Sunteți pe pagina 1din 10

This article was downloaded by: [INFLIBNET India Order]

On: 11 June 2010


Access details: Access Details: [subscription number 920455929]
Publisher Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-
41 Mortimer Street, London W1T 3JH, UK

Journal of the Textile Institute


Publication details, including instructions for authors and subscription information:
http://www.informaworld.com/smpp/title~content=t778164490

Agave sisalana, a biosorbent for the adsorption of Reactive Red 120 from
aqueous solution
Venkateshwarapuram Rengaswami Giri Devab; Jayarama Reddy Venugopalb; Thamdiannan Senthil
Kumara; Lima Rose Mirandac; Seeram Ramakrishnab
a
Department of Textile Technology, A.C. College of Technology, Anna University, Chennai, India b
Nanoscience and Nanotechnology Initiative, Division of Bioengineering, National University of
Singapore, Singapore c Carbon Research Engineering Laboratory, Department of Chemical
Engineering, A.C. College of Technology, Anna University, Chennai, India

First published on: 08 January 2010

To cite this Article Dev, Venkateshwarapuram Rengaswami Giri , Venugopal, Jayarama Reddy , Kumar, Thamdiannan
Senthil , Miranda, Lima Rose and Ramakrishna, Seeram(2010) 'Agave sisalana, a biosorbent for the adsorption of
Reactive Red 120 from aqueous solution', Journal of the Textile Institute, 101: 5, 414 — 422, First published on: 08 January
2010 (iFirst)
To link to this Article: DOI: 10.1080/00405000802445289
URL: http://dx.doi.org/10.1080/00405000802445289

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.informaworld.com/terms-and-conditions-of-access.pdf

This article may be used for research, teaching and private study purposes. Any substantial or
systematic reproduction, re-distribution, re-selling, loan or sub-licensing, systematic supply or
distribution in any form to anyone is expressly forbidden.

The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses
should be independently verified with primary sources. The publisher shall not be liable for any loss,
actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly
or indirectly in connection with or arising out of the use of this material.
The Journal of The Textile Institute
Vol. 101, No. 5, May 2010, 414–422

Agave sisalana, a biosorbent for the adsorption of Reactive Red 120 from aqueous solution
Venkateshwarapuram Rengaswami Giri Deva,b∗ , Jayarama Reddy Venugopalb , Thamdiannan Senthil Kumara ,
Lima Rose Mirandac and Seeram Ramakrishnab
a
Department of Textile Technology, A.C. College of Technology, Anna University, Chennai-25, India; b Nanoscience and
Nanotechnology Initiative, Division of Bioengineering, National University of Singapore, Singapore 117576;
c
Carbon Research Engineering Laboratory, Department of Chemical Engineering,
A.C. College of Technology, Anna University, Chennai-25, India
(Received 29 February 2008; final version received 1 September 2008)

The textile industry is one of the largest producers of dye effluent. Treatment of these effluents has to be cost effective hence
a number of precursors have been studied as a viable alternative adsorbent. Sisal fibre was converted to activated carbon by
chemical methods. Sisal fibre was activated with different activating agents such as H3 PO4 , HCl, HNO3 , NaOH and KOH.
The adsorption of Reactive Red 120 (RR 120) dye onto sisal fibre activated carbon (SFAC) from aqueous solution was
Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

investigated. Adsorption experiments were carried out at different dye concentrations, initial solution pH and carbon dosage.
Batch adsorption studies were carried out using activated carbon produced using phosphoric acid yielded better carbon as it
good results in terms of Methylene Blue number and Iodine number. These carbons were used to study the batch adsorption
studies. Methylene Blue number and Iodine number of SFAC were found to be 240 mg/g and 855 mg/g, respectively. The
BET surface area of the carbon was 885 m2 /g. The batch experiments adsorption isotherm studies fitted well to Langmuir
isotherm and the adsorption capacity was found to be 110 mg/g. Adsorption kinetics data were tested using pseudo-first-order
and pseudo-second-order models. Kinetic studies showed that the adsorption data followed a pseudo-second-order reaction.
Keywords: sisal fibre; Agave sisalana; activated carbon; Reactive Red 120; adsorption kinetics; Methylene Blue

