Mesoporous carbonaceous material from fish scales as low-cost adsorbent for reactive orange 16 adsorption

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Mesoporous carbonaceous material from fish scales as low-cost adsorbent for reactive orange 16 adsorption F. Marrakchi a, Muthanna J. Ahmed b, W.A. Khanday a, M. Asif c, B.H. Hameed a,∗ a

School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia Department of Chemical Engineering, University of Baghdad, P.O. Box 47024, Aljadria, Baghdad, Iraq c Chemical Engineering Department, College of Engineering, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia b

a r t i c l e

i n f o

Article history: Received 7 June 2016 Revised 5 December 2016 Accepted 19 December 2016 Available online xxx Keywords: Adsorption Carbonization Fish scales Reactive dye Kinetics

a b s t r a c t This work investigates the possibility of utilizing carbonized fish (Labeo rohita) scales (CFS) as low-cost materials for the adsorption of reactive orange 16 dye (RO16) through batch processing. The textural and morphological characteristics of CFS were evaluated which showed mesoporous structure with BET surface area of 213.82 m2 /g and average pore diameter of 5.116 nm. The effects of initial RO16 concentration (25–400 mg/l), solution pH (3–13), and temperature (30–50 °C) on the adsorption efficiency of the prepared CFS were demonstrated. The equilibrium isotherm data were best correlated using the Freundlich equation. The prepared CFS exhibited maximum adsorption capacities of 105.8, 107.2, and 114.2 mg/g at 30 °C, 40 °C, and 50 °C, respectively. The pseudo-second-order model well represented the adsorption kinetics. The prepared CFS had a high adsorption capacity for RO16 and could be utilized effectively for the removal of reactive dyes from wastewater. © 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction Water pollution caused by synthetic organic dyes through the discharge of common effluents from textile and dyestuff industries is a worldwide environmental problem. Commercial dyes have over 1,0 0,0 0 0 types and a yearly production higher than 7,0 0,0 0 0 tons; moreover, about 2% of the produced dyes are discharged directly in aqueous effluent [1]. Given the variety of color shades and flexibility of utilization, reactive dyes are one of the widely used colorants in the textile industry [2]. During the dying process, 10–50% of these dyes are lost, which produce highly colored effluents. The direct disposal of these effluents into the aquatic environment is extremely deleterious because most of the dyes are carcinogenic and mutagenic; therefore, from the environmental viewpoint, the efficient removal of reactive dyes from wastewaters is very significant [3]. Many technologies have been applied for removal of synthetic dyes; however adsorption appears to be the most convenient and popular method due to its simplicity and high efficiency [4,5]. Although, zeolites and activated carbon are commonly used adsorbent for treatment of dyes and other pollutants [6–9], char represents an alternative, effective, and inexpensive adsorbent, wherein

∗

Corresponding author. E-mail address: [email protected] (B.H. Hameed).

the production of activated carbon requires higher temperature and additional activation process [10]. Char is a carbon-rich solid produced by the pyrolysis of organic wastes under the partial or full absence of oxygen. The favorable properties including surface characteristics, considerable hydrophobicity and aromaticity, and more surface functional groups, render char a suitable adsorbent for the treatment of organic and inorganic contaminants [11,12]. Several fish species are consumed daily in different parts of the world. Consequently, a large amount of wastes, which account for 50–70% of original materials, are generated in fish shops and processing factories [13]. The total fish output in Malaysia in 2010 was approximately 1.77 million tons at a value of RM 6.8 million; of the total production, 30% are solid wastes consisting of skin, scale, and bone [14]. The accumulation of these wastes leads to acute environmental contamination with undesirable odor and health problems. Therefore, the optimized treatment of these wastes to generate value-added products is the best solution. Solid fish wastes have been utilized for the production of a porous carbon with high performance for attraction of acid dye pollutant [15]. The high organic composition of fish scales, which are mainly of collagen fibers, provides the carbon for porous carbonaceous materials [16]. The objective of this work is to utilize carbonized fish scales as low-cost adsorbent for the adsorption of reactive orange 16 dye (RO16). In addition, the adsorption behavior of RO16 dye onto carbonized fish scales (CFS) is illustrated in terms of isotherms, kinetics, and thermodynamics.

http://dx.doi.org/10.1016/j.jtice.2016.12.026 1876-1070/© 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: F. Marrakchi et al., Mesoporous carbonaceous material from fish scales as low-cost adsorbent for reactive orange 16 adsorption, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.12.026

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F. Marrakchi et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–8 Table 1 Characteristics and structure of RO16 dye. Structure

Formula

Molecular weight (g/mol)

λmax (nm)

C20 H17 N3 Na2 O11 S3

617.54

492

with an automated Micromeritics ASAP 2020 surface area analyzer. The Brunauer–Emmett–Teller (BET) surface area was calculated by the BET equation. The micropore volume and total pore volume were determined using t-plot method. The surface morphologies of the raw FS and CFS were imaged using Zeiss Supra 35VP scanning electron microscope. The functional groups was examined by a Fourier transform infrared (FTIR) spectrometer (Model 20 0 0 FTIR, USA) with the wave number ranging from 40 0 0–40 0/cm. 2.3. Adsorption studies

Fig. 1. Images of (a) raw and (b) carbonized FS.

2. Materials and methods 2.1. Materials The raw fish scales (hereafter FS) were obtained from a local shop in Penang, Malaysia and repeatedly washed with distilled water to remove soluble impurities. The FS were then placed in an oven at 60 °C for 24 h and stored in tightly sealed containers until further use. RO16 dye was supplied by Sigma-Aldrich, Malaysia and was used as an adsorbate. The characteristics and chemical structure of RO16 dye are shown in Table 1. 2.2. Preparation and characterization of CFS The carbonization of FS was conducted in an electrical furnace under N2 (99.99%) at a flow rate of 100 cm3 /min and a heating rate of 10 °C/min. The sample was placed in a tubular stainless steel reactor and maintained at 600 °C for 90 min. After carbonization, the prepared CFS was cooled under N2 gas flow to room temperature. To remove residual inorganic matters from the prepared CFS and to open up its pores, CFS was washed with 1 M HCl. It was then rinsed with hot distilled water until the filtrate became neutral. The CFS were then dried at 105 °C for 24 h and were subsequently ground and sieved to a fraction of fine particles through a mesh of 250–500 μm. Raw and carbonized FS are shown in Fig. 1. The yield of prepared CFS was calculated using following equation [17]:

Yield (% ) =

Wf × 100 Wo

(1)

where Wf and Wo (g) are the mass of CFS and FS, respectively. To assess the effect of carbonization temperature on FS, thermo-gravimetric analysis (TGA) of FS was conducted with a Perkin–Elmer STA 60 0 0 TG/DTG analyzer. The elemental composition was performed using Quanta FEG 450 equipped with Oxford Instrument X-Max for energy-dispersive X-ray (EDX). The surface characteristics of CFS were measured using N2 adsorption and desorption isotherms at 77 K over a wide range of relative pressures

Batch equilibrium experiments were conducted by adding CFS powder (0.20 g) to a set of 250 ml conical flasks containing 200 ml of RO16 solutions with initial concentrations of 25, 50, 100, 150, 20 0, 30 0, and 40 0 mg/l. The sealed flasks were shaken at 125 rpm at various temperatures (i.e., 30 °C, 40 °C, and 50 °C), and pH was kept natural without any adjustment until equilibrium was reached. Solution pH was calibrated by adding a few drops of 0.1 M NaOH and 0.1 M HCl before each run to study the effect of the solution pH on the removal of RO16 by CFS adsorbent. The operating conditions were as follows: amount of CFS = 0.1 g; initial concentration of dye solution = 100 mg/l; temperature = 30 °C; and contact time = 24 h. For the point of zero charge (pHpzc) determination the initial pH (pHi ) of aqueous solutions (100 ml) were adjusted to a pH range of 2–12 using 0.1 M HCl or NaOH. Then, 0.1 g of CFS was added to each adjusted solution. The dispersions were shaken for 48 h at 30 °C, and the final pH of the solutions (pHf ) was determined. The point of zero charge (pHpzc) is the point where the curve pHf vs. pHi intersects the line pHf = pHi . Aqueous samples were taken from each RO16 solutions at precise time intervals. The concentrations of the RO16 in the supernatant solution before and after adsorption were determined using a double-beam UV–visible spectrophotometer (UV-1700 Shimadzu, Japan) at maximum wavelength, λmax = 493 nm. The percentage removal (%) of RO16 by the CFS adsorbent is described by the following:

Removal (% ) =

Co − C × 100 Co

(2)

where Co and C (mg/l) are the initial and final concentrations of RO16, respectively. The adsorbed amount at equilibrium, qe (mg/g), was computed from the concentration of the dye solution according to following relation:

qe =

(Co − Ce )V W

(3)

where Co and Ce (mg/l) are the initial and equilibrium liquid-phase concentrations of RO16, V is the volume of the dye solution (l), and W is the weight of CFS powder (g). The experimental equilibrium data were fitted using two well-known isotherm models, namely, Langmuir and Freundlich

Please cite this article as: F. Marrakchi et al., Mesoporous carbonaceous material from fish scales as low-cost adsorbent for reactive orange 16 adsorption, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.12.026

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F. Marrakchi et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–8 Table 2 Elemental compositions and molar ratios of FS and CFS.

isotherms [18,19]:

qL kLCe 1 + kLCe

Langmuir isotherm

qe =

Langmuir isotherm

qe = kF C e1/n

(4) (5)

where qL (mg/g) is the Langmuir maximum adsorbed amount of RO16 per unit mass of CFS, kL (l/mg) is the Langmuir parameter proportional to the rate of adsorption, kF (mg/g (l/mg)1/ n ), and n are Freundlich parameters. To obtain a more accurate comparison, root-mean-squared error (RMSE) and correlation coefficient (R2 ) were applied in this study according to the following equations [20]: n 

R2 = 1 −

i=1 n  i=1

 RMSE =

(qe, exp −qe, cal )

2

(qe, exp )2 − [(

n  i=1

2

(6)

qe, exp ) /n]

n 1  (qe, exp −qe, cal )2 n−1

(7)

i=1

where qe ,exp and qe ,cal are the experimental adsorption capacity and the calculated adsorption capacity at equilibrium from the models, respectively, and n is the number of data points. 2.4. Kinetic studies Kinetic experiments were conducted to determine the adsorption rate constants and equilibrium time of the adsorption process. Samples with different dye concentrations were taken at predetermined periods under the same conditions as applied in the equilibrium studies. The adsorbed amount at time t, qt (mg/g), was determined by equation [21]:

qt =

(Co − Ct )V

(8)

W

where Ct (mg/l) is the liquid-phase concentration of the dye at time t. The kinetic data were then fitted using the pseudo-first-order and the pseudo-second-order models. These models are expressed by following equations [22,23]:

P seudo- f irst -order P seudo-second-order

qt = qe (1 − e−k1 t ) qt =

k2 q2e t 1 + k2 qe t

(9) (10)

where qe and qt (mg/g) are dye uptakes at equilibrium and time t (min), respectively; k1 (1/min) and k2 (g/mg min) are the rate constants of first- and second-order models, respectively. The applicability of each kinetic model to describe the adsorption process was further validated by the correlation coefficient (R2 ) and RMSE [20]. 2.5. Thermodynamic studies The thermodynamic behavior of RO16 adsorption on CFS was demonstrated by evaluation of changes in Gibbs free energy (࢞G° ), enthalpy (࢞H° ), and entropy (࢞S° ) using following equations [24]:

In(K ) =

S ◦ R

−

H ◦ RT

G◦ = −RT In(K )

3

(11) (12)

where, K is equilibrium constant, R (J/mol K) represents the gas constant (8.314) and T (K) is adsorption temperature.

Sample

FS CFS

Elemental composition (%) C

N

O

P

Ca

S

46.08 65.37

26.64 23.55

24.86 6.62

0.91 1.82

1.27 2.55

0.24 0.00

Table 3 Surface area, pores size and pore volume of CFS. Property

Value

BET surface area (m2 /g) Langmuir surface area (m2 /g) t-plot micropore area (m2 /g) t-plot external surface area (m2 /g) Total pore volume of pores (cm3 /g) BJH average pore diameter (nm)

