You are on page 1of 9

Chemical Engineering Journal 174 (2011) 117–125

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal
journal homepage:

NaOH-activated carbon of high surface area produced from coconut shell:
Kinetics and equilibrium studies from the methylene blue adsorption
André L. Cazetta a , Alexandro M.M. Vargas a , Eurica M. Nogami a , Marcos H. Kunita a ,
Marcos R. Guilherme a , Alessandro C. Martins a , Tais L. Silva b , Juliana C.G. Moraes a , Vitor C. Almeida a,∗
Department of Chemistry, Universidade Estadual de Maringá, Av. Colombo 5790, CEP 87020-900, Maringá, Paraná, Brazil
Department of Civil Engineering, Universidade Estadual de Maringá, Av. Colombo 5790, CEP 87020-900, Maringá, Paraná, Brazil

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

Article history: Activated carbons (ACs) of coconut shell produced by NaOH activation at impregnation ratios of
Received 5 July 2011 NaOH:char (w/w) equal to 1:1 (AC-1), 2:1 (AC-2) and 3:1 (AC-3) were prepared. The properties of these
Received in revised form 20 August 2011 carbons, including BET surface area, pore volume, pore size distribution, and pore diameter, were char-
Accepted 22 August 2011
acterized from N2 adsorption isotherms. It was found that the ACs are essentially microporous and that
the BET surface area was in order of 783 m2 g−1 for AC-1, 1842 m2 g−1 for AC-2, and 2825 m2 g−1 for
AC-3. Scanning electron microscopy images showed a high pore development while Boehm method and
NaOH-activated carbon
Fourier-transform infrared spectroscopy spectra indicated the presence of acid functional groups which
Coconut shell
Methylene blue
was confirmed by pH drift method. The adsorption equilibrium and kinetics of methylene blue (MB) onto
Adsorption AC-3 were carried out. Experimental data were fitted to the four isotherm models (Langmuir, Freundlich,
Toth and Redlich–Peterson), and was found that Langmuir model presented the best fit, showing maxi-
mum monolayer adsorption capacity of 916 mg g−1 . The kinetic studies showed that experimental data
follow pseudo-second-order model. The mechanism of the adsorption process was described from the
intraparticle diffusion model. The AC-3 has a high surface area and showed to be an efficient adsorbent
for removal of MB from aqueous solutions.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction production of ACs from cheap and renewable precursors, such as
olive husk [3], coffee endocarp [4], cotton stalks [5], plum kernels
The impacts caused by a variety of industrial pollutants and [6], fir wood [7,8], pistachio shell [8], olive stone [9], bamboo [10]
growing concern for environmental issues have led to the search and flamboyant pods [11].
for new methods of treatment, and development of new materials The coconut shell is a potential precursor for the production of
that are able to reduce these environmental problems. Among the ACs, because it corresponds to 35% of the fruit mass. Brazil is the
various types of existing effluent treatment, the adsorption pro- fourth largest producer of coconut in the world: its current produc-
cess using activated carbon is of easy application, good efficiency tion is equivalent to 6% of world, which generates a large amount
and economically viable [1]. of waste from this fruit. The use of coconut shell for the production
Activated carbons (ACs) are porous materials that have a high of ACs has been studied by some researchers, which reported the
surface area and high adsorption capacity, which can remove a chemical activation of the material from chemical reagents, such
wide variety of pollutants such as dyes, heavy metals, pesticides as KOH [12–14], H3 PO4 –NaHCO3 [15] and ZnCl2 [16]. The produc-
and gases. Due to its adsorptive properties, the ACs are used to tion of ACs from coconut shell by chemical activation with NaOH,
purify, detoxify, deodorize, filter, discolor or alter the concentra- so far, has not been reported in the literature yet. NaOH has been
tion of many liquid and gaseous materials. These applications are used in studies for production of ACs with high surfacial area from
of great interest in various industrial sectors such as food, phar- fir wood [17], plum kernels [6] and flamboyant pods [18]. Among
maceutical, chemical, oil, mining, and especially in treatment of the basic reagents, Tseng [19] reported that NaOH activation in
drinking water [2]. comparison with KOH activation has advantages such as: (i) lower
Because of the high cost and non-renewable source of commer- dosage (weight measurement), (ii) cheaper, (iii) more environmen-
cially available AC, in recent years, researchers have studied the tally friendly, and (iv) less corrosive.
Methylene blue (MB) is a cationic dye that is most com-
monly used for coloring. It is generally used for dyeing cotton,
∗ Corresponding author. Tel.: +55 44 3261 3678; fax: +55 3261 4334. wool, and silk. MB can cause eye burns in humans and animals,
E-mail address: (V.C. Almeida). methemoglobinemia, cyanosis, convulsions, tachycardia, dyspnea,

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.

