength on the
the RP isotherm model gives the best t results as it is a adsorption of reactive dyes and found that the adsorption capaci-
three-parameter model and the combined model can provide a ties of reactive dyes increased with ionic strength of solution,
Freundlich style exponent but which is not as rigorous as in the although, the electrostatic interaction between the dye molecules
Freundlich model. and the carbon surface is attractive. This was attributed to aggrega-
tion of reactive dyes molecules when the ionic strength of the solu-
3.5. Effect of salt on dye adsorption tion increased thus increasing the number of intermolecular forces
to explain this aggregation [42].
The effect of salts (NaCl and Na2PO4) on adsorption was varied The adsorption capacities of bamboo activated carbon BACX2 is
and it depends on the interactions of salts with adsorbents and higher than BACX6 when salt is added, whereas, the order is
adsorbates. As shown in Table 4, the adsorption capacity of the reversed without salt. This suggests that the electrostatic repul-
adsorbents increases signicantly under the effect of salts, except sions between the surface of the bamboo activated carbon and
bone char. The results showed that same ndings were obtained the dye molecules is more signicant in the micropores. The dye
A.W.M. Ip et al. / Journal of Colloid and Interface Science 337 (2009) 3238 37

Table 5 in chemically-activated carbon which has more acidic surface

Percentage of dye desorbed from the adsorbents at different pH. functional groups than the physically-activated carbon. Similar re-
Solution F400 Bone char BACX2 BACX6 Peat sults were obtained in the present study, as F400 (physically acti-
pH 6 water 0.01 8.01 13.50 31.24 5.87 vated, basic properties) has a much lower reversibility than
pH 7 water 0.02 7.85 13.46 31.46 6.06 bamboo activated carbons (chemically activated, acidic proper-
pH 8 water 0.01 7.81 13.97 31.36 6.32 ties). Once again, different surface characteristics would help to ex-
pH 9 water 0.01 8.24 13.59 31.45 6.13 plain the reversibility of adsorption. Walker and his co-workers
Salt solution 0.00 5.93 0.63 0.63 7.44
[14] have studied the adsorption and desorption of F400 and bone
char. It was found that the desorption of acid dye by F400 is neg-
ligible and about 50% of dye is desorbed from bone char. They sug-
molecules are restricted from further diffusion into the narrower gested that irreversible chemical reactions occurred between the
pores by the repulsions due to the negative charges which can be functional groups on the dye and the surface of F400 based on its
screened when salt is added. Therefore, the dye molecules can irreversibility of adsorption and lower effective solid diffusion rate,
now access the more narrow pores. and physisorption involves the formation of weak bonds between
hydrophilic groups on the dye and hydroxyl groups on the bone
3.6. Desorption study char surface based on its high reversibility of adsorption and higher
effective solid diffusion rate.
The results in Table 5 show that there is very little desorption
from F400, bone char and peat but for bamboo BACX2 it is 13
14% and for BACX6 it is 31% in the deionized water. It was found 4. Summary
that pH has no effect on dye desorption, however, the pH range
studied is limited and a conclusion cannot be made in the present The adsorption capacities of Reactive Black 5 on F400, bone
study. More acidic and alkaline conditions should be selected in or- char, peat, bamboo BACX2 and bamboo BACX6 are 176, 157, 7,
der to have a more thorough understand on the effect of pH on 477 and 545 mg dye/g adsorbent. Although the surface area of
desorption which always has a great impact. BACX2 > BACX6, the reversal in trend of their adsorption capacities
The desorption abilities of both bamboo activated carbons in is due to the difculty in the large dye ion penetrating all the
deionized water were much higher than the other three adsor- micropores of BACX2 whereas the mesopores of BACX6 are readily
bents. However, it is interesting that salt solution (pH 7) affected accessible. But since the relative capacities are reversed in the
the reversibility a lot. The reversibility of most adsorbents (except presence of salt and an initial dye concentration of 1000 mg/L, then
peat) decreased and only a small amount of dye desorbed from the the adsorbent surface area and acidity must also be very signicant
bamboo activated carbons. For F400, it hardly desorbed the reac- in determining the adsorption capacity for this system.