213.82 311.92 49.885 163.94 0.215 5.116

3. Results and discussion 3.1. Characterization of adsorbent The elemental analyses (EDX) of the raw FS and prepared CFS are presented in Table 2. The relative element contents show the loss of oxygen and nitrogen and the enrichment of carbon, which are resulted from the carbonization of FS. The diminishing of sulfur content in CFS reveals its capability for adsorption processes. This is due to the elimination of volatiles during pyrolysis that results in the reduction of non-carbon content and enhancement of carbon and hence adsorption. The yield of CFS calculated from Eq. (1) is 12.18%. The surface characteristics of prepared CFS have been evaluated and presented in Table 3 where the results show that the BET surface area and total pore volume are 213.82 m²/g and 0.215 cm3 /g respectively. The BJH average pore diameter of 5.116 nm also reveals that CFS has a mesoporous structure according to the IUPAC classification. The nitrogen adsorption–desorption isotherm along with pore size distribution of CFS are shown in Fig. 2a and b, respectively. It can be observed that the isotherm of CFS is thoroughly classified as a type IV, which is associated with a mesoporous structure. Also, the structure of CFS has pores mainly located in the mesoporous region. Extreme distance between the atoms of RO-16 dye molecule is 1.68 nm [25], while BJH average pore diameter of CFS adsorbent is 5.116 nm (Table 3). Ratio of average pore diameter of CFS to the maximum distance among the atoms of RO16 molecule is 3.05. Thus, the average pore diameter of the CFS adsorbent can accommodate three RO16 molecules which are diffused from the bulk of dye solution to the pores of CFS. This favorable mesoporous structure of prepared CFS enhances its performance for attraction of large molecules like RO16 dye. The dependence of adsorbent performance on its mesoporosity has already been demonstrated for adsorption of large dye molecules such as Rhodamine B and methylene blue onto activated carbons [26]. Fig. 3a and b shows the characteristic morphology associated to the FS and CFS respectively. The comparison of Fig. 3a with b reveals that the carbonization was effective in the formation and opening of pores on the surface of the CFS resulting from the elimination of organic and volatiles compounds during thermal decomposition process. The FTIR spectra for original and carbonized FS with and without dye loading are displayed in Fig. 4. Fish scales are mainly composed of collagen fibers and hydroxyapatite. Thus, many active functional groups are present on the surface of fish scales such as hydroxyl, amino, nitro, carbonyl, and phosphate. The broad band at

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Fig. 2. Plot of (a) N2 adsorption–desorption isotherm and (b) pore size distribution of CFS.

Fig. 3. SEM micrographs of (a) FS (30 0 0×) and (b) CFS (30 0 0×).

3336 cm−1 corresponds to O–H groups [27,28]. Band at 2974 cm−1 relates to C–H group (alkanes). The spectra of FS also show peaks at 1650 and 865 cm−1 , corresponding to NH bending in amines I and II of collagen. Additionally, bands at 1542, 1335 cm−1 indicates the presence of nitro groups due to N–O asymmetric stretching of nitro compounds. Two successive peaks at 1451 and 1412 cm−1 relate to carbonate CO3 2− group. Furthermore, the three medium peaks at 1115, 1245 and 1038 cm−1 are representative of C–O groups (alcohols, carboxylic acids, esters, and ethers). Bands at 600 and 565 cm−1 indicate the vibration of phosphate group due to the P–O asymmetric stretching of PO4 3− group. Accordingly, the hydroxyl and carbonyl groups are the main functional groups on the surface of raw FS. These observations are in good agreement with the previously published FTIR data for fish scales [29]. Generally, FTIR spectrum of CFS has nine bands at 3405, 2980, 1620, 1465, 1410, 1042, 885, 600, and 565 cm−1 . These bands relates to the structure of natural hydroxyapatite, which mainly contains hydroxyl and carbonyl groups [30]. Similar findings were also reported for bone char which is considered as a good adsorbent and the adsorption is contributed by carbon and hydroxyapatite [31,32]. After adsorption of RO16 on CFS, there is a clear disappearance of the bands at 1465, 1410, 600, and 565 cm−1 . The disappearance of these peaks can be attributed to the transport of Na+ ions from RO16 molecule to CO3 2− and PO4 3− anions on the CFS surface [33]. The disappearance of functional groups after dye adsorption was also observed by Karmaker et al. [34] for reactive orange 13 dye adsorption onto jackfruit seed flakes.

Fig. 4. FTIR of FS and CFS before and after RO16 adsorption.