nausea. was defined as the volume of liquid nitrogen cor. 1. titration [23] and pH drift method [24]. The parameters obtained from the different mod- using the Brunauer–Emmett–Teller equation (BET). various initial concentrations (100–1000 mg L−1 ). The surface organic struc- The focus of this research was to prepare ACs from coconut shell tures of the raw material and AC were studied by FT-IR spectra by NaOH activation and evaluate its potential for adsorption in recorded at 4 cm−1 of resolution and 20 scans min−1 between 4000 removal of MB from the aqueous solution.99 [22]. respectively. This dye has been out for raw material.1.5 values of 3. The surface area. In the washing step. In order to establish the removal capacity of this adsorbent. qe (mg g−1 ) was a vertical stainless steel reactor under magnetic stirring for 2 h and calculated by Eq. often serves as a model compound for removing organic contami. Yield (%) = × 100 (1) wo where wc and wo are the final activated carbon dry weight (g) and 2. The comparing absorbance to a calibration curve previously obtained. Cazetta et al. VT . but the aqueous activated carbon was separated using 0. was placed in a horizontal stainless steel reactor and spectrophotometer (Varian Cary 50 UV/Vis) at its maximum wave- heated in a furnace at the rate of 20 ◦ C min−1 from room temper. Textural characterization of the ACs was carried out by N2 The application of adsorption isotherms is very useful to adsorption at 77 K using QuantaChrome Nova 1200 surface area describe the interaction between the adsorbate and the adsorbent analyzer. Previous tests were performed the raw material used in this study by ASTM-D1762 Standards [21] varying the solution pH from 2 to 10 and the MB removal of approx- revealed moisture.28. length () of 664 nm. and drying. was calculated as the difference between VT and V␮ . respectively. The aver.5 h. Batch adsorption studies isotherms and adsorption kinetics were fitted to the experimental data. volatile matter. AC-2. After that. the experiment was carried out for 2. The fruits were washed with dis. was selected because it favors the adsorption system MB-AC-3.5 to eliminate activating agent residues and other inor. A stock solution of 1. Scanning electron ference in the physical interpretation. 900. The prepared activated carbon time. Brazil. Initial concentrations of 800. Raw material appropriate amount of MB in 100 mL and completing the volume of 1000 mL with distilled water. and 1000 mg L−1 of the dye wc and an adsorption time of 150 min were studied. The concentrations of The carbon obtained was dried at 110 ◦ C for 24 h and kept in tightly MB were similarly measured. and 400 cm−1 using a Bomem MB-100 spectrometer. Therefore. the resulting mixture was where C0 and Ce (mg L−1 ) are the initial and equilibrium liquid- washed with a 0. 0. The amount of tilled water.118 A. was calculated by Eq. washing. was determined from isotherms of any system. (C0 − Ct )V and AC-3.0 h.45-␮m membrane 2. 2:1. The proximate analysis of to ensure equilibrium was reached.4. and W (g) is the mass of dry adsorbent used.5 h ground and granulometrically separated. The MB concentrations in the supernatant solu- The raw material.52. On Vm . Materials and methods the molecular weight of 319. solution. / Chemical Engineering Journal 174 (2011) 117–125 irritation to the skin. and if ingested. The amount of MB adsorbed onto AC. which had particle size between 250 ␮m tions before and after adsorption were determined using a UV–vis and 425 ␮m. Batch adsorption was performed in Coconuts used for preparation of AC were obtained from local a set of 50 mL plastic flasks containing 25 mL of MB solutions with market in Maringá. dried at 110 ◦ C for 48 h. All samples were filtered prior to analysis (using 0. model SS 550) was carried nal tract. and subsequently dried at 110 ◦ C for 48 h. the same procedure was followed. The cationic dye. In this study. ical characterizations of the ACs were also performed. For batch ganic species formed during the process. which was maintained for 1. Germany). SBET . MB or Basic Blue 9 (B. (2): then dried at 130 ◦ C for 4 h.60%. was used as an adsorbate. AC-2 and AC-3 to study the development studied because of its known strong adsorption onto solids. qt = (3) W The activated carbon yield was defined as the final weight of product after activation. samples were taken at preset time intervals. and 20. V␮ . microscopy (SEM) analysis (Shimadzu. ash. was calculated using the relation 4VT /SBET . vomiting. The MB concentration was determined by ature to 500 ◦ C. The total pore els provide important information on the sorption mechanisms volume. and heated qe = (2) W at the rate of 20 ◦ C min−1 to the final temperature of 700 ◦ C.85 g mol−1 . and diarrhea [20]. at the ratios of 1:1. an interesting trend in the isotherm modeling is age pore diameter. The micropore volume. and 3:1 (NaOH:char) in reported.60. AC-1. (3): at NaOH:char ratios of 1:1. and fixed carbon content imately 90% in all pH range was determined. The reactor containing the dry mixture (C0 − Ce )V was set into a furnace under N2 flow of 100 cm3 min−1 . qt (mg g−1 ). the pH 6. The Langmuir and Freundlich models are the most the Dubinine–Radushkevich equation and the mesopore volume. Paraná.L. was determined with librium data.025 g of AC was added to each flask and kept at 25 ◦ C on a shaker. the kinetic studies. The surfaces of ACs were chemically characterized by Boehm nants and colored bodies from aqueous solutions [10]. respectively. Herzog. For equilibrium studies. and maintained at this temperature for 2. and 3:1 were labeled as AC-1.3. different models of 2. V (L) is the volume of the until pH ∼6. 74.2. The textural and chem. 2:1. irritation to the gastrointesti. the isotherms of . respectively. obtained char was mixed with varying amounts of NaOH pellets All experiments were duplicated and only the mean values were and 10 mL of water. the derivation in more than one approach.0 g L−1 was prepared by dissolving the 2. and the surface properties and affinities of the adsorbents. The amount of MB adsorbed at any closed bottles for further analysis. Preparation and characterization of activated carbon filters) in order to minimize the interference of small particles of the activated carbon. the shells were removed from the fruits. Adsorption isotherm and kinetic models the precursor dry weight (g). thus directing to the dif- and the pore size distribution. and it of porosity. accepted surface adsorption model for single solute systems.1 M solution of HCl followed by hot distilled water phase concentrations of MB. the other hand. There responding to the amount adsorbed at a relative pressure of are several equations for analyzing experimental adsorption equi- P/P0 = 0. by the BJH method. After cooling. It has the molecular formula C16 H18 N3 SCl and 2.45-␮m membrane filters. Dp . The percent yield where Ct (mg L−1 ) is the liquid-phase concentration of MB at any was determined from the relation: time.

