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Journal of Hazardous Materials 153 (2008) 709–717

Preparation of activated carbon from coconut husk: Optimization study on removal of 2,4,6-trichlorophenol using response surface methodology
I.A.W. Tan, A.L. Ahmad, B.H. Hameed ∗
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang, Malaysia Received 17 July 2007; received in revised form 30 August 2007; accepted 3 September 2007 Available online 6 September 2007

Abstract Activated carbon was prepared from coconut husk using physicochemical activation method which consisted of potassium hydroxide (KOH) treatment and carbon dioxide (CO2 ) gasification. The effects of three preparation variables (CO2 activation temperature, CO2 activation time and KOH:char impregnation ratio) on the 2,4,6-trichlorophenol (2,4,6-TCP) uptake and activated carbon yield were investigated. Based on the central composite design, two quadratic models were developed to correlate the preparation variables to the two responses. From the analysis of variance (ANOVA), the most influential factor on each experimental design response was identified. The activated carbon preparation conditions were optimized by maximizing both the 2,4,6-TCP uptake and activated carbon yield. The predicted 2,4,6-TCP uptake and carbon yield from the models agreed satisfactorily with the experimental values. The optimum conditions for preparing activated carbon from coconut husk for adsorption of 2,4,6-TCP were found as follow: CO2 activation temperature of 750 ◦ C, CO2 activation time of 2.29 h and KOH:char impregnation ratio of 2.91, which resulted in 191.73 mg/g of 2,4,6-TCP uptake and 20.16 % of activated carbon yield. © 2007 Elsevier B.V. All rights reserved.
Keywords: Coconut husk activated carbon; Adsorption; 2,4,6-Trichlorophenol; Central composite design; Optimization

1. Introduction Chlorophenols are a group of chemicals in which chlorines have been added to phenol. Chlorophenols have been prescribed as priority pollutants by the US Environmental Protection Agency (EPA) due to their toxicity and adverse effects upon human [1]. They are the most common organic pollutants used widely in agriculture, industry and public health. The most important chlorophenol sources are wastewaters from pesticide, paint, solvent, pharmaceutics, paper and pulp industries as well as water disinfecting process [2]. Chlorophenols are weak acids and permeate human skin by in vitro and are readily absorbed by gastro-intestinal tract. The acute toxicity of chlorophenols includes increased respiratory rate, vomiting and nausea [3]. Chlorophenols also create complicated problems to water bodies such as bad odour and taste in drinking water, death of aquatic life, inhibition of normal activities of microbial population in wastewater treatment plant, etc. Therefore, the efficiency of tra-

Corresponding author. Tel.: +604 599 6422; fax: +604 594 1013. E-mail address: chbassim@eng.usm.my (B.H. Hameed).

ditional biological treatment method is not satisfying due to chlorophenol’s structural stabilization and toxicity [2]. Besides, they also display a pronounced undesirable effect in potable water at concentration as low as 0.1 mg/l [3]. As one type of the most hazardous materials, they are carcinogenic, mutagenic and resistant to biodegradation, and thus have to be decomposed before discharging into receiving waters, in order to avoid the biomagnified toxicity to aquatic flora and fauna through various food chains [4]. Adsorption on activated carbon has been found to be superior compared to other chemical and physical methods for wastewater treatment in terms of its capability for efficiently adsorbing a broad range of pollutants, fast adsorption kinetics and its simplicity of design. However, commercially available activated carbons are still expensive due to the use of non-renewable and relatively high-cost starting material such as coal, which is unjustified in pollution control applications [5,6]. Therefore, in recent years, many researchers have tried to produce activated carbons for removal of various pollutants using renewable and cheaper precursors which were mainly industrial and agricultural byproducts, such as coconut shell [3], waste apricot [7], sugar beet bagasse [8], molasses [9], rubberwood sawdust [10], rice straw

0304-3894/$ – see front matter © 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jhazmat.2007.09.014

The mixture was then dehydrated in an oven overnight at 105 ◦ C to remove moisture and was then activated under the same condition as carbonization. This is because activated carbon preparation variables such as activation temperature. activation time and chemical impregnation ratio will influence the pore development and surface characteristics of the activated carbon produced.6-TCP uptake.4.6-TCP uptake and the carbon yield to the three variables were then developed. CO2 activation time and KOH:char impregnation ratio) on the two responses. Turkish lignite [19] and hazelnut shell [22]. The procedure used to prepare the activated carbon was referred to our previous work [15]. about 151. A central composite design (CCD) was selected to study simultaneously the effects of three activated carbon preparation variables (CO2 activation temperature. To make better use of this cheap and abundant