tive dye from the solution used. The performance of bone char
was better than both F400 and peat and it desorbed the reactive References
dye under any conditions experienced. Although the reversibility
of peat seems to be better than F400, the results of peat are quite [1] T. Robinson, G. McMullan, R. Marchant, P. Nigam, Bioresour. Technol. 77 (2001)
unique in that both the amount of the dye adsorbed and desorbed [2] J.R. Easton, in: P. Cooper (Ed.), Colour in dyehouse efuent, Society of Dyers and
were extremely low and insignicant. Colourists, Bradford, 1995, p. 9.
The reversibility of adsorption depends on whether there is a [3] A. Reife, H.S. Freeman, Environmental chemistry of dyes and pigments, Wiley,
New York, 1994. p. 265.
strong binding bond such as ionic or covalent bonding or weak
[4] M.A. Brown, S.C. DeVito, Crit. Rev. Environ. Sci. Technol. 23 (1993) 249.
binding forces such as Van der Waals forces or a dipoledipole [5] C. ONeill, F.R. Hawkes, D.L. Hawkes, N.D. Lourenco, H.M. Pinheiro, W. Delee, J.
interaction formed between the adsorbent surface and the dye Chem. Technol. Biotechnol. 74 (1999) 1009.
molecules. It suggested that only weak binding forces are present [6] G. Crini, Bioresour. Technol. 97 (2006) 1061.
[7] B.H. Hameed, A.T.M. Din, A.L. Ahmad, J. Hazard. Mater. 141 (2007) 819.
between the reactive dyes and bamboo activated carbon surface. [8] L.S. Chan, W.H. Cheung, G. McKay, Desalination 218 (2008) 304.
The weak interactions such as Van der Waals attraction and pp [9] A.W.M. Ip, J.P. Barford, G. McKay, Bioresour. Technol. 99 (2008) 8909.
interactions seem to be dominant and control the adsorption of [10] N.A. Medellin-Castillo, R. Leyva-Ramos, R. Ocampo-Perez, R.F.G. De La Cruz, A.
Aragon-Pina, J.M. Martinez-Rosales, R.M. Guerrero-Coronado, L. Fuentes-
bamboo activated carbon. In addition, the electrostatic interaction Rubio, Ind. Eng. Chem. Res. 46 (2007) 9205.
between the dye molecules and the bamboo carbon is repulsive [11] C.W. Cheung, J.F. Porter, G. McKay, Water Res. 35 (2001) 605.
which may further weaken the binding force and lead to high [12] C.W. Cheung, J.F. Porter, G. McKay, Sep. Purif. Technol. 19 (2000) 55.
[13] B.S. Girgis, A.A. Kader, A.N.H. Aly, Adsorpt. Sci. Technol. 15 (1997) 277.
reversibility of adsorption. However, in salt solution, the repulsive [14] G.M. Walker, L.R. Weatherley, Process Saf. Environ. Prot. 76 (1998) 177.
force was screened and the attractions between the surface and [15] H.A. Arafat, M. Franz, N.G. Pinto, Langmuir 15 (1999) 5997.
dye molecules became stronger and no desorption occurred. Con- [16] M.I. Bautista-Toledo, J.D. Mendez-Diaz, M. Sanchez-Polo, J. Rivera-Utrilla, M.A.
Ferro-Garcia, J. Colloid Interface Sci. 317 (2008) 11.
versely, the electrostatic interaction between the dye molecules [17] J. Wang, C.P. Huang, H.E. Allen, D.K. Cha, D.W. Kim, J. Colloid Interface Sci. 208
and F400 and bone char is attractive and lead to low reversibility (1998) 518.
of adsorption. The reversibility of BACX6 is higher than that of [18] C. Moreno-Castilla, M.A. Alvarez-Merino, M.V. Lopez-Ramon, J. Rivera-Utrilla,
Langmuir 20 (2004) 8142.