Introduction et al., 1998), myrobalan, rubber seed coat, cashew nut


Over the last 35 years, India has become a major producer of sheath, palm seed coat, palm tree flower, pongam seed coat
dyes and pigments catering to the needs of not only the tex- (Rengaraj, Arabindoo, & Murugesan, 1999), saw dust, rice
tile industry but also other industries such as paper, rubber, husk (Malik, 2003), rice shells, peanut shells, cotton seed
plastic, paints, printing inks, arts and crafts, leather, food, shell (Kim, Baek, Jeoung, & Park, 2003), cornelian cherry,
drugs and cosmetics. Effluents from the above-mentioned apricot stone, almond shell (Demirbas, Kobya, Senturk, &
industries contain dyes, which are highly dispersible and Ozkan, 2004) and oak wood waste, corn hulls, corn stover
contribute to aquatic toxicity. Therefore, removal of dyes (Zhang et al., 2004).
before discharging the waste water is essential. It is also of significant interest to note that lignocel-
Among the various treatment methods, adsorption is lulosic fibres such as coir (Namasivayam & Kadirvelu,
one of the most effective methods for lowering the concen- 1997), banana pith (Kadirvelu et al., 2003) and jute
trations of the dissolved organic substances. Adsorption (Senthilkumaar, Varadarajan, Porkodi, & Subbhuraam,
using activated carbon has received considerable interest 2005) have also been used as a precursor to produce car-
from researchers around the globe due to its high efficiency bon for waste water treatment. In this work, colour re-
in the treatment of effluents. In pursuit of finding low-cost moval studies using a reactive dye have been carried out
and effective carbon, attempts have been made by various on activated carbon prepared from sisal fibre precursor.
researchers to produce carbon from different precursors Sisal fibre is one of the most widely used natural fi-
such as chitosan (Muzzarelli & Rocchetti, 1986), goethite bres and is very easily cultivated (Murherjee & Satya-
(Johonson, 1990), silica gel (Filho, Gushiken, Polito, & narayana, 1984). Nearly 4.5 million tonnes of sisal fibre
Moreiza, 1995), bituminous coal (Singh & Rawat, 1994), is produced every year throughout the world. Tanzania and
paper mill sludge (Calace, Nardi, Petronio, Pietroletti, & Brazil are the two major sisal fibre-producing countries
Tosti, 2003), cotton stalks (Attia, El-Hendawy, Khedr, & El- (Chand, Tiwari, & Rohatgi, 1988). Sisal fibre is a hard
Nabarawy, 2004), red mud (Apak, Tutean, Hugul, & Hizal, fibre extracted from the leaves of the sisal plant (Agave
1998; Lopez et al., 1998), blast furnace sludge (Lopez sisalana). Although native to tropical and sub-tropical


Corresponding author. Email: vrgiridev@yahoo.com
ISSN 0040-5000 print / ISSN 1754-2340 online
Copyright 
C 2010 The Textile Institute
DOI: 10.1080/00405000802445289
http://www.informaworld.com
The Journal of The Textile Institute 415

Table 1. Characteristics of the adsorbent. using a hot-air oven. It was then activated at 400◦ C for a
period of 1 h in a muffle furnace. The resulting carbon was
Characteristics Values washed with distilled water till a constant pH of the slurry
Ash (%) 0.85 was reached and then dried. The carbon was then sieved
Carbon (%) 65.62 using 170 mesh to obtain uniform particle size and stored
Moisture (%) 2.08 in an airtight container for further use.
Volatile (%) 31.45
B.E.T. surface area (m2 /g) 885
Iodine number (mg/g) 855
Methylene Blue number (mg/g) 240 Adsorbent characterisation
Iodine number and Methylene Blue number
The iodine number and Methylene Blue number tests were
North and South America, the sisal plant is now widely done on sisal fibre activated carbon (SFAC) according to
grown in tropical countries of Africa, the West Indies, ASTM D4607 and IS 877 (1989) procedure. Iodine number
India and the Far East (Bisanda & Ansell, 1992). A sisal is indicative of the surface area that exists in pores of 10 Å
plant produces about 200–250 leaves, and each leaf con- diameter and greater, whereas Methylene Blue number is
tains 1000–1200 fibre bundles each of which is composed indicative of adsorption capacity of carbon for Methylene
of 4% fibre, 0.75% cuticle, 8% dry matter and 87.25% water Blue molecules that are 15 Å in diameter and of molecular
(Murherjee & Satyanarayana, 1984). Chemically, sisal fi- weight 320.
Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