agricultural waste. Deionized water was then added to dissolve all the KOH pallets. In the present study.4. Response surface methodology (RSM) has been found to be a useful tool to study the interactions of two or more variables [19]. Luscar char [21].A. Generally. as a domestic fuel and as a source of fibre for rope and mats. However. the activated carbons were prepared using physiochemical activation method by varying the preparation variables using the CCD. Some of them are adsorption of arsenic on copper impregnated coconut husk carbon [16]. value-added adsorbents and second. First.1 molar hydrochloric acid until the pH of the washing solution reached 6–7 [15]. In Malaysia. Throughout the carbonization process. but to a different final temperature. Materials and methods 2. Acid Red 27 dye and Cu2+ ions [18] and our recent work on preparation of activated carbon from coconut husk for adsorption of basic dye [15]. the use of an adequate experimental design is particularly important. preparation of activated carbon from digested sewage sludge with the additive coconut husk using ZnCl2 as activating agent [17]. Therefore.6-trichlorophenol (2. Conversion of coconut husk into activated carbon will serve a double purpose.4. (ii) x2 . A standard RSM design called a central composite design (CCD) was applied in this work to study the variables for preparing the activated carbons. (1): IR = wKOH wchar (1) where wKOH is the dry weight (g) of KOH pallets and wchar is the dry weight (g) of char. Tan et al.W.710 I.000 ha of land was being used for coconut plantation in year 2001.995%) was flown through at flow rate of 150 cm3 /min. The precursor was first washed to remove dirt from its surface and was then dried overnight in an oven at 105 ◦ C. as calculated using Eq. the use of agricultural by-products represents a potential source of adsorbents which will contribute to solving part of the wastewater treatment problem in Malaysia [15]. indicating that altogether 20 experiments . / Journal of Hazardous Materials 153 (2008) 709–717 [11]. This method is suitable for fitting a quadratic surface and it helps to optimize the effective parameters with a minimum number of experiments. 2. 2. The activated product was then cooled to room temperature under nitrogen flow and then washed with hot deionized water and 0. Activated carbon preparation Coconut husk used for preparation of activated carbon was obtained locally. Empirical models correlating the 2. The variables studied were (i) x1 . The char produced was mixed with KOH pallets with different impregnation ratio (IR). CO2 activation time and (iii) x3 . Some of the previous studies found in applying RSM in preparation of activated carbons used precursors such as olive-waste cakes [20]. coconut husks are used as fuel for coconut processing. The focus of this research was to explore the feasibility of coconut husk-based activated carbon being utilized in removal of 2.280 kg of dry husks were become available per hectare per year. the CCD consists of a 2n factorial runs with 2n axial runs and nc center runs (six replicates). unwanted agricultural waste is converted to useful. Coconut husk is the mesocarp of coconut and a coconut is consists of 33–35% of husk. The most important characteristic of an activated carbon is its adsorption capacity or uptake which is highly influenced by the activated carbon preparation conditions. In assessing the effect of treatments on quality attributes. For each categorical variable. Carbonization of the precursor was carried out by ramping the temperature from room temperature to 700 ◦ C with heating rate of 10 ◦ C/min and hold for 2 h. rattan sawdust [13]. 6 axial points and 6 replicates at the center points were employed. it is proposed to convert coconut husk into activated carbon. Design of experiments Response surface methodology (RSM) is a collection of mathematical and statistical techniques that are useful for modeling and analysis of problems in which a response of interest is influenced by several variables [23]. the preparation conditions for coconut husk-based activated carbon have been successfully optimized for basic dye adsorption [15]. not many studies have been carried out on coconut husk-based activated carbon.6-TCP) from aqueous solutions and also to optimize the activated carbon preparation conditions which would result in high activated carbon yield and high 2. the nitrogen gas flow was switched to CO2 and activation was held for different period of time. CO2 activation temperature. the challenge in activated carbon production is to produce very specific carbons which are suitable for certain applications. The dried husk was cut and sieved to desired mesh size (1–2 mm) and loaded in a stainless steel vertical tubular reactor placed in a tube furnace. Once the final temperature was reached.2. consisting of 8 factorial points.4. oil palm fibre [14] and coconut husk [15]. bamboo [12]. purified nitrogen (99. a 23 full factorial CCD for the three variables. At present. In our previous work. It was estimated that 5. Optimization of experimental conditions using RSM was widely applied in various processes. KOH:char impregnation ratio. production of activated carbons from coconut fibres for removal of phenol. as well as to analyze the interaction between the parameters [21].1.