26% and 18.0.94%. kid = intraparticle 0.5 nm (25 Å). 2.P) two parameters (Langmuir and Freundlich [25]) and three param- eters (Redlich–Peterson [26] and Toth [27]) were applied. The yield values based on the original weight of the raw material The pore size distributions of the prepared ACs are shown in were of 33. bT 0. The values of correlation coefficients )/qe.9 and nT = Toth constants.3 second order [29] and intraparticle diffusion model [25] were used to understand the adsorption dynamics in relation to time for the 0. qe. and that the the experimental and calculated equilibrium adsorption capacity material in question consists mostly of micropores [30]. showing a linear relationship of SBET with increasing of the NaOH:char ratio.21 0 and pseudo-second order were fitted employing the non-linear fit. pseudo- 0.4 0. 1(b) shows the linear fits for the isotherms of AC- 1. Addi- the AC-1. Both adsorption isotherms and kinetic models of pseudo-first 0.8 AC-2 diffusion constant.L. from coconut shell by NaOH activation. respectively. also showed that the increase of the NaOH:char promoted and increase in the SBET value. K1 and K2 = rate constants for the pseudo-first and pseudo. The decrease in the yield for ACs is justified by Table 2 lists the physical properties of activated carbon derived action of the dehydrating reagent (NaOH). where na is the amount in moles adsorbed at the relative 3. was calculated for kinetic studies by Eq. N−1 which also are known as Langmuir. A.03 0. 3. Table 1 0.1. the val- AC-2 and AC-3.80% for Fig. value. 0.7 0. AC-2 and AC-3.12 0. the isotherms that show reversibility are classified as type I. (4). which used the fir wood [17] and Siberian 3. The BET equation requires a linear fit that relates P/na (P0 − P) and P/P0 . b KF and nF = Freundlich constants. increase in the impregnation ratio (NaOH:char) caused a decrease indicating a development of microporosity of the material in the yield values.exp and qe. a progressive increase in ues of VT . V␮ and Vm increased with the NaOH:char. 1. AC-2 and AC-3 were of approximately reaction: 1000 m2 g−1 . Relative Pressure (P/P ) ting method. As can be observed in Table 2. using the software Origin 6.15 0. As can be observed. / Chemical Engineering Journal 174 (2011) 117–125 119 Table 1 Non-linear forms of kinetic and isotherm models. a 1000 Models Names Expression 900 Adsorbed Volume at STP (cm g ) -1 AC-3 qe = Qm Ka Ce 800 3 Isotherm Langmuir 1+Ka Ce Freundlich RL = 1 700 1+Ka Ce qe = KF Ce1/nF 600 Redlich–Peterson qe = ARP Ce 500 AC-2 g 1+BRP Ce Qmax bT Cf 400 Toth Q = nT [1+(bT Cf )1/nT ] 300 Kinetic Pseudo-first order qt = qe [1 − e−K1 t ] 200 AC-1 h0 = K1 qe 100 K2 q2 t Pseudo-second order qt = e 1+K2 qe t 0 0.4 The kinetic models such as pseudo-first order [28]. a 0. the tionally. qe (%).5 + C Qm = maximum adsorption capacity. 23. as well as the value of SBET . Addition- ally. According to qe (%) = 100 (4) IUPAC. Fig. R2 . Ka = Langmuir constant. 1(a) shows the N2 adsorption isotherms obtained for AC-1. Researches. ARP .0 h0 = K2 q2e 0 Relative Pressure (P/P ) Intraparticle diffusion qt = kid t0.8 1. AC-2 and AC-3. C = intercept.9999.1 shown in Table 1. the N2 volume was observed for whole range of relative pressure. The differences between the the activation mechanism with NaOH is according to the following SBET values of AC-1 and AC-2.9998 for AC-1.exp − qe.9992 and 0. N2 adsorption (closed symbols) and desorption (open symbols) isotherms at 77 K (a) and linear fits for the adsorption isotherms (b) of the AC-1. which provided elimi. AC-3 0. respec- tively.06 0.exp ]2 and that the higher initial volume was shown for AC-3.5 0 shows the equations and parameters of such isotherms.2. Results and discussions pressure P/P0 . system were chosen from the correlation coefficient (R2 ). and intraparticle diffusion model. BRP and g = Redlich–Peterson constants. AC-1 second order adsorption.   [(qe. respectively. An increase in pore volume was observed for the ACs. RL = separation factor. Tseng and co-workers [7] report that NaOH:char ratio increased from 1 to 3. breaking the bonds C–O–C and SBET of the ACs increased from 783 m2 g−1 to 2825 m2 g−1 when the C–C of the raw material [22]. respectively. The theoretical models most appropriate that describe the experimental data of MB-AC-3 Fig. Textural characterization anthracite [31] as a raw material.6 P / n (P . The data show that the nation and dehydration (mg g−1 ) are that the adsorbate and adsorbent have a high affinity. VT is directly . Yield were 0. Cazetta et al. This type of isotherm indicates where N is the number of data points. According to the figure.80% for the char and of 28. the increase in the 6NaOH + 2C  2Na + 2Na2 CO3 + 3H2 (5) NaOH:char promotes an increase of the SBET and a decrease in the AC yields. AC-2 and AC-3. h0 = initial adsorption rate.6 0. The equation and parameters of these models are 0. According to the results. AC-2 and AC-3.18 0. the most of the pores had sizes smaller than 2. Fig. the normalized standard deviation.2 0.09 0.2 MB-AC-3 system.