3.2. Adsorption behavior 3.2.1. Effect of initial concentration and time The percentage dye removal versus contact time data at initial concentrations from 25 mg/l to 400 mg/l are shown in Fig. 5. It can be seen that the adsorption improves with time until equilibrium is attained. Maximum removal occurred within a contact time of 450 min. Removal is gradual and the change in the extent of adsorption is no longer noticeable thereafter. Initially, many

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Fig. 5. Effects of initial concentrations and time for RO16 removal onto CFS. (Adsorption temperature = 30 °C, W = 0.20 g, V = 0.20 l, stirring rate = 125 rpm.)

active sites are present for adsorption but with the progresses of time, the active sites get occupied due to competitive adsorption of sorbate molecules. Equilibrium is deduced to have been attained within 23 h for all of the studied concentrations. An equilibrium time of 5 h was reported for RO16 adsorption on pine shellactivated carbon [25]. This finding shows that the equilibrium state is related to the adsorbent type. An increase in initial dye concentration up to 50 mg/l enhances percentage removal by up to 94.96%, whereas the percentage dye removal at 100 mg/l is 82.59%. The percentage dye removal reduces with an increase in initial concentration and when equilibrium has been attained within a longer time because high dye concentration and the collision of sorbate molecules decrease adsorption rate. At higher dye concentration, greater number of dye molecules would quickly saturate the binding sites found on the surface area of asorbent. This would cause a decrease in the % removal due to the limited adsorption sites [35]. This finding confirms longer adsorption times for the dye samples with high initial concentrations. High dye concentrations are preferable for adsorption because of the high driving force for the transfer of sorbate molecules to adsorption sites [36]. 3.2.2. Effect of solution pH and mechanism The pHpzc is the pH where the adsorbent net surface charge corresponds to zero, and it offers the possible mechanism about the electrostatic interaction between adsorbent and adsorbate. The pHpzc value of 4.41 was obtained for CFS as shown in Fig. 6a. To determine the optimal pH, the adsorption behavior of RO16 onto CFS at pH 3–13 is presented in Fig. 6b. The maximum uptake can be observed at pH values lower than 3. In liquid solution, the reactive orange 16 dye molecule dissolves and transformed into their corresponding dye ions DSO3 − and Na+ . The surface of CFS is positively charged when the pH of solution is below than 4.41. Therefore, the adsorption occurs between the dissociated dye anions (DSO3 − ) and CFS surface sites [37]. When the pH is increased (3–7), the uptake reduces from its maximum value of 87.91 to 80.38 mg/g as a consequence of the decrease in electrostatic interactions between the dye anion and CFS due to deprotonation of surface active sites. Such mechanism can demonstrate the cause for the achieving maximum adsorption under strongly acidic conditions. However, further increasing the pH from 7 to 9 improves the uptake from 80.38 to 89.84 mg/g. Finally, the adsorbed dye is desorbed again under strongly alkaline conditions. Such observations infer that adsorption at basic medium is represented by a binding

Fig. 6. Effect of pH on the RO16 removal percentage at 30 °C. (CFS concentration = 1 g/l, the initial concentration of RO16 = 100 mg/l, adsorption temperature = 30 °C, contact time = 25 h.)

technique rather than an electrostatic interconnection. This behavior indicates the possibility of the sorption–desorption of RO16, as explained by Won et al. [38] for RO16 adsorption onto C. glutamicum biomass fermentation wastes. 3.3. Adsorption isotherm RO16 adsorption onto CFS equilibrium data, which was calculated using Eq. (2), are fitted to the Langmuir and Freundlich isotherms, which are respectively expressed in Eqs. (3) and (4). The results show the best fitting of equilibrium data by the Freundlich model compared to the Langmuir model at studied temperatures (Table 4). High R2 values (0.933–0.965) and low RMSE (7.452–9.912) have been obtained for data correlation by Freundlich isotherm (Fig. 7). Empirical parameter n of Freundlich equation is proportional to the extent of heterogeneity and adsorption intensity and also describes the apportionment of adsorbate ions on the sorbent surface. Favorable adsorption can be deduced when n > 1. In this study, the values of n are considerably greater than unity (4.69–6.94) at all studied temperatures, which indicate a favorable process. Previous studies also suggest that Freundlich isotherm has been found applicable for the adsorption of RO16 onto various adsorbents [39,20]. Freundlich isotherm has also been found applicable for the adsorption of metal ions onto various adsorbents [40]. The satisfactory representation of the isotherm data by the Freundlich model indicates the multiple-

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Table 4 Langmuir and Freundlich isotherm parameters for the adsorption of RO16 onto CFS at different temperatures. Isotherms

Parameters

Temperature (°C)

Langmuir

q0 (mg/g) kL (l/mg) R2 RMSE

Freundlich

kF ((mg/g) (l/mg)1/ n ) n R2 RMSE

30

40

50

105.80 0.269 0.958 8.168

107.20 0.484 0.895 13.478

114.20 0.612 0.916 12.778

36.520 4.690 0.965 7.452

48.280 6.050 0.933 9.912

54.940 6.940 0.953 9.551

Fig. 8. Nonlinear plots of kinetics models for RO16 adsorption onto CFS at 30 °C.

pseudo-second-order models, which are respectively expressed in Eqs. (8) and (9), at several initial dye concentrations (25–400 mg/l). The correlation results are summarized in Table 6 and the nonlinear fitted plot are presented in Fig. 8 for both kinetic models. It can be deduced that the adsorption kinetics of RO16 onto CFS is better described by the pseudo second-order kinetic model; because of the high R2 and low RMSE values than the pseudo first-order model at all studied initial concentrations. The best fitting of experimental data on the pseudo second-order kinetic model depicts that the adsorption rate of RO16 onto CFS does not depend on the dye concentration in solution but depends on the availability of the adsorption sites. These findings are supported by literature reports for the adsorption of reactive orange dye [47]. According to pseudo-second order model, increasing RO16 initial concentration from 25 mg/l to 400 mg/l improves adsorption capacity from 24.76 mg/g to 135.90 mg/g at 30 °C. The best correlation with pseudo-second-order kinetic model was also reported for RO16 dye adsorption onto the modified rice husk and chitosan adsorbents [48,49]. Moreover, it can be observed from results of Table 6 that the values of adsorption rate constant, k2 , for pseudo-second order model decrease from 2.59 × 10−4 to 3.89 × 10−5 g/mg min with increasing RO16 initial concentration from 25 to 400 mg/l, respectively. This behavior can be related to lower competition for the surface active sites at lower initial dye concentration. In contrast, at higher concentration, the competition for the adsorption sites is high, so lower adsorption rate will be obtained [4]. Similar observations were reported by Rosa et al. [49] for kinetic analysis of RO16 adsorption on chitosan. The experimental data were best fitted by the pseudo-second-order model and the adsorption rate constant, k2 , was decreased from 9.18 × 10−4 to 2.70 × 10−5 g/mg min with increasing RO16 initial concentrations from 500 to 10 0 0 mg/l, respectively.

Fig. 7. Freundlich isotherm plot for RO16 adsorption onto CFS at different temperatures.

layer adsorption of RO16 dye onto the heterogeneous surface sites of the CFS. Moreover, the value of kF improves from 36.52 to 54.94 (mg/g) (l/mg)1/ n when the temperature increases from 30 °C to 50 °C, confirming the endothermic behavior of the adsorption process. For the Langmuir isotherm, the maximum capacities of RO16 are reported as 105.8, 107.2, and 114.2 mg/g at temperatures of 30 °C, 40 °C, and 50 °C, respectively. This endothermic nature of RO16 adsorption was also observed onto residual brewery yeast and polyaniline/polysaccharides composite [41,42]. The capacity of the prepared CFS for RO16 is compared with several carbonaceous adsorbents toward various reactive dyes [43–46], as summarized in Table 5. Fish wastes represented by scales are good precursors for producing an efficient organic sorbent in terms of CFS with better adsorption capacity for RO16 dye. 3.4. Adsorption kinetics The experimental adsorption dye uptakes of CFS versus contact time data determined using Eq. (7) are presented in Fig. 8. These kinetic data have been correlated by pseudo-first-order and

Table 5 Comparison of reactive dye capacities onto different adsorbents. Sorbent

Reactive dye

T (°C)

pH

t (h)

Dose (g/l)

qmax (mg/g)

Ref.