bij the interaction coefficients. (3) [24]: n n 2 n−1 n where Co and Ce (mg/l) are the liquid-phase concentrations of 2. respectively.3. was calculated by Eq. The independent variables are coded to the (−1. V is the volume of the solution (l) and W is the mass of dry adsorbent used (g). For both responses of 2. All samples were filtered prior to analysis in order to minimize interference of the carbon fines with the analysis.31x1 − 0.4. Deionized water was used to prepare all the solutions and reagents.23 to 23. wc Yield(%) = × 100 (5) wo where wc is the dry weight (g) of final activated carbon and wo is the dry weight (g) of precursor.6-TCP supplied by Sigma–Aldrich (M) Sdn Bhd.6. The two responses were 2.6-TCP uptake (Y1 ) and activated carbon yield (Y2 ). CCD was used to develop correlation between the activated carbon preparation variables to the 2.A. Each response was used to develop an empirical model which correlated the response to the three activated carbon preparation variables using a seconddegree polynomial equation as given by Eq. bii the quadratic coefficients and xi. Malaysia was used as the adsorbate in this study. 2.83x2 x3 Y = bo + i=1 bi xi + i=1 bii xi + bij xi xj i=1 j =i+1 (3) where Y is the predicted response. The experimental sequence was randomized in order to minimize the effects of the uncontrolled factors. Results and discussion 3. Runs 15–20 at the center point were used to determine the experimental error. xj are the coded values of the activated carbon preparation variables.04x2 − 1. respectively. 0) and (0. the quadratic model was selected. bi the linear coefficients.11x1 − 2.4.07 mg/g.1 g of each of the prepared activated carbon. The pH of the solution was natural without any pH adjustment. (0.93 − 5. Chemical structure of 2.4. Characterization of the prepared activated carbon Scanning electron microscopy (SEM) analysis was carried out on the activated carbon prepared under optimum conditions.83x1 2 2 − 1.I. whereas the carbon yield obtained ranged from 3. 2. 2.4. and was not purified prior to use. Model fitting and statistical analysis Design Expert software version 6. with molecular weight of 197.5.. According to the sequential model sum of squares. 1) interval where the low and high levels are coded as −1 and +1. was added to each flask and kept in an isothermal shaker of 120 rpm at 30 ◦ C until equilibrium was reached. by using FTIR spectroscope (FTIR-2000. / Journal of Hazardous Materials 153 (2008) 709–717 711 were required. (4): qe = (Co − Ce )V W (4) where N is the total number of experiments required and n is the number of factors. The concentrations of 2.6-TCP is shown in Appendix A. Fourier transform infrared (FTIR) analysis was applied on the same activated carbon to determine the surface functional groups.35x3 − 3. 0. The 2. ± α.1. USA) was used for regression analysis of the experimental data to fit the equations developed and also for the evaluation of the statistical significance of the equations. The final empirical models in terms of coded factors after excluding the insignificant terms for 2.4.6-TCP uptake (Y1 ) and carbon yield (Y2 ) are shown in Eqs. The complete design matrix of the experiments carried out. the models were selected based on the highest order polynomials where the additional terms were significant and the models were not aliased.4. as suggested by the software. Aqueous samples were taken from the solutions and the concentrations were analyzed. In this study.6-TCP has a chemical formula of C6 H3 Cl3 O.W. (2) [21]: N = 2 + 2n + nc = 2 + 2 ∗ 3 + 6 = 20 3 n (2) wavelength of 296 nm.4.45x1 + 7.4. the α value was fixed at 1. (6) and (7).37x1 x2 − 17. Development of regression model equation The complete design matrix together with the values of both the responses obtained from the experimental works are given in Table 1. 2. Activated carbon yield The activated carbon yield was calculated based on Eq.62x3 −2.14 to 192.682 (rotatable). 0. Perkin Elmer). Batch adsorption was performed in 20 sets of 250 ml Erlenmeyer flasks where 100 ml of 2.6-TCP solution with initial concentration of 200 mg/l was placed in each flask.24x2 x3 (7) .72x3 − 1. ± α) where α is the distance of the axial point from center and makes the design rotatable.6 (STAT-EASE Inc. The center points are used to determine the experimental error and the reproducibility of the data.6-TCP in the supernatant solutions before and after adsorption were determined using a double beam UV–vis spectrophotometer (UV-1601 Shimadzu.94x3 − 2. The axial points are located at (± α.6-TCP at initial and at equilibrium.60x2 2 + 0.0. where the spectra were recorded from 4000 to 400 cm−1 .46 g/mol. 0). Japan) at its maximum (6) 2 2 Y2 = 17. are shown in Table 1.4.6-TCP uptake and carbon yield.61x1 x2 + 0.4. qe (mg/g). respectively. Batch equilibrium studies 2. 0.6-TCP uptake was found to range from 44.86 + 7.4. to study its surface texture and the development of porosity.85x2 + 29.32x1 x3 − 6. The 2. as calculated from Eq. (5).16 x2 − 25. together with the results obtained. bo the constant coefficient.42%.37x1 x3 + 1. 2.4. 3. Tan et al. Minneapolis.6-TCP uptake and carbon yield. 2 Y1 = 188. with particle size of 200 ␮m.6-TCP uptake at equilibrium.4.