152 83. Vm = mesopore volume.775 0. Cazetta et al.2. The methodology consists of a series of titrations in which it is possible to quan- Fig.75 0 1.120 A.75 0. AC-2 and AC-3.378 0.37 0 0. 2:1 (AC-2) and 3:1 (AC-3).4 AC-3 2825 1. lactones and phenolics.3 for the AC-1.25 5.73 1. AC-2 and AC-3 were 0. The acti- vation process rearranges the carbon structure producing a more ordered structural skeleton.6 1.356 0. The values of Vm and Dp for AC-1.63 28. 1.3 2. respectively (Table 2).75 0.6 and 76.00 AC-2 0. related to the development of porosity of the material.00 1.009 0. 2. SEM images of the AC-1.63 nm.01 .022 cm3 g−1 . (iii) widening of the existing pores and (iv) merger of the existing pores due to pore wall breakage [32]. Chemical surface characterization The method described by Boehm [23] was used in chemical surface characterization of the prepared ACs.27 18. the increase of NaOH:char pro- moted a development of mesopore and consequently a decrease in the micropore percentages (V␮ /Vt (%)). In addition. which occurred when large amounts of NaOH were used [3].003 0. The activation method with NaOH provided the development of many pores with varying sizes and materials of high surface area.62 0 0. 0. The values of V␮ /Vt (%) were 94.927 0.2 1. 3.3. Dp = average pore diameter. The micropores were the responsible for the increase of VT .38 0.022 94.9 AC-2 1842 0. there was a tendency of increase of Vm and Dp with the increase of NaOH:char.80 nm and 2.47 6. Pore size distribution of AC-1. 3(a–c) shows the SEM images for the ACs.498 1.8 SBET = BET surface area.80 23. VT = total pore volume. SBET (m2 g−1 ) VT (cm3 g−1 ) V␮ (cm3 g−1 ) Vm (cm3 g−1 ) V␮ /VT (%) Dp (nm) Yield (%) AC-1 783 0.75 2.006 0.27 nm. respectively. 83.143 0. According to the results. V␮ /VT = percentage of micropores. Table 3 Results of the Boehm and pH drift methods for the AC-1.75 2.355 76.018 AC-3 0. 3.355 cm3 g−1 and 1. Carboxylic (mmol g−1 ) Lactonic (mmol g−1 ) Phenolic (mmol g−1 ) Acid (mmol g−1 ) Basic (mmol g−1 ) Total (mmol g−1 ) pH drift AC-1 0. / Chemical Engineering Journal 174 (2011) 117–125 Table 2 Textural characteristics of the activated carbons in the NaOH:char ratio of 1:1 (AC-1). (ii) cre- ation of new pores. 0.09 AC-3 0.88 1. The pore development occurs from four stages: (i) opening of previously inaccessibly pores. AC-2 and AC-3. AC-2 and AC-3.5 0. The Boehm method results are shown in Table 3. tify chemical groups such as carboxyls. The presence of mesopores and micropores in AC enhances their adsorption capacities. AC-2 and AC-3.152 cm3 g−1 and 0. This tendency can be justified by the micro- pore merge and collapse.000 15 20 25 30 35 40 45 50 55 60 Diameter (Å) Fig.021 AC-1 3 AC-2 0. V␮ = micropore volume. especially for large molecules of adsorbates as dye molecules [33]. Fig.012 0.L.015 0.50 5.024 Incremental Pore Volume (cm g ) -1 0.

the RL values decreased from 5. which et al. The Langmuir and Freundlich isotherms are known as by Boehm method and by other researchers which produced ACs two-parameter models. which provide information on the adsorp- from a chemical activation [36. the pHpzc value of 6.37]. the basic character is presented for materials produced from thermal treat.5 30 Coconut shell AC-3 Transmitance (%) Transmitance (%) 29 19. The presence of hydroxyl groups. on the are distributed between the liquid phase and solid phase when the graphene layer. rial.26 mg g−1 and bonyl group. tion mechanism. Fig. The Qm is close to the experimental value of lignocellulosic structure of coconut shell as also observed in oth.0 for the Freundlich.L. there was a gradual increase in decrease in the functionality of the raw material. and are shown The acid characteristic of the ACs agrees with the results obtained in Fig.5 AC-2 4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500 -1 -1 Wavenumber (cm ) Wavenumber (cm ) Fig. the Qm and R2 val- located at 580 cm−1 [40]. MB-AC-3. The The FT-IR spectra were obtained to evaluate qualitatively the Redlich–Peterson isotherm is known as three-parameter model. [18]. linear (RL = 1).0 26 25 17. Redlich–Peterson and Toth isotherms in their non- AC-1 was lower than for AC-2 (5. char. it resembles the empirical proposal. The broad band at 1058 cm−1 is form a monolayer of adsorbate on the surface of the mate- attributed to the angular deformation symmetrical of ethers [39]. In addition. and cotton stalks [5]. The band caused by O–H out-of-plane bending vibrations band is According to the results presented in Table 4.01). is attributed to axial deformation of carbonyl groups (C O). A. The region between 1700 cm−1 and 1500 cm−1 are attributed to C C lactonic groups have not been detected and basic groups had values symmetrical stretching of pyrone groups and C O of carboxylic of approximately 0. The values of the maximum adsorption capacity (Qm ). in which the molecules of 1300 cm−1 and 1100 cm−1 . The Toth isotherm is of three-parameters and was material. ethers and aromatic compounds is an evidence of the 0. Langmuir isotherm that can be used to verify if the adsorption in the The FT-IR spectra of the ACs obtained are shown in Fig. oxygen free.0 28 18.5 27 AC-1 18. jackfruit peel by Weber and Chakkravorti [46] is an important parameter of the waste [24].25 mg g−1 . 4(b). Qm that is equal to 955. The basicity is due to Lewis basic sites. other bands decreased drastically. boyant pods. The adsorption isotherms describe how the adsorbate molecules ment. pyrone. four adsorption isotherm models namely the Langmuir. The region of the spectrum of 1612 cm−1 tems [27]. Axial and angular deformation of ketones arises in the region which occurs in a homogeneous surface. which was developed groups. / Chemical Engineering Journal 174 (2011) 117–125 121 a 32 b 20. The correlation coefficient (R2 ). On the other hand. The use of chemical reagents in the activation process provides an increase in the amount of acid groups present in the ACs surface. respectively. saturating the pores and preventing the transmigration [45].75 mmol g−1 for prepared ACs. broken during the carbonization process followed by the activa. which indicated various surface functional groups. tion capacity and constants related to the activation energy.4. car. The spectra shown in Fig.8805. characteristics of acidity and basicity of activated carbons. were applied to the equilibrium data. it can be observed that there was dis. models from experimental data are shown in Table 4. As can be observed in Table 3. The developed to explain adsorption process in heterogeneous sys- broad band at around 3404 cm−1 is typically attributed to hydroxyl tems. favorable (0 < RL < 1) According to the results. by fitting them to different models is important to find a sustainable The pH drift method provides important information about the model that can be used [44]. acteristics of aromatic rings appear in the region of 1465 cm−1 The Langmuir model assumes that the adsorption is a process [38]. The heterogeneity fac- . respectively. The Freundlich model is an empirical equation based on the tion. and other constants obtained for the stretching vibration of the molecular plane of C C bonds. and from some surface groups containing oxygen system reaches the equilibrium [43]. 4(b) are similar to those reported can be seen that acid characteristics are more evident for AC-2 and by Vargas et al. or irreversible (RL = 0). Cazetta et al. Montes-Morán the amount of acid groups (carboxylic and phenolic) for ACs.55 × 10−5 . [42] reported that the bands which were observed in the consequently caused an increase in the amount of total groups. 4. The spectra are which incorporates the factors of Langmuir and Freundlich equa- shown in Fig. Adsorption isotherms as observed in other studies [18. indicating that the chemical bonds were to 5.34].09) and AC-3 (5. which produced activated carbons from flam- AC-3. as the In order to optimize the design of an adsorption system of pHpzc value. The separation factor (RL ) defined ers materials such as Tunisian olive-waste cakes [41]. FT-IR spectra for the raw material (a) and ACs (b). 3. and chromene type structures [35]. Additionally. system is unfavorable (RL > 1).0 31 19. indicating a adsorption on heterogeneous surface [47]. indicating that the MB-AC-3 system is favorable. 5. The band located at around 2900 cm−1 corresponds to by Freundlich to explain the adsorption phenomenon of these sys- C–H stretching vibration. 4(a) shows the FT-IR spectrum of the raw tion in a single. chemical structures of the raw material and ACs. which has helped in the understanding of the adsorp. The analysis of isotherm data such as carbonyls. linear forms. According to Table 3. For the value range of concentrations stud- appearance of bands when comparing the raw material spectrum ied (100–1000 mg L−1 ).52 × 10−3 with the ACs spectra. 4. it groups. ues obtained from Langmuir isotherms were of 916.

and that the experimental models: pseudo-first order and pseudo-second order. -1 500 Langmuir Redlich–Peterson model is used as a compromise between Lang- 400 muir and Freundlich models [49]. it describes the formation of monolayer 800 coverage of dye molecule at the outer surface of the AC-3 [50].47 × 103 (L mg−1 )−g Ka = 1. Non-linear fits of the isotherm models.27 nm. which means that the isotherms 0 conform to Langmuir model better than Freundlich model. 900 The Toth model is a combination of the characteristics of 800 the Langmuir and Freundlich isotherms [45]. The Toth equation (Table 1) reduces to Langmuir for nT = 1. Additionally. The NaOH-activated carbon pre- -1 Ce (mg L ) pared in this work presented a high surface area (SBET ). In the present study. / Chemical Engineering Journal 174 (2011) 117–125 Table 4 Langmuir. The parameter g in the equation 300 indicates which of the two models. the Langmuir isotherm is favored. the values of nF = 20.8 [12] ZnCl2 /steam 2114 Methane 122.8805 R2 = 0. According to the adsorption process.8796 nT = 0. The negative surface of AC-3 interacts effectively with the MB. The data of adsorption kinetics for the AC-3-MB results shown in Table 4. Redlich–Peterson and Freundlich (b).08 and 1/nF = 0.42 nm [25]. respectively.050 system were analyzed by non-linear fitting of two different kinetic indicate that the adsorption is physical.81 mg g−1 ARP = 24.26 mg g−1 describes the high adsorption 700 capacity of the AC-3. the Redlich-Peterson MB molecules can diffuse from solution into the AC. the model provided values of Qm and R2 qe (mg g ) Toth equals to 720. The Qm value of 916.L.122 A. 100 Table 5 lists a comparison of the surface area (SBET ) and maxi- 0 mum adsorption capacity (Qm ) of ACs from coconut shell produced 0 10 20 30 40 50 60 70 80 from various activation methods.08 bT = 0. Redlich–Peterson and Toth isotherm model parameters and correlation coefficients for adsorption of MB on activated carbon. bet- 200 ter fits the experimental data. which was proven by the high adsorption capacity of the MB dye. Additionally.5.8796.41 [15] KOH/CO2 – 2. Langmuir and Toth (a). Fig. and the Dp of AC-3 is 2. In addition.95 g = 0. Kinetic studies tor (nF ) indicates whether the adsorption process is linear (nF = 1). it can be observed that the -1 Ce (mg L ) Langmuir model yielded the best fit with the highest R2 value. Freundlich or Langmuir.031 BRP = 32. For g = 1. Freundlich. The fit of the experimental data to the Langmuir model indicates a homogeneous nature of the AC- 900 3 surface.78 [50] KOH/CO2 1026 Phenol 205. the value reaction in terms of order of the rate constant. Since the kinetics of 1/nF < 1 indicates a normal Langmuir isotherm while 1/nF > 1 parameters provide information for designing and modeling the is an indicative of cooperative adsorption [48].8796 R2 = 0. which reduces the Langmuir Experimental values 600 equation.26 This work . 3. Additionally. The R2 value for the Freundlich model was 0. Langmuir Freundlich Toth Redlich–Peterson Qm = 916. which is directly related to high surface are 600 Experimental values (SBET ) and the average pore diameter (Dp ). 0 10 20 30 40 50 60 70 80 Comparing the R2 values (Table 4).6-Trichlorophenol 191.95 is close to the unit value. which was described by 200 Boehm and pH drift methods. Kinetic studies are important to understand the dynamic of the chemical (nF < 1) and or physical (nF > 1).36 [52] Steam – Methylene blue 277. which justifies 400 the high value of Qm . Activation methods SBET (m2 g−1 ) Adsorbate Qm (mg g−1 ) Reference H3 PO4 902 Zinc 60.4. Cazetta et al.95 R2 = 0.8796. Considering that width of qe (mg g ) Freundlich -1 500 the MB molecules is 1. 700 nT = 0.90 [53] NaOH 2885 Methylene blue 916.35 L g−1 R2 = 0.32 mg g−1 Qm = 720. and g = 0 the equation of Freundlich is favored. the g value is close to unity. In this 100 study. The suitability of the Langmuir model to experimental data was con- firmed by the constant Redlich–Peterson model and the value 1/n b 1000 described by the Freundlich model.32 mg g−1 and 0. the adsorption is favored due to 300 the acid characteristics of the AC-3 surface.80 L mg−1 nF = 20.73 [13] KOH/CO2 1940 Methylene blue 434.85 [51] ZnCl2 /CO2 1884 Methylene blue 14. due to cationic property of the dye. which are Table 5 The BET surface area (SBET ) and maximum adsorption capacity values (Qm ) of coconut activated carbons produced from various activation methods.26 mg g−1 KF = 747.8796 a 1000 data fit preferentially the Langmuir isotherm. 5.

A. Additionally.00097 (g g−1 min−1 ) h0 = 333.18 ((mg g−1 ) min−1 ) R2 = 0.exp values. applied to the AC-3-MB system. the AC-3-MB system reached adsorption process is preferably controlled by chemisorption.14 (mg g−1 ) K1 = 0.9705 in different concentrations. being the first stage was completed Table 6 Pseudo-first order and pseudo-second order kinetic model parameters for different initial MB concentrations.59%).9909 R2 = 0. Ci .00104 (g g−1 min−1 ) h0 = 413.54 (mg g ) qe = 802. 6.exp (mg g−1 ) Pseudo-first order Pseudo-second order −1 800 795. The data from the three different initial concentrations fitting agreed with qe.96 (mg g−1 ) qe = 900.9758 R2 = 0.20 (mg g−1 min−1 ) h0 = 763.94 (mg g−1 min−1 ) h0 = 746. the intraparticle diffusion adsorption kinetic models. and the intercept model was confirmed by the low value of normalized standard value. Table 6 shows the parameters obtained from the fits of the To identify the diffusion mechanism.47 (min−1 ) K2 = 0. / Chemical Engineering Journal 174 (2011) 117–125 123 a 1000 1000 800 800 600 600 Experimental values qt (mg g ) qt (mg g ) Experimental values -1 -1 Pseudo-first order Pseudo-first order 400 Pseudo-second order 400 Pseudo-second order 200 200 0 0 0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160 Time (min) Time (min) c 1000 800 600 Experimental values qt (mg g ) Pseudo-first order -1 Pseudo-second order 400 200 0 0 20 40 60 80 100 120 140 160 Time (min) Fig.15 qe = 774. the qe values obtained by the ary layer. being that the highest values were observed for the pseudo-second Fig.64 (mg g−1 ) K1 = 0. 6.05 (mg g−1 min−1 ) h0 = 624.9959 qe (%) = 5.59 . Cazetta et al.50 qe = 826.34 ((mg g−1 ) min−1 ) R2 = 0. C0 (mg L−1 ) qe. The applicability of the pseudo-second-order kinetic responds to intraparticle diffusion constant. The value of the slope cor- kinetic model.9745 R2 = 0.69 (mg g−1 ) K1 = 0. According to Fig.L. 7 shows the plots of qt versus t1/2 . Non-linear fits of pseudo-first order and pseudo-second order kinetics for the MB concentration of 800 (a). at an approximate value of the thickness of bound- deviation (qe = 2.43 (min−1 ) K2 = 0.39 (mg g−1 ) qe = 856. 900 (b) and 1000 (c) mg L−1 .79 qe (%) = 2.13 ((mg g−1 ) min−1 ) R2 = 0.30 qe = 867. The correlation coefficients (R2 ) for model based on the theory proposed by Weber and Morris [54] was all models were greater than 0. 6.9998 900 868. as the equilibrium after 30 min.00092 (g g−1 min−1 ) h0 = 407. [50] which studied the methylene blue the adsorbent and adsorbate were favorable. suggesting that interactions between also reported by Tan et al. kdi . This suggests that the rate of the showed two stages of linearity.9932 1000 911. shown in Fig. adsorption onto KOH/CO2 -activated carbon from coconut.50 (min−1 ) K2 = 0.

G. not agree well with the intraparticle diffusion model Mater. D1762-84 (1984) 292–293. E. High adsorption capacity NaOH-activated carbon for of MB from the aqueous solution over a wide concentration range dye removal from aqueous solution. B.6-trichlorophenol using face area.L. S. Intraparticle diffusion plots for the adsorption at different initial MB concen- schemes on porous.74 795. 7. Hameed. and the second region is the gradual adsorption stage where from fir wood by KOH activation for adsorption of dyes and phenols from water. J. C.R. R. Hazard. Biochem. Fairén-Jiménez. from coconut shell presented good development and high BET sur.L.J.A. Garcia. R. A. G. Bioresour. A. 92 (2011) 178–184. order model.79 0. K. A. [22] A. 147 (2007) 1020–1027.G.C. Celzard. so the qexp value did [10] B. [13] I. [20] S.F. commonly encountered in olive mill wastewaters. pseudo-second order and intraparti. Hazard. Freundlich.C. 27 (1999) 11–18. Moreno-Castilla.L. E. [18] A.08 463. R. The kinetic data were tested for the Colloid Interface Sci. Some aspects of the surface chemistry of carbon blacks and other some organic pollutants. Technol. Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies. A.H. Tseng. Chen. Vargas. Ahmad. Influence of prepa- 0 1 2 3 4 5 6 7 8 9 10 11 12 13 ration conditions in the textural and chemical properties of activated carbons 1/2 1/2 from a novel biomass precursor: the coffee endocarp. F.9995 0. Colloid Interface Sci. Lenzi. J. V.F.T. Juang. Adsorption kinetics of a basic dye from aque- 1000 mg L ous solutions onto apricot stone activated carbon.86 730.P.A.57 10. Bioresour. carbons. Tseng. ficient R2 obtained for the plots.S. Mater. Juangm. V.59 471. J. Technol. Mesopore control of high surface area NaOH-activated carbon. Basta. M. Both the linear line [8] F. R. B. J. C. Purif. Din. 141 (2007) 819–825.V. [7] F. Preparation of highly microporous carbons tion.124 A. A. A. Carrott. Comparisons of porous and adsorption properties did not pass through the origin. 161 (2008) 65–72. [9] R. Appl. Cazetta et al. Giwa. within the first 10 min.M. The textural characterization showed that the ACs are essentially [14] Z. J. which suggests that the process was controlled by [21] ASTM-D1762-84. Crini. Preparation of high-surface-area activated carbons from microporous and that BET surface area of 2825 m2 g−1 was obtained coconut shell. Sep.09 4. El-Saied.C.L. 200 Bioresour.07 12. The adsorption process follows the pseudo-second of methylene blue onto jute fiber carbon: kinetics and equilibrium studies. 99 Time (min ) (2008) 7224–7231. Almeida. showed that the ACs has acid characteristics and carboxylic groups. E. Subbhuraam.T. C. Carrasco-Marín. [6] R. 97 (2006) 1061–1085. Bello. Carbon 32 (1994) 759–769. showing a maximum adsorption capac. 303 (2006) 494–502.C. Ubago-Pérez. Anal. Tan.9834 0.M. linear models of Langmuir. N. material in the water and wastewater treatment for the removal of [23] H. NaOH-activated carbon from flamboyant (Delonix regia) pods: optimization of 4.M.M.C. [12] A. Mater. The (R2 )2 values are lower than Microporous Mesoporous Mater. Toth and Redlich–Peterson. Costa. [19] R.L. The ACs properties were related with NaOH:char ratio.71 0.H. Chemosphere phenolic groups and pyrone groups in its structure. Removal of heavy metal from industrial for AC-3. Michailof. 99 (2008) 300 5368–5373. The adsorption potential of the AC-3 produced for the removal [17] F.Z.L. Physical and chemical properties and adsorption type of activated carbon prepared from plum kernels by NaOH activation. SEM analysis. Ahmad. Fierro. I. Garcia. [15] O.A. [5] A. Hu. this suggests that the intraparticle of carbons activated by steam and KOH. The equilibrium data were fitted for the non.9087 900 89. D. on olive husk 0 derived activated carbons. M. Din. 47 (2005) 10–19. 92 (2006) 64–70. the experimental data. A. Gran- process. Environ. The well-developed porous structure was confirmed by wastewater using modified activated coconut shell carbon. surface and thermal properties of activated carbons pre- trations. R. Amuda. [4] J. The Boehm and pH drift methods and FT-IR analysis 36 (2007) 174–181.S.L. Reis. Bioresour. 1267.G.H. Technol. models of pseudo-first order. Wu.97 345.L. [16] J. J. Non-conventional low-cost adsorbents for dye removal: a review. 284 (2005) 78–82. P. R.M. 100 [3] C. Costa. Technol. Varadarajan. Cazetta.P. Colloid Interface Sci. Technol. [11] A. W. Mater. J. Preparation and characterization of activated carbon being that the Langmuir model was which better fitted to from a new raw lignocellulosic material: flamboyant (Delonix regia) pods. Forrest.V. Wu. A. X. Moraes. H. Conclusion preparation conditions using central composite rotatable design. El-Hendawy. Graham.H. Chem. Tseng.A. Vargas. Alexander. P. Hameed. J. Ci and correlation coef- ular and monolithic activated carbons from KOH-activation of olive stones. Hameed. Book ASTM Stand. G. V. Andrews. 100 (2009) 3941–3947. Carrott. Hazard. A. pared from cotton stalks. Tseng. Almeida. Adsorption cle diffusion. Enhanced adsorption of phenolic compounds. J. [2] G. Preparation of activated carbon from coconut husk: optimization study on removal of 2. Mater. Hazard. The first stage is the instantaneous adsorp. Ahmad. J. Luz. Ann. chemisorption. predicted by the pseudo-second order model.M. Microporous Mesoporous Mater.J. Ortiz. Senthilkumaar. J. Demirbas.9070 1000 104.L.R.9112 1000 Acknowledgement 900 The authors acknowledge Fundação Araucária and CAPES for the 800 financial support. / Chemical Engineering Journal 174 (2011) 117–125 Table 7 Intraparticle diffusion model constants and correlation coefficients for adsorption MB on prepared activated carbon. Wu. ity (Qm ) of 916. 283 (2005) diffusion was not the only limiting mechanism in the adsorption 49–56. J. Optimising the preparation of activated carbon from digested sewage sludge and coconut husk. E. Nabais. Eng. Lenzi. the intraparticle diffusion is the rate limiting. Batch adsorption of phenol onto The results of this study showed that the NaOH-ACs obtained physiochemical-activated coconut shell.A. Technol.14 739.S. Jeyaseelan. 44 (2001) 45–51. W. C. Panayiotou. Pyrolysis 82 (2008) 272–278. Boehm. Due to their chemical and textural characteristics. Sulak. M.L. 700 600 -1 800 mg L References qt (mg g ) -1 500 -1 900 mg L 400 -1 [1] E. J. C. Stavropoulos.W.L. Tay. Srinivasan.A.37 0.4. Manage. Porkodi.L. C0 (mg L−1 ) Intraparticle diffusion model kdi1 (mg g−1 min−1/2 ) kdi2 (mg g−1 min−1/2 ) C1 (mg g−1 ) C2 (mg g−1 ) R12 R22 800 119. Eng. 99 (2008) 6400–6408. Table 7 shows the values of kdi . M. Nogami.H. 152 (2008) 1256– was investigated.M.C. 162 (2010) 43–50. V.M. 153 (2008) 709–717. Effects of activation Fig. Bioresour.9865 0. Hazard. Tseng.26 mg g−1 . Kobya.M. 2-Steps KOH activation of rice the coconut shell activated carbon obtained in this work is potential straw: an efficient method for preparing high-performance activated carbons. response surface methodology. .

4- surface area activated carbon from coconut shells using microwave heating. Brasil. J. Chem. L. J.J. John Wiley & Sons. B. B. pp. H. B133 (2006) 304–308. 8 (2) (1991) 255–271. studies on equilibrium isotherm. Zhao. Microporous Mesoporous Mater. Quim. [54] W. Freundlich.L. Montes-Morán. Cazetta. A useful adsorption isotherms.J. M.S. Azevedo. J. J. A.C. Lima. [47] H. K.C. Qiu. AiChE J. [52] J. Hazard. 7th ed. Hartono. R.L. A. Webster.L. On the nature of basic solutions. Suárez. Royer. A.F. Han. R. Victoria. Hameed. Organic Spectroscopy: An amon. Barreto. B. Sainsbury. [53] N. Eng. chemical activated and their application for methylene blue removal.L. Tan. Preparation and characterization of activated carbon produced from coffee [46] T. N. 100 activated carbons: influence of surface chemical groups. Applications of Brazilian pine-fruit shell in natural and carbonized forms Eng. bon. S.J. Mater. M. Jaguaribe. 158 (2008) 65–72.R. E.H. Srinivasakannan. A. Cestari.L. J. Cardoso. El-Guendi. X. C. Menéndez. Adsorption isotherm. . R. Almeida. Costa Júnior. 101 (2010) 6163–6169. Bastos-Neto.W.C. Palanivelu. N. Feki.F. Hazard. Perg- [38] S. Adsorption of valeric acid from aqueous solution thermodynamic studies. Pietrzak. Introduction.F. onto activated carbons: role of surface basic sites.L. Colloid Interface Sci. Biosorption of [43] B. V. Gonçalves. Ind. Mater. Senthamarai. Silverstein. Penguin Books.P. Theobald.M. Z. Ahmad. Study of equilibrium. Dyke. 385–470. Adsorption of dyes on chemical activation with zinc chloride.P. Fuel 87 (2008) 2037–2040. D.L. 154 (2008) 337–346.F.M. Homogeneous surface diffusion model of basic dyestuffs on nat- Tartour phosphate rock. and thermodynamic parameters about methylene blue adsorption onto natural S. kinetic modeling nickel(II) ions onto Sargassum wightii: application of two-parameter and three. A. Zhang.H. 11 (2005) 864. Chem. J.S. Tunisian olive-waste cakes and its application for adsorption of heavy metal [26] J. Hazard. Mater.L. Malash. Vaghetti. Ahmad. J. Figueiredo.N. E. J.S. J.M.L. Siberian anthracite as a precursor mate.. Oxford. S.L. Eng. Pecan nutshell as biosorbent to remove Cu(II).I. Fuente.S. J. M.H.C. J. Sorption–desorption behavior of 2. Vijayalakshmi. Ringwood. [32] K. E. B.M. Y. [40] J. [30] S. J. (2011) 722–730. Sundaram. Chakkravorti.B. Indraswati. Australia. Dyes Pigment 51 studies on the adsorption of basic dye by a low-coast adsorbent: coconut (Cocos (2001) 25–40. Colloid Interface Sci. J. Floyd. Adsorption of dye from aqueous solution by cashew nut shell: zeolite.B.A. Pereira. L. M. Technol. Chem. Silva.W. Padmesh. Chem. [27] K. Chem. Int. I.C. 1st ed. Carreño. [31] P. Peterson. F. Brum.H.6-trichlorophenol on coconut husk-based activated car- parameter isotherm models. Desalination 261 (2010) 52–60. characterization. kinetics and thermodynamics of interactions. N. J. Silva. Cavalcante. Chem. Almeida. A. 144 (2008) 235–244. [44] M. Bioresour. Colloid Interface Sci. Methylene blue adsorption by the waste of Abu. 1962. Mahmound. J. Activated carbon from jackfruit [39] R. Han. Redlich.A. New York. Chem. Voudrias. Phys.L. C. Equilibrium modeling and kinetic blue by adsorption on various carbons – a comparative study. Y. Kinetics and mechanism of removal of methylene [37] B. S.K. 1971. Oliveira. Morris. M. Baccar. N. P. Tan. J. Y. J. Eng.C. Vargas. H.C. T. 811–821.J. Niranjanaa. Weber. kinetic [45] P. 168 coir dust. Ahmad. 162 (2009) 1522–1529.J.2. ural clay in batch adsorbers.S. I.B. Simon. M. T. J.F. J.K. Cunha. T. Technol. Microporous activated carbon prepared from coconut shells using [35] M. R. D.F.S. Ueber die adsorption in loesungen.M. Zhang. E. Sudaryanto. Adsorption of Gimezez. [28] G. 2005. M. Mn(II) and Pb(II) from aqueous [42] M. Conf.V. W. Macedo. 20 (1974) 228–238. Cazetta et al. D. Vaghetti.A. P.W. Órfão.C. Z. L. Araújo. Pore and solid diffusion models for fixed-bed waste.S. Adsorpt. M.L. Soares. Torres. Ramalingam. Kumar.A. El-Sayed.M. Kokkalis. Velan. El-Khaiary. Water pollution symposium vol. L.F. (2004) 64–72. Carbon 41 (2003) (2007) 361–364. adsorbers. Montiel. Tang. Duan. Eng. Peng. Bianch.4. Kannan. [36] A. Irawaty. kinetic and [34] Y. J.. Hameed. / Chemical Engineering Journal 174 (2011) 117–125 125 [24] D. A.L. Kiemle. K. Preparation of activated carbon from and equilibrium study. E. Mater. N.F. 140 (2008) 32–42. Eng. Hameed.R. Weber. from the timber industry as a precursor of activated carbon for the removal of [50] I. 63 (1959) [33] S.M. Veses. 145 (2009) 496–504. V. Nowicki. Proc. Vieira. C. E. 231-266. Wachowska. N. Yang. 298 (2006) 515–522. Chemosphere 40 (2000) 3–6. Phys. Prahas. Cardoso. Vijayaraghavan. Kunita. A. J.C.L. Bouzid. Chem. J. [29] R. Calvete. J.V. Bandosz.C. M. Ismadji. Mater. Royer. area activated carbon prepared from coconut husk: equilibrium. and mechanism of 2. Hazard. Carbon 41 (2004) 1219–1225. Wang. Preparation of activated carbon from walnut shells via vacuum [25] B. dchlorophenol by marine sediments. nucifera) bunch waste. Kartika. Dias. J.E. 348 (2010) 537–545. Fytianos.S. 164 (2009) 1213–1222. [49] O.M. M.X. 162 (2009) 270–280. E. S. M. 273 [51] D.P. as adsorbents to removal of methylene blue from aqueous solutions—kinetic [41] R. Sci. T. J. Kinetic and calorimetric study of the methylene blue on activated carbon produced from flamboyant pods (Delonix adsorption of dyes on mesoporous activated carbon prepared from coconut regia): study of adsorption isotherms and kinetic models. sites on carbon surfaces: an overview.A. M. 165 (2010) 209–217. Utilization of teak sawdust 1024–1026. Hazard. Sivanesan. S. Guerreiro. Yang. Lima. Mater. Hazard. A. Ismadji. Xia. J. Adsorption of basic dye on high-surface- dyes from synthetic effluents. Spectrometric Identification of peel waste by H3 PO4 chemical activation: pore structure and surface chemistry Organic Compounds. 57A (1907) rial for microporous activated carbons.F. Preparation of high [48] K.E.C. Nova 5 (2008) 1048–1052. ions.