bre (Wilson, 1971) contains 78% cellulose, 8% lignin, 10%


hemicellulose, 2% waxes and about 1% ash by weight. The
traditional applications of sisal fibre are in the manufac- Kinetic procedure
turing of carpets, ropes, gunny bags, mats, cordage and
twines. Batch adsorption studies were conducted in a shaker using
This work is aimed at studying the usefulness of sisal 100 ml of adsorbate solution and a fixed adsorbent dosage
fibre as a precursor for the production of activated car- of 0.15 g. The agitation speed of the shaker was fixed at
bon. Chemical activation of the fibre was carried out using 180 r.p.m. for all batch experiments. The samples at differ-
hydrochloric acid, nitric acid, phosphoric acid, sodium hy- ent time intervals (0–420 min) were taken and centrifuged.
droxide and potassium hydroxide, and the activated carbon The concentrations of the samples at different time intervals
thus produced was characterised by their iodine number, were analysed in an ultraviolet spectrophotometer (Hitachi,
Methylene Blue number and Brunauer, Emmett, and Teller UV-2000, Japan) at a wavelength of 536 nm (Senthilku-
(B.E.T.) surface area. The impregnating reagent used for maar, Kalaimani, Porkodi, Varadarajan, & Subbhuraam,
activation that gave high iodine number and Methylene 2006).
Blue number was then selected for the adsorption studies
of Reactive Red 120 dye (Table 1).
Isotherm experiments
Isotherm studies were conducted in a series of 250-ml Er-
Experimental procedure lenmeyer flasks. Each flask was filled with 100 ml of dif-
Materials and methods ferent initial dye concentrations and adjusted to a pH 2.0.
All the reagents used were of analytical grade. The impreg- After equilibration (i.e. 240 min), the solution was cen-
nating agents for the chemical activation of the sisal fibre trifuged and analysed. Adsorption studies were also per-
were hydrochloric acid, nitric acid and phosphoric acid. The formed at different concentrations to obtain the equilibrium
dye used for the study is color index (CI) Reactive Red 120. isotherms. The initial concentrations of solutions taken for
The aqueous solution of the reactive red dye was prepared the studies were 50,100,150 and 200 mg/l. The equilibrium
by dissolving reactive dye in double-distilled water. The adsorption capacity was calculated using the following for-
pH of the solution was adjusted using hydrochloric acid mula (Helen Kalavathy, Karthikeyan, Rajgopal, & Miranda,
and sodium hydroxide. 2005):

(C0 − Ce )V
Preparation of adsorbent qe = (1)
M
Sisal fibre obtained from the plant was chosen as a precursor
for the production of activated carbon. Sun-dried sisal fibre where qe (mg/g) is the equilibrium adsorption capacity; C0
was carbonised with 50% acid (HCl, HNO3 and H3 PO4 ) by and Ce are the initial and equilibrium concentration (mg/g)
weight and 1 N alkali solution (NaOH and KOH). The fibre of the reactive dye in solution; V is the volume; and M is
was soaked for a period of 24 h and dried for 1 h at 110◦ C the weight of the adsorbent.
416 V.R. Giri Dev et al.

300 100
Methylene blue number (mg/g)

250

% of colour removal
200 90

150

100 80

50

0 70
200 300 400 500 600 700 0 2 4 6 8 10 12
Temperature pH of the dye solution
H3PO4 HNO3 HCl NaOH KOH
Figure 3. Effect of pH on the removal of Reactive Red 120 dye.
Conditions: adsorbent load 0.2 g/100 ml, concentration 100 mg/l
Figure 1. Effect of temperature on Methylene Blue number of and room temperature.
SFAC for different activating agents.
Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

Effect of pH
Results The removal of dyes as a function of pH is shown in
Effect of activating agent on activated Figure 3. The removal of dyes by SFAC was found to be the
carbon quality maximum in the acidic pH range below 2. The pH value of
The quality of carbon depends mainly on its adsorption ca- the dye solution plays an important role in the adsorption
pacity. Higher adsorption capacity requires large pore vol- process and particularly on the adsorption capacity. Sim-
ume in the carbon produced, that is, the iodine number and ilar observations have been reported by other workers for
Methylene Blue number must be high. It is observed in Fig- adsorption of reactive dyes indicating that the carbon ac-
ures 1 and 2 that carbons produced using phosphoric acid quired net positive charges on its surface (Bousher, Shen,
activation had higher Methylene Blue number and iodine & Edyvean, 1997); as the pH of the adsorbate was lowered,
number than the carbons produced using other impregnat- the positive charges on the surface increased. This would
ing agents. attract the negatively charged functional groups located on
the reactive dyes (Santhy & Selvapathy, 2006). In subse-
quent adsorption studies, a pH of 2.0 was maintained.

900

800 Effect of initial concentration and


700 contact time
Iodine number (mg/g)

600 The effect of initial dye concentration and contact time


500
on the removal of Reactive Red 120 is shown in Figure
4. It is evident that the amount of adsorption increased
400
with increase in contact time. It was observed that equi-
300 librium was attained at 240 min, and the equilibrium time
200 was found to be the same for all the concentrations studied.
During the adsorption of dyes, the dye molecules initially
100
reach the boundary layer, they have to diffuse into the ad-
0
sorbent surface and finally diffuse into the porous structure
200 300 400 500 600 700
of the adsorbent. Hence, this phenomenon will take a rela-
Temperature tively longer contact time (Senthilkumaar et al., 2005). The
H3PO4 HNO3 HCl NaOH KOH amount adsorbed increased from 48 to 100 mg/g when the
initial concentration was increased from 50 to 200 mg/l for
Figure 2. Effect of temperature on iodine number of SFAC for the adsorbent dosage of 0.15 g/100 ml at pH 2 and room
different activating agents. temperature.
The Journal of The Textile Institute 417

120 0.6
Amount of adsorption (mg/g)

100 0.5

0.4
80

Ce/qe
0.3
60

0.2
40
0.1
20
0
0 10 20 30 40 50 60
0
0 100 200 300 400 500 Ce
Time (min)
Figure 6. Langmuir adsorption isotherm for Reactive Red
50 ppm 100 ppm 150 ppm 200 ppm 120 dye.

Figure 4. Effect of initial concentration and time on the re-


Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

Isotherm studies
moval of Reactive Red 120 dye. Conditions: adsorbent loading
0.15 g/100 ml, pH −2 and room temperature. The salient features of isotherms are needed before the
kinetics of the adsorption process is interpreted. The dy-
namic adsorptive separation of solute from solution onto
Effect of carbon dosage an adsorbent depends on a good description of the equi-
The effect of carbon dose on the removal of dyes is shown librium separation between the two phases. Many models
in Figure 5. The adsorption of Reactive Red dye on SFAC have been proposed to explain adsorption equilibria, but
was studied by varying the carbon concentration (0.05– the most important factor is to have applicability over the
0.4 g/100 ml) for different reactive red dye concentrations entire range of process conditions. The most widely used
(50, 100, 150 and 200 mg/l) at pH 2.0. The percent ad- isotherm models for solid–liquid adsorption are the Lang-
sorption increased with shorter equilibrium time, and the muir and Freundlich isotherms.
carbon concentration increased. The adsorption increased
from 60%, 35%, 18.8% and 15% to 100% for the initial
reactive red concentrations 50, 100, 150 and 200 mg/l, re- Langmuir isotherm
spectively. This can be attributed to increased carbon sur- The experimental data were analysed according to the linear
face and availability of more adsorption sites. form of the Langmuir isotherm and are shown in Figure 6.
The Langmuir isotherm is based on monolayer adsorption
(constant heat of adsorption for all sites) on the active sites
100
of the adsorbent. It is given by
90
80
 
KL Ce
% of colour removal

qe = . (2)
70 1 + aL Ce
60
50 The linear form of the Langmuir isotherm is given by
40
Ce 1 aL Ce
30 = + (3)
qe KL KL
20
10 where KL (L/g) and aL (L/mg) represent the Langmuir
0 constants. The theoretical maximum monolayer adsorption
0 0.1 0.2 0.3 0.4 0.5 capacity qmax (mg/g) is given by KL /aL . The maximum
Carbon dosage (g) adsorption capacity qmax was 110 mg/g for Reactive Red
50 ppm 100 ppm 150 ppm 200 ppm 120 dye onto SFAC. The comparison of the qmax for vari-
ous adsorbents is shown in Tables 2 and 3. Serial numbers
Figure 5. Effect of carbon dosage on the removal of Reactive 1–6 represent the commercially available activated carbon.
Red 120 dye. Conditions: time 240 min, pH −2, carbon loading It can be seen from the table that the adsorption capacity of
0.05–0.4 g and room temperature. commercial activated carbon for Reactive Red 120 dye is
418 V.R. Giri Dev et al.

Table 2. Comparison of adsorption capacity of various materials for Reactive Red 120.

S. no. Adsorbent Capacity (mg/g) References

1 Activated carbon 400 Kharaisheh, Al Degs, Allen, and Ahmad (2002)


2 Activated carbona 190 Ozacar and Sengil (2002)
3 Activated carbonb 157 Ozacar and Sengil (2002)
4 Activated carbonc 201 Ozacar and Sengil (2002)
5 Activated carbond 246 Ozacar and Sengil (2002)
6 Activated carbone 223 Ozacar and Sengil (2002)
7 Waste metal hydroxide 49 Netpradit, Thiravetyan, and Towprayoon (2003)
8 Coconut tree flower carbon 190 Senthilkumaar, Kalaimani, Porkodi, Varadarajan, and Subbhuraam (2006)
9 Jute fibre carbon 125 Senthilkumaar, Varadarajan, Porkodi, and Subbhuraam (2005)
10 Sisal fibre activated carbon 110 This study

Note: a NORIT GAC 1240 PLUS.


b NORIT GAC 1240 PLUS activated by 6-M HNO .
3
c NORIT GAC 1240 PLUS activated by 10-M H O
2 2.
d NORIT GAC 1240 PLUS AC3 activated in H .
2
e NORIT GAC 1240 PLUS AC4 activated in N .
2
Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

found to be higher than that of SFAC. However, it should 4.9


be noted these carbons are costly making it economically
unviable for effluent treatment plants. Serial numbers 8 4.7

and 9 represent the activated carbon prepared from non- 4.5


conventional precursor like jute and coconut male flowers.
The adsorption capacities of these activated carbons were 4.3
lnq e

found to be slightly higher than those of SFAC. However,


4.1
the collection of coconut male flowers for the purpose of
converting to activated carbon in industrial scale might be 3.9
tedious and time consuming. Moreover, it should be noted
that jute plant is an annual plant that thrives best in moist 3.7
soil in a hot and humid climate. Jute plants are grown as
3.5
a seasonal crop in India, relying on the monsoon rains,
0 1 2 3 4 5
and the cultivation of the fibres needs proper care in con-
trast to sisal plant that grows easily without much atten- lnCe
tion and is found in abundance making it a good precursor
for activated carbon. It should also be noted among the Figure 7. Freundlich adsorption isotherm for Reactive Red
120 dye.
reported works given in Table 2, the adsorption of Reac-
tive Red 120 dye was found to be lowest for waste metal
hydroxide. equation can be expressed in terms of a dimensional sepa-
The Langmuir equation gave an accurate description ration factor RL , which is given by the following equation:
of the experimental data, which was confirmed by the ex-
tremely high values of correlation coefficient (0.99). The 1
applicability of the Langmuir isotherm suggested the mono- RL = (4)
(1 + KL C0 )
layer coverage of the Reactive Red dye 120 on the surface
of the SFAC. The essential characteristics of the Langmuir
where, C0 is the highest initial dye concentration (mg/g),
and RL values indicate the shape of the isotherm. The RL
values between 0 and 1 indicate favourable adsorption. The
Table 3. Adsorption isotherms of SFAC at different value of RL obtained was found to be 0.002, which con-
concentration. firmed that the adsorption process was favourable.
Freundlich Langmuir

af (mg/g) bf R2 qm (mg/g) KL (L/g) aL (L/mg) R2 Freundlich isotherm


3.5185 0.2867 0.976 109.89 20.3665 0.1853 0.9995 The experimental data were analysed according to the linear
form of the Freundlich isotherm and are shown in Figure 7.
The Journal of The Textile Institute 419

Freundlich isotherm gives the relationship between equilib- 2.5


rium liquid and solid-phase capacity based on the multilayer
2
adsorption on heterogeneous surface. This isotherm is de-
rived from the assumption that the adsorption sites are dis- 1.5
tributed exponentially with respect to the heat of adsorption

log (qe–qt )
and is given by 1

0.5
qe = af Cebf (5)
0
0 100 200 300 400 500
–0.5
and linearised as
–1
Time (min)
log qe = ln af + bf ln Ce (6)
50 ppm 100 ppm 150 ppm 200 ppm
where, af and bf represent the multilayer adsorption capac-
ity and the intensity of adsorption, respectively. Figure 8. Pseudo-first-order kinetics for Reactive Red 120 dye
The experimental adsorption capacity and the adsorp- adsorption onto SFAC. Conditions: adsorbent dosage 0.15 g/
100 ml, pH −2, room temperature and time 4 h.
Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

tion capacity predicted by the two isotherms are compared,


and the corresponding Langmuir and Freundlich isotherm
parameters, along with the regression coefficients, are listed Pseudo-first-order model
in Table 3. The validity of the Langmuir model suggests that The kinetic data were treated with the Lagergren first-order
the adsorption process is monolayer and adsorption of each model
molecule has equal activation energy. From the regression
coefficient, value Langmuir adsorption is found to fit the dq
= k1 (qe − qt ). (7)
data better than the Freundlich isotherm. dt