6-TCP uptake.45 345.49 211.87 2. (7) in the other hand.94 373.00 2.693.54 13.01 4.25 implied that the model was significant.34 0.6-TCP uptake Source Model x1 x2 x3 2 x1 2 x2 2 x3 x1 x2 x1 x3 x2 x3 Residual Sum of squares 25.682 0 0 0 0 0 0 750.4. / Journal of Hazardous Materials 153 (2008) 709–717 Activated carbon preparation variables Activation temperature.222 23.6-TCP uptake is listed in Table 2.90 3.43 34.79 16.38 757. However.548 190. Y2 (%) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 −1 +1 −1 +1 −1 +1 −1 +1 −1.854.4. Values of Prob > F less than 0.021 190.682 +1.4526 0. (6) and (7) was 18.40 6.93 F value 8.6-TCP uptake predicted from this model.00 1.53 44.6-TCP uptake. the R2 of 0.09 17.31 19.73 21.00 825.63.60 and 1. Tan et al.90 3.00 2.400.45 2.68 2. for Eq.) 9 1 1 1 1 1 1 1 1 1 10 Mean square 2.682 0 0 0 0 0 0 0 0 −1 −1 −1 −1 +1 +1 +1 +1 0 0 0 0 −1.00 2.4.00 2.57 9.45 2.8171 0. The closer the R2 value to unity and the smaller the standard deviation.4.00 900. respectively.61 0.00 3. (6) was considered as moderate to validate the fit.987 187.25 23.87 2.00 3.00 0.080 190.682 0 0 0 0 0 0 0 0 0 0 −1 −1 +1 +1 −1 −1 +1 +1 0 0 −1. indicating that there was a good agreement between the experimental and the predicted carbon yield from this model.00 1.31 19.0250 0. R2 and also the standard deviation values. The adequacy of the models was further justified through analysis of variance (ANOVA).761.00 825.00 2.42 18. was attributed to the experimental variables studied.459.25 2.00 750.94 1.6-TCP uptake and carbon yield.4.00 825. x2 (h) 1.070 176.45 0.682 +1.00 2.00 KOH:char impregnation ratio.53 44.69 841. Further investigations need to be carried out in order to verify this.820 188. the more accurate the response could be predicted by the model.00 2.45 2.45 2.30 Degree of freedom (d.00 1.00 3.00 698. CO2 activation time and KOH:char impregnation ratio) being studied in this work. x1 (◦ C) Activation time.712 Table 1 Experimental design matrix and results Run Levels I.69 841.00 900. (6) could be there were other parameters affecting the 2.W.456.45 2.562 44. respectively.45 2.82 16.7262 0.0002 0.30 Positive sign in front of the terms indicates synergistic effect.723 187.45 2.51 9. The R2 of 0.315 190.00 825.6-TCP uptake.00 900.1499 0.903 128.7% of the total variation in the 2. The R2 value for Eqs.080 190.25 17.13 6.00 3.23 21.00 0.6-TCP uptake.0004 0. This shows that the predicted value for carbon yield would be more accurate and closer to its actual value. In this case.00 2.1697 0.3233 – . The possible reason for the lower superiority and higher error of estimation given by Eq.881 for Eq.293 189.775 192.90 2.00 750.94 373.45 3.00 1.00 825.398 184.222 189.87 951.00 825. other than the three variables (CO2 activation temperature. respectively.957.90 3. Y1 (mg/g) Carbon yield.00 86.05 indicated that the 2 and x x were model terms were significant.f.87 17.556 161.00 3. The standard deviation for Eqs.66 18.840 166.650 157.45 2. From the ANOVA for response surface quadratic model for 2.00 900.90 3.89 2.82 757. which might lead to large variation in the 2. whereas negative sign indicates antagonistic effect.456.54 17.45 2.36 21. x3 1.957 was considered relatively high as the value was close to unity.74 6.4.400.4.51 11.08 – Prob > F 0.43 18. x3 .881 and 0.00 825.00 1.A. This indicated that 88.761.4.13 825.682 +1. x3 1 3 Table 2 Analysis of variance (ANOVA) for response surface quadratic model for 2.32 3.00 750.65 18.00 2.51 9.19 2.140 166. The quality of the model developed was evaluated based on the correlation coefficient.51 11.00 1. (6) and (7) was found to be 0.49 211.00 825.1% and 95.0014 0.056 27. The ANOVA for the quadratic model for 2.00 825. as compared to the predicted value for 2. the model F-value of 8.