BACX2 because more dye is adsorbed onto the surface of BACX6
[19] M.A. Alvarez-Merino, V. Lopez-Ramon, C. Moreno-Castilla, J. Colloid Interface
(qe) which is the driving force of desorption. In addition, as shown Sci. 288 (2005) 335.
in Fig. 2, more dyes were adsorbed on BACX6 than BACX2 when the [20] G. Newcombe, M. Drikas, Carbon 35 (1997) 1239.
equilibrium dye concentration in solution was high and increased [21] M.A. Fontecha-Camara, M.V. Lopez-Ramon, M.A. Alvarez-Merino, C. Moreno-
Castilla, Langmuir 23 (2007) 1242.
(>100 mg/L). As a result, more dyes were desorbed when the sur- [22] S.H. Wu, P. Pendleton, J. Colloid Interface Sci. 243 (2001) 306.
rounding concentration was low. [23] C.Y. Kuo, C.H. Wu, J.Y. Wu, J. Colloid Interface Sci. 327 (2008) 308.
Aktas and Cecen [43] have investigated the effect of the type of [24] M. Bjelopavlic, G. Newcombe, R. Hayes, J. Colloid Interface Sci. 210 (1999) 271.
[25] Q. Qin, J. Ma, K. Liu, J. Colloid Interface Sci. 315 (2007) 80.
activation on adsorption of phenol and its reversibility. It was [26] H.P. Boehm, Carbon 32 (1994) 759.
found that the reversibility of carbon produced from physical acti- [27] M.J. Selles-Perez, J.M. Martin-Martinez, J. Chem. Soc. Faraday Trans. 87 (1991)
vation is much lower than carbon produced from chemical activa- 1237.
[28] S.J. Gregg, K.S.W. Sing, Academic Press Limited, San Diego, 1982.
tion as chemisorption is the dominant adsorption mechanism for [29] F.S. Baker, C.E. Miller, A.J. Repik, E.D. Tolles, in: R.E. Kirk, D.F. Othmer (Eds.),
physically-activated carbon, whereas physisorption is dominant Wiley, New York, 2004, p. 741.
38 A.W.M. Ip et al. / Journal of Colloid and Interface Science 337 (2009) 3238

[30] A.M. Puziy, O.I. Poddubnaya, A. Martinez-Alonso, F. Suarez-Garcia, J.M.D. [37] I. Langmuir, J. Am. Chem. Soc. 40 (1918) 1361.
Tascon, Carbon 43 (2005) 2857. [38] H.M.F. Freundlich, J. Phys. Chem. 57 (1906) 385.
[31] G.S. Miguel, G.D. Fowler, C.J. Sollars, Ind. Eng. Chem. Res. 37 (1998) 2430. [39] O. Redlich, D.L. Peterson, J. Phys. Chem. 63 (1959) 1024.
[32] C.T. Hsieh, H. Teng, Carbon 38 (2000) 863. [40] A. Deryo-Marczewska, Langmuir 9 (1993) 2344.
[33] M. Valix, W.H. Cheung, G. McKay, Langmuir 22 (2006) 574. [41] Y.S. Al-Degs, M.I. El-Barghouthi, A.H. El-Sheikh, G.M. Walker, Dyes Pigm. 77
[34] Y.S. Ho, G. McKay, Chem. Eng. J. 70 (1998) 115. (2008) 16.
[35] L.R. Radovic, I.F. Silva, J.I. Ume, J.A. Menendez, C.A. Leon, Y. Leon, A.W. Scaroni, [42] G. Alberghina, R. Bianchini, M. Fichera, S. Fisichella, Dyes Pigm. 46 (2000)
Carbon 35 (1997) 1339. 129.
[36] C. Michailof, G.G. Stavropoulos, C. Panayiotou, Bioresour. Technol. 99 (2008) 6400. [43] O. Aktas, F. Cecen, J. Chem. Technol. Biotechnol. 81 (2006) 94.