Integrating Equation (7) with respect to integrating condi-


tions q = 0 at t = 0 and q = qt at t = t, the kinetic rate
Kinetic studies expression becomes
The kinetics of adsorption describes the rate of reactive
red dye uptake on activated carbon, and this rate controls k1 t
the equilibrium time. The kinetics of adsorbate uptake is log(qe − qt ) = log qe − . (8)
2.303
required for selecting optimum operating conditions for
the full-scale batch process. The kinetic parameter, which The first-order rate constant k1 can be obtained from the
is helpful for the prediction of adsorption rate, gives im- slope of the plot of log (qe − qt) versus time, as shown
portant information for designing and modelling the pro- in Figure 8. The adsorption first-order rate constants were
cesses. Thus, the effects of initial concentration, contact found to be 0.0088, 0.0094, 0.0108 and 0.0115 min1 for ini-
time and adsorbent dosage were analysed from the kinetic tial reactive red concentrations of 50,100,150 and 200 mg/l,
point of view. Preliminary studies on the adsorption rate respectively. The variation in rate should be proportional to
show that the amount adsorbed increased with increased the first power of concentration for strict surface adsorption.
reactive red concentration. The maximum amount of reac- However, the relationship between initial solute concentra-
tive red dye was adsorbed within 120 min (80%–90% of tion and rate of adsorption will not be linear when pore
the total dye was adsorbed), and thereafter the adsorption diffusion limits the adsorption process. It was observed
proceeds at a slower rate until equilibrium was reached. from Figure 8 that the Lagergren model fits well for the
The equilibrium time was found to be at 240 min for the first 120 min, and thereafter, the data deviate from the the-
initial dye concentration range studied. The rate of uptake ory. Thus, the model represents the initial stages where
increased as the adsorbent dosage increased because it leads rapid adsorption occurs well but cannot be applied for the
to more surface area for adsorption. However, there is no entire adsorption process. A similar trend was previously
significant change in adsorption above 0.3 g for the initial observed by Ho and McKay (1998) for basic dyes on peat
concentration range studied. Hence, this amount was fixed particles. The sorption data were represented well by the
and assumed for all the adsorption studies. The kinetics Lagergren first-order model only for the rapid initial phase
of the sorption data were analysed using different kinetic that occurs for the time of 0–120 min. This conforms that it
models such as pseudo-first-order and pseudo-second-order is not appropriate to use the Lagergren kinetic model to pre-
models. dict the adsorption kinetics for reactive red dye onto SFAC
420 V.R. Giri Dev et al.

Table 4. Comparison of the pseudo-first-order and pseudo-second-order adsorption rate constants for different initial concentrations.

Pseudo-first-order kinetics Pseudo-second-order kinetics

qe (exp) qe (calculated, k1 qe (calculated, h (mg/ k2


C0 (mg/L) (mg/g) mg/g) (min1 ) R2 mg/g) g/min) (min1 ) R2

50 46.48 18 0.0088 0.8727 47 5.8331 0.0027 0.9991


100 61.71 26 0.0094 0.8968 63 7.2354 0.0019 0.9988
150 85.92 37 0.0108 0.8949 88 8.8587 0.0012 0.9991
200 99.29 46 0.0115 0.9004 102 9.8585 0.0010 0.9991

for the entire sorption period. The regression coefficient initial sorption rate, given by
values were found to be in the range of 0.8727–0.9004 in
Table 4. This shows that the model can be applied but it is h = k2 qe2 . (11)
not appropriate to describe the entire process.
The second-order rate constants and the calculated initial
sorption rate values are shown in Table 4. It was observed
Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

Pseudo-second-order model that the pseudo-second-order rate constant (k2 ) decreased


Adsorption kinetics were explained by the pseudo-second- the initial concentration, and the initial sorption rate (h)
order model given by Ho and McKay (1998) as follows: was found to increase with increased initial reactive red
dye concentration. The calculated qe values agree very well
dq
= k2 (qe − qt )2 . (9)
dt Table 5. Intra-particle rate parameters and diffusion coefficients
at different concentrations.
Integrating Equation (9) for the boundary conditions q = 0
to q = qt at t = 0 to t = t is simplified as Concentration Kid (mg/ D1 × 10−8 D2 × 10−8
(mg/g) g min0.5 ) (cm2 /s) (cm2 /s)
 
t 1 t 50 0.9429 4.9 1.9
= + (10)
qt k2 qe2 qe 100 1.3722 8.9 1.8
150 2.6957 9.2 2.9
200 3.5312 10.2 2.3
where k2 (g/mg/min) is the second-order rate constant de-
termined from the plot of t/qt versus t, as shown in Figure 9.
The second-order rate constants were used to calculate the
120

10 100
9
8 80
qt (mg/g)

7
6 60
t /q t

5
4 40
3
2 20
1
0 0
0 100 200 300 400 500 0 5 10 15 20 25

Time (min) t /2 (min )


50 ppm 100 ppm 150 ppm 200 ppm 50 ppm 100 ppm 150 ppm 200 ppm

Figure 9. Pseudo-second-order kinetics for Reactive Red 120 Figure 10. Intra-particle diffusion plot at different concentrations
dye adsorption onto SFAC. Conditions: adsorbent dosage 0.15 g/ for the initial pH −2 and carbon dosage 0.15 g, room temperature
100 ml, pH −2, room temperature and time 4 h. and time 4 h.
The Journal of The Textile Institute 421

1.2 red dye on SFAC was found to follow the second-order


kinetics; also, diffusion to the pore is found to be predomi-
1 nant at longer times whereas film diffusion was observed at
shorter times. The easy availability of the sisal fibre because
0.8 of its low cost and the feasibility of producing good-quality
activated carbon make it a viable adsorbent for the removal
q t/ qe

0.6 of reactive red from aqueous solution.

0.4
References
0.2 Apak, R., Tutean, E., Hugul, M., & Hizal, J. (1998). Heavy metal
cation retention by conventional sorbents. Water Research,
0 32, 430–440.
0 5 10 15 20 25 Attia, A.A., El-Hendawy, A.A., Khedr, S.A., & El-Nabarawy, Th.
(2004). Textural properties and adsorption of dyes onto car-
t /2 bons derived from cotton stalks. Adsorption Science Technol-
50 ppm 100 ppm 150 ppm 200 ppm ogy, 22, 411–426.
Bisanda, E.T.N., & Ansell, M.P. (1992). Properties of sisal–CNSL
composites. Journal of Material Science, 27, 1690–1700.
Figure 11. Determination of diffusion coefficient (D1 ) for dif- Bousher, A., Shen, X., & Edyvean, R.G.J. (1997). Removal of
ferent initial concentrations at pH −2.
Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

coloured organic matter by adsorption onto low cost waste


materials. Water Research, 31, 2084–2092.
Calace, N., Nardi, E., Petronio, B.M., Pietroletti, M., & Tosti, G.
0 (2003). Metal ion removal from water by sorption on paper
0 50 100 150 200 mill sludge. Chemosphere, 51, 797–803.
–0.5 Chand, N., Tiwary, R.K., & Rohatgi, P.K. (1988). Bibliography re-
source structure properties of natural cellulosic fibre—an an-
–1 notated bibliography. Journal of Materials Science, 23, 381–
387.
ln(1–qt /qe )

–1.5 Demirbas, E., Kobya, M., Senturk, & Ozkan, T. (2004). Adsorp-
tion kinetics for the removal of chromium(VI) from aqueous
–2
solution on the activated carbons prepared from agricultural
wastes. Water SA, 30, 533–539.
–2.5
Filho, N.L.D., Gushiken, Y., Polito, W.L., & Moreiza, J.C. (1995).
–3
Sorption and preconcentrations of materials in ethanol solu-
tions with silica gel modified with benzinmidazole. Talanta,
–3.5 42, 1630–1663.
Helen Kalavathy, M., Karthikeyan, T., Rajgopal, S., & Miranda,
Time (min)
L.R. (2005). Kinetic and isotherm studies of Cu(II) adsorption
50 ppm 100 ppm 150 ppm 200 ppm onto H3 PO4 —activated rubber wood saw dust. Journal of
Colloid and Interface Science, 292, 354–362.
Ho, Y.S., & McKay, G. (1998). The kinetics of sorption of basic
Figure 12. Determination of diffusion coefficient (D2 ) for dif- dyes from aqueous solution by sphagnum moss peat. Cana-
ferent initial concentration at pH −2. dian Journal of Chemical Engineering, 79, 822–827.
Johonson, B.B. (1990). Effect of pH, temperature and concentra-
tion on the adsorption of cadmium on goethite. Environmental
with the experiment values, and a regression coefficient of Science and Technology 24, 112–118.
above 0.9988 shows that the model can be applied for entire Kadirvelu, K., Kavipriya, M., Karthika, C., Radhika, M., Ven-
process and confirms the chemisorptions of reactive red dye nilamani, N., & Pattabhi, S. (2003). Utilization of various
agricultural waste for activated carbon preparation and appli-
onto SFAC (Table 5 and Figures 10–12). cation for the removal of dyes and metal ions from aqueous
solutions. Bioresource Technology, 81, 87–89.
Karthikeyan, T., Rajgopal, S., & Miranda, L.R. (2005). Chromium
Conclusion (VI) adsorption from aqueous solution by Hevea brasiliensis
saw dust activated carbon. Journal of Hazardous Materials,
Agave sisalana, naturally occurring fibre, was converted B124, 192–199.
to activating carbon using chemical method. The carbon Kharaisheh, M.A.M., Al Degs, Y.S., Allen, S.T., & Ahmad, M.N.
activated using phosphoric acid was found to be the best (2002). Elucidation on controlling steps of reactive dye ad-
in terms of Methylene Blue number, iodine number and sorption on activated carbon. Industrial and Engineering
surface area. SFAC was also found to be a good adsorbent Chemistry Research, 41, 1651–1657.
Kim, T.Y., Baek, I.H., Jeoung, Y.D., & Park, S.C. (2003). Manu-
for the treatment of effluent with the reactive red dye. The facturing activated carbon using various agricultural wastes.
Langmuir adsorption isotherm fits the data better than the Journal of Industrial and Engineering Chemistry (Seoul), 9,
Freundlich adsorption isotherm. The adsorption of reactive 254–260.
422 V.R. Giri Dev et al.