4. Predicted vs.4. 3 shows the three-dimensional response surfaces which was constructed to show the interaction effects of the activated carbon preparation variables (activation temperature and chemical impregnation ratio) on the 2. had the most significant effect on the 2.4. the quadratic effect of KOH 2 on the 2. x1 2 3 2 1 2 were all insignificant to the response. The predicted carbon yield values were quite close to the experimental values.4. x3 significant as well. It was also reported in literature that too long or too short activation time could reduce the surface area and the adsorption capacity of acti- . especially when 2. leading to widening of the pores [29].6-TCP uptake was higher than 150 mg/g.19 and 2. Predicted vs. From the statistical results obtained. in this work.6-TCP uptake (Y1 ). respectively.2. indicating that it Fig. Fig.28].6-TCP uptake of the activated carbons prepared. all the three variables studied were found to have synergistic effects on the 2. Besides.00. 2 . 1. experimental 2. respectively. For this plot. KOH:char impregnation ratio (x3 ) showed the largest F value of 34. x x and x x significant model terms whereas x1 . As expected.4. 2. 3. In this case. The effects of other variables on this response need to be further determined. the increase in temperature also caused the CO2 and the surface metal complex to further gasify the carbon. From the ANOVA for response surface quadratic model for activated carbon yield [15].4. Tan et al. [26] also found that activation time did not show much effect on the surface area obtained for activated carbons prepared from apricot stones using steam activation. 2. 3. However. x2 .A. the model F-value of 24. 3.6-TCP uptake were quite similar. As can be seen from Fig. However. x1 1 2 model terms.6-TCP [20. t = 2 h). x2 . Three-dimensional response surface plot of 2.4.6-Trichlorophenol uptake Based on the F values (Table 2). S ¸ entorun-Shalaby et al.6-TCP uptake.6-TCP uptake and the carbon yield within the range of variables studied. x2 . resulting in increasing devolatilization which further developed the rudimentary pore structure in the char and also enhanced the existing pores and created new porosities.4. The increase in activation temperature and time also entailed an opening and enlargement of the pores. x1 .6-TCP uptake generally increases with increase in activation temperature and chemical impregnation ratio.4.6-TCP uptake was relatively impregnation ratio.43. Figs.4.6-TCP uptake. it was shown that the above models were adequate to predict the 2. indicating that the model developed was successful in capturing the correlation between the activated carbon preparation variables to the carbon yield.W. which were considered moderate. This was due to the low R2 and high standard deviation values of the model. the activation time was fixed at zero level (t = 2 h). which enhanced the adsorption of 2.6-TCP uptake and carbon yield. experimental activated carbon yield. some of the 2. as explained earlier. and the pore characteristics changed significantly with the activation temperature and also the KOH impregnation ratio. compared to CO2 activation temperature (x1 ) and CO2 activation time (x2 ). However.27. Fig.I.4. The effects of activation temperature and activation time on the 2. x3 .4. / Journal of Hazardous Materials 153 (2008) 709–717 713 Fig.4. there was a maximum activation temperature above which would probably lead to the melting of the pores formed at previous stage.4.6-TCP uptake (effect of activation temperature and chemical impregnation ratio. the errors between the predicted and actual carbon yield were smaller compared to the errors between the predicted and actual 2. 1 and 2 show the predicted values versus the experimental values for 2.6-TCP uptake for the prepared activated carbon. Besides.6-TCP uptake values predicted by the model were less accurate. the 2. [25] which reported that activation time gave no significant effect on the pore structure of activated carbon produced from cassava peel.75 implied that the model was signifi2 and x x were significant cant as well. with F value of 2.4. This was expected as the progressive temperature rise and longer activation time would increase the C–KOH and C–CO2 reaction rates. The results obtained agreed with the works by Sudaryanto et al.

4.23. leading to increase in the weight loss of carbon [25]. with the highest F value of 134. KOH:char impregnation ratio played a decisive role in the formation of pores. As the KOH:char IR increased. / Journal of Hazardous Materials 153 (2008) 709–717 Table 3 Comparison of carbon yield for various activated carbons Activated carbon Coconut husk-based Fir wood-based Pistachio-nut shell-based Corncob-based Pistachio shell-based Oil-palm shell-based Activation method KOH treatment and CO2 gasification KOH etching and CO2 gasification KOH activation KOH activation KOH activation CO2 activation Carbon yield (%) 3. the function of desirability was applied using Design Expert software version 6.80–29.30 19.6-TCP uptake. 3. the activated carbon produced should have a high carbon yield and also a high adsorption capacity for economical viability. there was a maximum point for the KOH:char IR beyond which would reduce the 2.23–23. the pore development was mostly due to the intercalation of potassium metal in the carbon structure [25]. activation of apricot stones became more extensive and resulted in a lower solid yield with a more widened porous stucture. to optimize both these responses under the same condition is difficult because the interest region of factors are different.6 (STAT-EASE Inc. the interaction effects between the variables were less significant. Tan et al. the increase in activation temperature quickens the gasification reactions of carbon and therefore. thereby resulting in decreasing yield [28. Table 3 lists the comparison of carbon yield for various activated carbons. This was because excessive amount of KOH could cause further reaction between KOH and carbon.0. Therefore. Y2 will decrease and vice versa. activation time and chemical impregnation ratio on yield were studied as all the three variables were found to be significant terms in the model for activated carbon yield. Process optimization In the production of commercial activated carbons.42 4. over gasification might have occurred with the detrimental effect of reducing the surface area. At high KOH impregnation ratio.. [26] observed that at higher activation temperature. However.A. the catalytic oxidation also caused the widening of pores. 3. therefore increasing the 2.31].714 I. The activated carbon yield was also strongly affected by the chemical impregnation ratio where increasing impregnation ratio decreased the yield and increased the carbon burn-off. However. The effects of activation temperature. the gasification of surface carbon atoms was the predominant reaction.4.14 15. the weight losses were due to increasing release of volatile products as a result of intensifying dehydration and elimination reactions [31]. The results obtained in the present work were comparable with the works reported in the literature.4. This was because when higher impregnation ratio was used. The experimental conditions with the highest desirability . while activation time and chemical impregnation ratio showed almost similar effects on the response.20 12. in order to compromise between these two responses.00 Reference Present work [29] [28] [33] [34] [35] vated carbon prepared.3. The variation in the carbon yields might be due to the different precursors as well as the activation methods and/or conditions used to prepare the activated carbons. which might destroy the pore structure formed at previous stage [30]. Indeed. The increase in temperature would release increasing volatiles as a result of intensifying dehydration and elimination reaction and also increased the C–KOH and C–CO2 reaction rate. The results obtained in this study were in agreement with the work done by Sudaryanto et al. which were less significant compared to activation temperature.4. KOH would promote the oxidation process. Minneapolis. Activation temperature was found to have the greatest effect on it. The quadratic effect of activation temperature on carbon yield was relatively large compared to quadratic effects of activation time and chemical impregnation ratio. When Y1 increases. Activated carbon yield The data obtained for activated carbon yield (Y2 ) were reported in our previous study [15]. USA). therefore with high KOH:char IR. activation time and chemical impregnation ratio [15]. The yield for activated carbon prepared from fir wood was also found to decrease gradually with increase in duration of CO2 gasification [29].6-TCP uptake [32]. However. The increase in KOH could accelerate the reaction rate and therefore the quantity of pores increased correspondingly.70–25.W.70 10. relatively high product yields are expected for economical feasibility and the most important property of activated carbon is its adsorption capacity. hence the reduction in 2. [25] where activation tem- perature was found to play an important role on the yield of activated carbon whereas activation time did not show much effect on the carbon yield. the attack of the amorphous components which obstruct the pores causes a decrease in the carbon yield [20]. It was concluded that the carbon yield decreased with increasing activation temperature. as longer activation time might destroy the pore structure formed previously whereas shorter activation time could not enrich the formation of porosity [30].20–25.00–22.35–21. S ¸ entorun-Shalaby et al. Therefore. The excessive KOH molecules might also decomposed into water which caused the following gasification process under high temperature: 2KOH → K2 O + H2 O H2 O + C → CO + H2 (8) (9) Therefore.6-TCP uptake as well [31].

4. 607. x1 (◦ C) Activation time.73 Carbon yield (%) Predicted 20.35 mg/g. x2 (h) KOH:char impregnation ratio.4. which was only 0.52%. which were the activation temperature.91). The performance of the prepared activated carbon on 2. on the 2. Characterization of activated carbon prepared under optimum conditions Fig. Through process optimization.98 cm−1 . Quadratic models were developed to correlate the preparation variables to the two responses. CO2 activation time = 2. The activated carbon was prepared under the experimental conditions given in Table 4.99 cm−1 : O H stretching vibrations. with the removal efficiency as high as 97.4.54 cm−1 .5. From literature. ethers. Pore development in the char during pyrolysis was also important as this would enhance the surface area and pore volume of the activated carbon by promoting the diffusion of KOH and CO2 molecules into the pores and thereby increasing the KOH–carbon and CO2 –carbon reactions.4. 3. The optimal activated carbon was obtained using preparation condition as: 750 ◦ C activation temperature.4.4. 4. 2380 cm−1 : C C stretching vibrations.6-TCP uptake (mg/g) Predicted 750. The well-developed pores on the prepared activated carbon could be the main factor that had lead to the high 2. Tan et al. The process was considered economically feasible as the precursor was cheap. Hameed [36] in the other hand reported that the maximum adsorption capacity for 2. 1052.4.46 mg/g. 2.6-TCP uptake in this study.2 cm−1 . activation time and chemical impregnation ratio. Radhika and Palanivelu [3] found that the maximum adsorption capacity for 2. 4.6-TCP uptake and carbon yield.32 cm−1 : C H out-of-plane deformation.6-TCP from aqueous solutions. The spectrum in the region of 1200–1000 cm−1 represented C O stretching vibrations of functional groups such as alcohols. This might be due to the activation process used. C C stretching absorption frequently occurs at this region [1].16 were selected to be verified. • 651.6-TCP on coconut shell-based activated carbon and a commercial activated carbon was 122. • 767. however. Conclusions A central composite design was conducted to study the effects of three activated carbon preparation variables. x3 2. This shows that the activated carbon prepared in this work was suitable to be used to remove 2.6-TCP uptake. 1138.6-TCP uptake and carbon yield. which would then create more pores in the activated carbon.4.29 2.A. Through analysis of the response . It was observed that the experimental values obtained were in good agreement with the values predicted from the models.8%.73 mg/g.4. which involved both chemical and physical activating agents of KOH and CO2 . coconut husk was proved to be a promising precursor for production of activated carbons with high carbon yield and high adsorption capacity on 2.4. carboxylic acids and esters. 1567. respectively for 2. / Journal of Hazardous Materials 153 (2008) 709–717 Table 4 Model validation Activation temperature. with relatively small errors between the predicted and the actual values. 1384.6TCP was highly satisfactory.4.91 KOH:char IR.6-TCP.336 and 112. 1017.91 192.29 h activation time and 2. Scanning electron micrograph (1250×) of activated carbon prepared under optimum conditions (CO2 activation temperature = 750 ◦ C.6-TCP on activated clay was 123.W. 2.48 cm−1 : C CH3 deformation. for most carbonaceous materials.07 Experimental 191. 4 shows the SEM image of the activated carbon prepared under optimum conditions (750 ◦ C activation temperature.73 mg/g of 2.5 cm−1 : C C stretching vibration.00 715 Experimental 20.4. for a solution concentration of 200 mg/l.16% of carbon yield and 191.18 and 0. which resulted in 20. The band in the region of ≈1600 cm−1 has been observed by many previous researchers but has not been interpreted definitely. yet it gave a high activated carbon yield besides giving high quality activated carbon with high adsorption performance.6-TCP uptake as high as 191.53 cm−1 : C O H stretching vibrations.I. respectively.23 cm−1 : C O H twist The FTIR spectra obtained were in agreement with the results reported in the study carried out on commercial granular activated carbons [1] and activated carbon prepared from cherry stones [37].00 2. together with the predicted and experimental values for 2. with 2.29 h and KOH:char impregnation ratio = 2.29 h activation time and 2.6-TCP uptake and activated carbon yield. The FTIR spectrum obtained for the prepared activated carbon displayed the following bands:• • • • • 3434. Fig.91 KOH:char impregnation ratio). Large and well-developed pores were clearly found on the surface of the activated carbon.

Study of adsorbent prepared from oil palm ash (OPA) for flue gas desulfurization. Radhika. Palanivelu. Lee. Y.A. [25] Y. S. [28] A. L. [18] N. H. Montgomery. Activated carbons developed from surplus sewage sludge for the removal of dyes from dilute aqueous solutions. J. A. A.N. 147 (2007) 313–318. A. B118 (2005) 259–263.716 I. Production of activated carbon from a new precursor molasses by activation with sulphuric acid.4. A. K. Hameed. M. Hartono. Mater. Hameed. A.. Rigola. H. Chemosphere 44 (2001) 45–51.W. Evaluation of coconut husk carbon for the removal of arsenic from water. Tan.J. large and well-developed pores were clearly found on the surface of the activated carbon. Preparation of steam activated carbon from rubberwood sawdust (Hevea brasiliensis) and its adsorption kinetics. Technol. D. K.L. 82 (2005) 79–85.T. 274 (2004) 594– 601.H. 145 (2007) 398–403. 27 (2007) 1212–1218. C. [20] A. [21] R. Mater. 32 (10) (1998) 3062– 3070. Production of fibrous activated carbons from natural cellulose (jute. [23] D. C ¸ . surfaces derived from the models. Hazard.C. Coq. S ¸ entorun-Shalaby. A. Din. Feng. A.T. Hazard.L. J. Textural development of sugar beet bagasse activated with ZnCl2 . J. Gao. J. Mater.A. Wu. Kim.L. Phan Tan Luu. Pallier. R. Khouya. Balaguer. Dahbi. S. 45 (2005) 50–60. Uc ¸ ak-Astarlıo˘ glu.L. Hazard. Microchem. Lua. Eng. K. The optimal activated carbon was obtained using 750 ◦ C activation temperature. Tseng. Eng. Mater. Effects of pH and temperature on isotherm parameters of chlorophenols biosorption to anaerobic granular sludge. C. / Journal of Hazardous Materials 153 (2008) 709–717 [9] K. Mater. [7] C. Irawaty.S. Tan et al.C. Colloid Interface Sci. Artola. Thermal Eng. Zainudin. Zabaniotou.H.A.R. Ezzine. Colloid Interface Sci. Moreno-Castilla. Paeng.G.Q. Graham. Preparation of highly porous carbon from fir wood by KOH etching and CO2 gasification for adsorption of dyes and phenols from water. B136 (2006) 922–929. Jeyaseelan. K. Dalai.16% of carbon yield and 191. Hindarso. Applicability of the various adsorption models of three dyes adsorption onto activated carbon prepared waste apricot. S ¸ ayan.L. Chemical structure of 2. coconut) fibers for water treatment applications. Process optimization was carried out and the experimental values obtained for the 2. E.L. W. Hazard. J. U. Lima Rose Miranda. J. Y. Rivera-Utrilla. Micropor. Appl. A. Chem. Mater. From the SEM image obtained. Effect of activation temperature on the textural and chemical properties of potassium hydroxide activated carbon prepared from pistachio-nut shell. Optimization of preparation conditions for activated carbons from coconut husk using response surface methodology. Equilibrium and kinetic studies on basic dye adsorption by oil palm fibre activated carbon. Mater. Latiff. Lee. Raji.L. Mater. J. Mohamed. A. Bac ¸ aoui. B. G. R. Y. Ahmad. J. M. Azargohar. [27] G. Anirudhan. R. