Process Biochemistry 39 (2003) 193 /202 www.elsevier.

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Evaluation of the use of raw and activated date pits as potential adsorbents for dye containing waters
Fawzi Banat *, Sameer Al-Asheh, Leema Al-Makhadmeh
Department of Chemical Engineering, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110, Jordan Received 1 October 2002; received in revised form 31 December 2002; accepted 2 February 2003

Abstract The adsorption kinetics and isotherms of methylene blue (MB) on raw and thermally activated date pits, an agricultural solid waste, were investigated. The effects of activation temperature, solution temperature, solution pH, adsorbent particle size, and solution salinity on methylene blue removal were studied. Dye removal increased with an increase in solution pH but decreased with an increase in solution temperature. Raw date pits were effective in removing MB from aqueous solutions and are a promising adsorbent material. Unexpectedly, it was found that physical activation of date pits reduced the adsorption capacity. The measured adsorption kinetics was well described by a pseudo-second order kinetic model. Furthermore, the Langmuir isotherm model fitted the experimental equilibrium data. # 2003 Elsevier Ltd. All rights reserved.
Keywords: Date pits; Kinetic models; Langmuir; Activation; Dyes

1. Introduction Activated carbons are the most popular adsorbents used for the removal of toxic substances from water. This could be related to their extended surface area, high adsorption capacity, microporous structure and special surface reactivity [1]. However, the adsorptive capacity of activated carbons depends mainly on the precursor nature, the operating conditions of adsorption (such as temperature and pH) and the nature of the adsorbate. The carbon precursors may be of botanical origin (wood, coconut shells, fruit seeds), mineral origin (coal, peat), or polymeric materials (rubber tyres, plastics). About 50% of industrially available activated carbons are derived from precursors of botanical origin [2]. These precursors are usually low-cost agricultural residues with no notable applications except as fuels for energy generation. Numerous agro-waste biomaterials have been used for the production of activated carbons, including coconut shells, almond shells, peach stones, apricot stones, plum stones, cherry stones, apple pulp,
* Corresponding author. Fax: '/962-2-709-5018. E-mail address: banatf@just.edu.jo (F. Banat). 0032-9592/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0032-9592(03)00065-7

and nutshells [2 /5]. Date pits have received less consideration as a source material for the preparation of activated carbon [2]. Raw agricultural solid waste materials generally do have some adsorption capacity, but are greatly enhanced by the activation process. Activated carbon can be made from many substances containing a high carbon content such as wood and coconut shells. The raw material has a very large influence on the characteristics and the performance of activated carbon. Activated carbons could be produced by either physical (thermal) activation or chemical activation. Thermal activation involves carbonisation or calcination of the raw materials at elevated temperatures (500 /900 8C) in an inert atmosphere followed by mild oxidation (gasification) of the substance with steam, air and/or carbon dioxide at high temperatures (800 /1000 8C). Simultaneous carbonisation and activation can also be obtained chemically by impregnation with dehydrating agents such as phosphoric acid and zinc chloride [6,7]. This work presents results on the adsorption of methylene blue dye by raw and thermally activated date pits. Date pits constitute roughly 10% of the date palm [8]. In Malaysia, which is the largest date pits producer in the world, more than a million ton of date

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pits are estimated to be generated annually [9]. Date pits as a waste stream have been a problem to the date industry, therefore, its recycling or re-utilisation is useful. In the United States, pulverised ground date pits are being used on a small scale, on dirt roads as a type of road base gravel. In the Middle East, it is sometimes used in animal feed [10]. Therefore, finding ways to use this agricultural by-product profitably will benefit date farmers substantially and offers an interesting alternative for their disposal. Many industries use dyes to colour their products. Wastewater effluents from such industries contain residues of dyes. The presence of very low concentrations of dyes in effluent is highly visible and undesirable [11]. The disposal of coloured wastewaters without sufficient treatment is toxic to aquatic life [12]. They also pose a problem because of their carcinogenicity and toxicity [13]. Therefore, it is necessary to decrease the concentration of dyes to the lowest possible limits accepted by the environmental agencies. Considerable research has been done on colour removal from these waters. The adsorption process provides an attractive alternative treatment, especially if the adsorbent is inexpensive and readily available. A number of low cost adsorbents have been examined for dye removal. These include wood [14], fullers earth and fired clay [15], fly ash [16], biogas waste slurry [17], waste orange peel [18], banana pith [19], coir pith [20,21], sugar industry mud [22], plum kernels [4]. Dyeing wastewater treatment using palm-fruit bunch has been reported by Nassar et al. [23,24]. The objective of the present study was to explore the feasibility of using date pits before and after thermal activation, as an adsorbent for the removal of methylene blue, a widely used dye in the textile processing industry. The effect of operating parameters such as temperature salts addition, solution pH, particle size, and dye initial concentration on the adsorptive capacity of the adsorbent was examined. Kinetic studies were conducted to determine the adsorption mechanism.