Fish scale-char Straw-char Pine shell-char Food waste-hydrochar Calcined animal bone Pecan shell-char Modified walnut shell

Orange 16 Brilliant blue Orange 16 Rhodamine 6 G Rhodamine B Blue 4 Brilliant red

50 25 50 40 55 30 40

7 6.5 2.5 8 – 7 2.5

24 24 6 2 24 92 3

1.0 0.8 2.5 0.5 0.4 10 1.0

114.20 282.80 314.00 71.43 64.54 39.66 568.10

This work [12] [25] [43] [44] [45] [46]

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Table 6 Kinetic parameters for adsorption of RO16 onto CFS at 30 °C and different initial concentrations. C0 (mg/l)

25 50 100 150 200 300 400

qexp (mg/g)

23.21 45.62 83.01 87.32 93.83 112.11 118.30

Pseudo-first order

Pseudo-second order

qcal (mg/g)

k1 (1/min)

R2

RMSE

qcal (mg/g)

k2 (g/mg min)

R2

RMSE

22.99 43.87 81.38 85.98 92.20 109.60 117.10

6.79E−03 3.99E−03 2.96E−03 3.12E−03 3.36E−03 3.11E−03 4.30E−03

0.998 0.990 0.981 0.966 0.969 0.972 0.976

0.325 1.351 3.392 4.679 4.758 5.446 5.407

24.76 51.56 95.82 103.00 109.70 131.70 135.90

2.59E−04 8.86E−05 3.24E−05 3.41E−05 3.51E−05 2.63E−05 3.89E−05

0.979 0.999 0.994 0.984 0.986 0.991 0.933

1.005 0.467 1.842 3.130 3.193 3.143 4.509

3.5. Adsorption thermodynamics The values of H° , G° and S° for RO16 adsorption on CFS are determined by correlation of In (K) versus 1/T data using a linear regression analysis. The positive H° (18.51 kJ/mol) confirms the endothermic adsorption nature which is also confirmed by improvement of RO16 uptake at high temperature due to increased diffusion rate through pores of CFS particle. The lower H° value (<20 kJ/mol) also indicates that the adsorption is physical in nature [50]. The endothermic adsorption of RO16 was also observed on activated carbon [25] and polyaniline–polysaccharides composite [42]. The S° value of 63.18 J/mol K reveals the affinity between the RO16 molecules and CFS with the increase in the degree of freedom. The negative G° values of −0.76, −1.18 and −2.04 kJ/mol at 30 °C, 40 °C and 50 °C, respectively confirm that adsorption of RO16 onto CFS is spontaneous and becomes more favorable at high adsorption temperatures [24]. 4. Conclusions CFS were utilized as low-cost materials for the adsorption of reactive orange 16 dye (RO16). The BET surface area and average pore diameter of CFS was found 2.13.82 m2 /g and 5.116 nm, respectively. The results revealed that CFS with well-developed mesoporous structure was very effective in the adsorption of RO16. Compared with the Langmuir isotherm, the Freundlich isotherm was more suitable for describing the isotherm data of RO16 adsorption onto CFS. Maximum monolayer capacities of 105.8, 107.2, and 114.2 mg/g were reported at 30 °C, 40 °C, and 50 °C, respectively. The pseudosecond-order model best represented the adsorption kinetics. Acknowledgments The third author acknowledges the award of USM postdoctoral fellowship in aid for research. The authors extend their appreciation to the International Scientific Partnership Program ISPP at King Saud University for funding this research work through ISPP# 0042. References [1] González JA, Villanueva ME, Piehl LL, Copello GJ. Development of a chitin/graphene oxide hybrid composite for the removal of pollutant dyes: adsorption and desorption study. Chem Eng J 2015;280:41–8. [2] Abidi N, Errais E, Duplay J, Berez A, Jrad A, Schäfer G, et al. Treatment of dye– containing effluent by natural clay. J Clean Prod 2015;86:432–40. [3] Ma Q, Wang L. Adsorption of reactive blue 21 onto functionalized cellulose under ultrasonic pretreatment: kinetic and equilibrium study. J Taiwan Inst Chem Eng 2015;50:229–35. [4] Cheng Z, Zhang L, Guo X, Jiang X, Liu R. Removal of Lissamine rhodamine B and acid orange 10 from aqueous solution using activated carbon/surfactant: process optimization, kinetics and equilibrium. J Taiwan Inst Chem Eng 2015;47:149–59. [5] Marrakchi F, Khanday WA, Asif M, Hameed BH. Cross-linked chitosan/sepiolite composite for the adsorption of methylene blue and reactive orange 16. Int J Biol Macromol 2016;93:1231–9.

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Please cite this article as: F. Marrakchi et al., Mesoporous carbonaceous material from fish scales as low-cost adsorbent for reactive orange 16 adsorption, Journal of the Taiwan Institute of Chemical Engineers (2016), http://dx.doi.org/10.1016/j.jtice.2016.12.026