Lopez, E., Soto, B., Arias, M., Nunez, A., Rubinos, A., & Barnal, Rengaraj, S., Arabindoo, B., & Murugesan, V. (1999). Prepara-
M. (1998). Adsorption properties of red mud and its use for tion and characterization of activated carbon from agricultural
wastewater treatment. Water Research, 32, 1314–1322. wastes. Indian Journal of Chemical Technology, 6, 1–4.
Malik, P.K., (2003). Activated carbon from sawdust and rice husk Santhy, K., & Selvapathy, P. (2006). Removal of reactive dyes
use of activated carbons prepared from sawdust and rice husk from wastewater by adsorption on coir pith activated carbon.
for adsorption of acid dyes: a case study of acid yellow 36. Bioresource Technology, 97, 1329–1336.
Dyes and Pigments, 56, 239–249. Senthilkumaar, S., Kalaimani, P., Porkodi, K., Varadarajan, P.R.,
Murherjee, P.S., & Satyanarayana, K.G. (1984). Structure and & Subbhuraam, C.V. (2006). Adsorption of dissolved reactive
properties of some vegetable fibres, part 1. Sisal fibre. Journal red from aqueous phase onto activated carbon prepared from
of Materials and Science, 19, 1925–1934. agricultural waste. Bioresource Technology, 97, 1618–1625.
Muzzarelli, R.A.A., & Rocchetti, R. (1986). Metal adsorption by Senthilkumaar, S., Varadarajan, P.R., Porkodi, K., & Subbhuraam,
modified chitins. In R. Thompson (Ed.), Trace metal removal C.V. (2005). Adsorption of methylene blue onto jute fibre
from aqueous solution (pp. 44–45). London: The Royal Soci- carbon: Kinetics and equilibrium studies. Journal of Colloid
ety of Chemistry. and Interface Science, 28, 78–82.
Namasivayam, C., & Kadirvelu, K. (1997). Activated carbons Singh, D., & Rawat, N.S. (1994). Bituminous coal for the treatment
prepared from coir pith by physical and chemical activation of Cd(II)-rich water. Indian Journal of Chemical Technology,
method. Bioresource Technology, 76, 63–69. 1, 266–270.
Netpradit, S., Thiravetyan, P., & Towprayoon, S. (2003). Eval- Wilson, P.I. (1971). Sisal (Vol. II). Hard fibres research series, no.
uation of metal hydroxide sludge for reactive dye adsorp- 8. Rome: FAO.
tion in a fixed-bed column system. Water Research, 38, 71– Zhang, T., Walawender, W.P., Fan, L., Fan, M., Daugaard, D., &
78. Brown, R.C. (2004). Preparation of activated carbon from for-
Ozacar, M., & Sengil, I.A. (2002). Adsorption of reactive dyes est and agricultural residues through CO2 activation. Chemi-
Downloaded By: [INFLIBNET India Order] At: 05:34 11 June 2010

on calcined alunite from aqueous solutions. Journal of Haz- cal Engineering Journal (Amsterdam, Netherlands), 105, 53–
ardous Materials, B98, 211–224. 59.

S-ar putea să vă placă și