internal diameter, fitted in a vertical tube electrical furnace (HERAEUS D-6450). About 10 g of the datepits was placed on a metal mesh in the reactor, then heated at a rate of 35 8C/min to 700 8C and held at this temperature for 2 h in a N2 atmosphere. The carbonised materials were then activated either at 500 or 900 8C for 30 min under a CO2 flush [25]. The resulting activated carbon materials were washed with 0.1 M H2SO4 to dissolve and remove any residual ash, followed by washing with distilled water and drying. 2.2. Batch adsorption experiments Batch adsorption equilibrium and kinetic experiments were undertaken by contacting a known amount of the adsorbent with 10 ml of MB solution in sealed glass bottles. The initial MB concentration was in the range of 20 /400 mg/l. The final adsorbent concentration was 5 mg/ml unless otherwise stated. The bottles were placed in a temperature-controlled shaker (Kottermann, Germany) and samples taken at known time intervals in order to investigate the kinetics of the adsorption process. Otherwise, the samples were allowed to reach equilibrium. Kinetic experiments showed that such an equilibrium was established within 4 h. However, to ensure equilibrium, bottles for all such experiments were left in the shaker for 24 h. The samples were then centrifuged and the residual concentration of MB in the supernatant was determined using a Spectronic 21 MV spectrophotometer. All measurements were performed at the wavelength corresponding to the maximum absorbance (610 nm) using distilled water as a blank. The uptake, q , was calculated from the difference between the initial and the final MB concentration as follows: q0 (Co ( Cf )V M (1)

2. Experimental 2.1. Preparation of activated carbons The raw material, date pits, were thoroughly washed with distilled water to remove all dirt and then ovendried overnight at 105 8C. The dried pits were then crushed, milled and sieved into different particle sizes. Studies were focused on a size fraction of 0.125 /0.212 mm. The process of converting date-pits to activated carbon comprises two stages: carbonisation and activation. Both carbonisation and activation were carried out in a stainless steel reactor of 400 mm length and 30 mm

where q is the uptake (mg/g), CO is the initial methylene blue concentration, Cf is the final MB concentration (mg/ml), M is the adsorbent dosage (g) and V is the solution volume (ml). Each experimental result was obtained by averaging the data from two parallel experiments. The effect of solution pH was studied by performing the adsorption experiments of MB at three different pH levels; 4, 6, and 8. The solution pH adjustment was achieved by addition of appropriate amounts of either 0.1 M HCl or 0.1 M NaOH solutions. Experiments were conducted at 25, 45, and 50 8C in order to investigate the effect of temperature on the adsorption process. The effect of particle size on the adsorption process was studied using four chosen sizes of date pits: 0.125 / 0.212, 0.212 /0.5, 0.5 /0.71, and 0.71 /1 mm. The adsorbent concentration was always kept constant at 5 mg/

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ml and adsorption was followed till reaching equilibrium.

3. Results and discussion 3.1. Kinetics of adsorption process The relationship between contact time and methylene blue uptake by raw date pits, and date pits activated at 500 and 900 8C was studied through batch experiments as shown in Fig. 1A /C, respectively, at different initial

methylene blue concentrations ranged from 20 to 400 mg/l. For concentrations up to 80 mg/l, the equilibrium time was reached within less than 20 min (Fig. 1). A longer time was needed to reach equilibrium when the initial dye concentration was above 80 mg/l (Fig. 1A). The rapid adsorption of methylene blue at concentrations below 80 mg/l indicates that methylene blue adsorption occurs mainly on the surface of the adsorbent. At concentrations in the range of 100 /400 mg/l (Fig. 1), the adsorption process could be divided into three regimes. The first regime was fast as a result of the rapid attachment of methylene blue to the surface of the

Fig. 1. Kinetics of methylene blue uptake by raw date pits (A), activated date pits at 500 8C (B), and activated date pits at 900 8C (C). Adsorbent concentration: 5 mg/ml.

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adsorbent. The second regime was slower possibly because adsorption took place in the pores (intraparticle diffusion) and in the third regime the adsorption process ceased indicating equilibrium. At high concentrations the three regimes were more obvious. As can be seen, the adsorption capacity increased with higher initial dye concentrations. In order to examine the controlling mechanism of the adsorption process such as mass transfer and chemical reaction, a pseudo-second order kinetic model as well as a diffusion model were used to test the experimental data. 3.1.1. Pseudo-second order model The adsorption kinetics may be described by a pseudo-second order reaction [26]. The linearised-integrated form of this model is: t qt 0 1 K 2 q2 e ' 1 qe t (2)

where K2 is the pseudo-second order rate constant of adsorption. 3.1.2. Diffusion model The intraparticle diffusion model presented here refers to the theory proposed by Weber and Morris [27] who concluded that the uptake is proportional to the square root of contact time during the course of adsorption. Accordingly, p qt 0 k d t (3) where kd is the rate constant of intraparticle transport (mg/g per min1/2). The applicability of the pseudo-second order kinetic model for raw date pits, and activated date pits at 500 and 900 8C, was examined by plotting (t /qt ) versus t at various initial dye concentrations as shown in Fig. 2A / C, respectively. The experimental data shows a good compliance with the model with an extremely high regression coefficients (R2 / 0.995). The change of the pseudo-second order rate constants with concentration for the raw and activated pits is given in Table 1. The values of the reaction rate constants decreased with the increase of MB initial concentration. The kinetic results were also subjected to analysis by the Morris and Weber model. According to this model, the plot of uptake, qt , versus the square root of time should be linear if intraparticle diffusion is involved in the adsorption process and if these lines pass through the origin then intraparticle diffusion is the ratecontrolling step. As shown in Fig. 3, the results can be represented by such a linear relationship but the lines do not pass through the origin. This indicates that particle diffusion is involved but is not the only rate-limiting mechanism. As shown in Fig. 3A and B, increasing the MB concentration in the solution promoted the diffu-

sion in the raw and 500 8C activated date pits particles and resulted in an increase in the intraparticle diffusion rate. This behaviour was less obvious for the 900 8Cactivated pits (Fig. 3C) where the lines were almost parallel indicating that intraparticle diffusion rate was roughly constant with respect to the initial MB concentration. The adsorption of MB takes place probably via surface exchange reaction until the surface functional sites are fully occupied; thereafter MB molecules diffuse into the pores of the adsorbent for further reaction. Similar results were reported by Ho and McCay [28] who found that the adsorption of the basic dye Red 22 onto pith adsorbent follows a pseudo-second order chemical reaction mechanism. The date pits and pith adsorbents are both partially composed of lignin component and MB and Red 22 are both basic dyes. The lignin component contains acid exchange groups due to fulvic and humic acids and these groups are believed to be involved in the exchange with the basic dye ions [28]. 3.2. Adsorption isotherms In order to facilitate the estimation of the adsorption capacities at various conditions, the Langmuir adsorption isotherm, a typical model for monolayer adsorption, was employed. The linearised Langmuir model can be written as 1 qe 0 1 Qm ' 1 bQm ( 1 Ce (4)

where qe is the amount (mg) of dye per gram of solid adsorbed at equilibrium, Ce is the concentration (mg/l) of dye in solution at equilibrium, Qm (mg/g) and b (mg/ l) (1 are the Langmuir constants, representing the maximum adsorption capacity for the solid phase loading and the energy constant related to the heat of adsorption, respectively. The constants Qm and b can be evaluated from the intercept and the slope of the linear plot of the experimental data of 1/qe versus 1/Ce , respectively. Fig. 4 shows a linear relationship of 1/qe versus 1/Ce for the adsorption of methylene blue on activated and raw date pits adsorbents, suggesting the applicability of the Langmuir model. The maximum adsorption capacity, Qm , presented in Table 2 indicates that raw date pits without activation is a superior adsorbent over that with activation. It is possible that the main functional groups involved in dye removal were destroyed upon activation, and thus the adsorption capacity was significantly reduced. Having in mind that only pores whose openings are larger than the molecular size of the adsorbate are accessible to the adsorbate, it is also possible that the pore sizes generated upon activation

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Fig. 2. Methylene blue uptake by raw date pits (A), activated date pits at 500 8C (B) and at 900 8C (C) according to the pseudo-second order model.

Table 1 Rate constants of the pseudo-second order kinetic model at various initial concentrations Initial concentration (mg/l) K2 Raw date pits 20 40 60 80 100 200 300 400 / 1.963 1.923 / 0.050 0.005 0.002 0.002 Activated (T 0/500 8C) 0.202 0.279 0.136 0.099 0.017 / / / Activated (T 0/900 8C) 0.987 0.098 0.144 0.137 0.055 / / /

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Fig. 3. Methylene blue uptake by raw date pits (A), activated date pits at 500 8C (B) and at 900 8C (C) according to the intraparticle diffusion model.

) thus were smaller than the molecular size of MB (15 A leading to lower adsorption. Phenol with a molecular showed an opposite trend where its size of 10 A adsorption capacity was significantly improved upon thermal activation of date pits at 500 8C [29]. These discrepancies indicate that the molecular size of solutes has a significant role in the adsorption process. The adsorption capacity of methylene blue on date pits activated at 900 8C was higher than that at 500 8C because larger area and pore volume are possibly formed at the high temperature. Similar findings were reported by Juang and Tseng [4] who found that increasing the activation temperature of plum kernels

produces carbons with higher adsorptive capacity towards methylene blue. Lafi [30] also observed a similar behaviour for the activation temperature effect on the methylene blue adsorption by activated carbons prepared from acrons and olive seeds. The maximum adsorption capacity of methylene blue, Qm , for the adsorbents used in this study along with that of other adsorbents are presented in Table 3. Although the adsorption capacity of raw date pits for methylene blue was low; it was much higher than that of other potential adsorbents such as cotton waste, orange and banana peel, activated olive stones and kaolin (raw and treated). According to the results obtained, raw date pits

F. Banat et al. / Process Biochemistry 39 (2003) 193 /202 Table 3 Materials used as adsorbents for methylene blue Adsorbent Capacity (mg/g) 84 24 150 0.51 16.1 22.1 200 120 130 80 1.3 12.7 26.5 20.8 18.6 15.55 20.49 8.88 227 80.3 12.9 17.3 [38]

199

Reference

Fig. 4. Langmuir isotherm for adsorption of methylene blue on raw and activated date pits. Adsorbent concentration: 5 mg/ml. Temperature: 25 8C.

Wood Cotton waste Bentonite Chrome sludge Activated olive stones with 40-wt.% ZnCl2 at 873 K Activated olive stones with 40-wt.% ZnCl2 at 873 K in a nitrogen atmosphere Activated furniture (850 8C) Activated sewage char (800 8C) Activated tyres (850 8C) Pyrolysed furniture Fly ash Zeolite Amorphous silica Banana peel Orange peel Pure kaolin NaOH-treated pure kaolin Calcined pure kaolin Activated tyre char Raw date pits Activated date pits (500 8C) Activated date pits (900 8C)

[35] [35] [35] [36] [37]

[39]

[40] [41]

Table 2 Langmuir constants for the adsorption of methylene blue using raw and activated date pits Adsorbent Raw date pits Activated date pits (T 0/500 8C) Activated date pits (T 0/900 8C) Qm (mg/g) 80.29 12.94 17.27 b (mg/l)( 1 0.157 0.330 0.373 R2 0.974 0.954 0.982

[42] Present work

could be employed as low-cost adsorbents and could be considered as an alternative to commercial activated carbons for the removal of colour. Because of the low adsorption capacity of the activated forms of date pits they were not used further. 3.3. Effect of adsorbent concentration In order to study the effect of adsorbent concentration on methylene blue removal, various amounts of raw date pits were contacted with a fixed initial methylene blue concentration of 50 mg/l. The percentage removal and the uptake of MB versus the adsorbent concentration are shown in Fig. 5. Although the uptake of MB decreased with an increase in adsorbent concentration, the residual concentration of MB in solution decreased. To explain this, the percentage removal of MB, for example, increased from 47.6 to 97.9% when the adsorbent concentration was increased from 0.5 to 5 mg/ml. Further increase in the adsorbent concentration above 5 mg/ml had no effect on the percentage removal of methylene blue (Fig. 5). Increasing the adsorbent

Fig. 5. Effect of raw date pits concentration on the removal of methylene blue. Initial methylene blue concentration: 50 mg/l.

concentration at a fixed MB concentration provided more available adsorption sites for MB and thus increased the extent of MB removal. The use of 5 mg/ ml adsorbent concentration in the experiments as such was reasonable.

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F. Banat et al. / Process Biochemistry 39 (2003) 193 /202 Table 4 Langmuir constants for raw date pits at several temperatures Temperature (8C) 25 40 60 Qm (mg/g) 80.29 73.71 70.38 b (mg/l)( 1 0.157 0.139 0.118 R2 0.974 0.970 0.998

3.4. Effect of temperature Adsorption isotherms of methylene blue on raw date pits at different temperatures namely 25, 40 and 60 8C, were generated in batch experiments. The adsorption isotherm data was fitted to the Langmuir model (Fig. 6). The Langmuir parameters obtained at different temperatures are listed in Table 4. There are good fit straight lines for all of the experimental data as revealed from the regression coefficients, a measure of the goodness-of-fit, listed in Table 4. The maximum adsorption capacity of methylene blue decreased with temperature. On increasing the temperature from 25 to 60 8C, the monolayer adsorption capacity, Qm , decreased from 80.3 to 70.4 mg/g. This may be due to a tendency of the dye molecules to escape from the solid phase to the bulk phase with an increase in temperature of the solution [31]. A similar observation was also reported in a study on the adsorption of Acid Blue 9 on activated clay / carbon mixture [26] and on the adsorption of Basic Blue 3 on silica [32]. The Langmuir constant b can be used to calculate the change in the apparent enthalpy, DH (kJ/mol), of adsorption using the following thermodynamic equation [33]: ln b 0 ln a ( DH RT (5)

where a is the adsorption energy constant, R is the universal gas constant and T (K) is the absolute temperature of the solution.

Fig. 7. Plot of ln b vs. 1/T for methylene blue adsorption by raw date pits.

The enthalpy change of adsorption, DH , was calculated by plotting ln b versus 1/T (Fig. 7) and found to be (/5.97 kJ/mol. The negative DH value confirms the exothermic nature of the adsorption process. Since adsorption is an exothermic process, it would be expected that an increase in solution temperature would result in a decrease in adsorption capacity. 3.5. Effect of initial pH The influence of the initial pH of the solution on the uptake of methylene blue by raw date pits was studied at three pH levels 4, 6, and 8. Dye solutions in the concentration range of 20 /100 mg/l were used in this study. The low uptake of methylene blue under acidic conditions (Fig. 8) may be related to the presence of excess H ' ions competing with the dye cation MB' for the adsorption sites. It is also possible that the surface properties of date pits are dependent on pH of the solution. A similar trend was also observed for the adsorption of methylene blue by coir pith adsorbent [21] and by various activated carbons [34].

Fig. 6. Effect of temperature on methylene blue adsorption according to the Langmuir isotherm model. Adsorbent concentration: 5 mg/ml.

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between the salt and the surface of the adsorbent nor between the salt and the solute (methylene blue). 3.7. Effect of particle size To examine the effect of particle size on the adsorption process, the dried raw date pits were crushed and sieved into different size fractions (0.125 /0.212, 0.212 / 0.5, 0.5 /0.71 and 0.71 /1.0 mm). Each of these sizes was exposed to a fixed initial methylene blue concentration, and adsorbent concentration 5 mg/ml. It is evident from the results shown in Fig. 10 that the uptake of methylene blue increased with the decrease in particle size, mainly because of the larger surface area available. Similar results of particle size effect were reported for the adsorption of dyes on palm stones (date pits) [23].

4. Conclusions
Fig. 8. Effect of pH on methylene blue adsorption at 25 8C. Adsorbent concentration: 5 mg/ml.

3.6. Effect of salt addition The effect of salinity on the adsorption of methylene blue was tested by the addition of sodium chloride to the solution. The concentration of NaCl used ranged from 0.01 to 0.5 M. Dye solutions of 50 and 80 mg/l were used in this study. The presence of salt had no effect on the adsorption of methylene blue by raw date pits (Fig. 9). This leads to deduce that there was no interaction

This study assessed the potential of thermally activated and raw date pits to remove methylene blue dye from water and compared their adsorption capacity to that of other adsorbents. Raw date pits showed a higher adsorption capacity towards MB than pits activated at 500 and 900 8C. Compared with other agricultural and non-agricultural solid wastes, raw date pits was found to be an effective adsorbent for dyes removal. Kinetic data of adsorption were well fitted by the pseudo-second order kinetic model while the equilibrium data were well fitted by the Langmuir model. Adsorption of MB by raw date pits was found exothermic in nature. Although the adsorption capacity of raw date pits is lower than

Fig. 9. Effect of NaCl concentration on methylene blue adsorption by raw date pits. Adsorbent concentration: 5 mg/ml.

Fig. 10. Effect of particle size on the uptake of methylene blue by raw date pits. Adsorbent concentration: 5 mg/ml.

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that of commercial activated carbons, raw date pits is an attractive alternative adsorbent because of its low cost. The utilisation of date pits for the removal of colour from water can provide an excellent disposal option for the date pits industry, at the same time would provide a cheap and effective adsorbent.

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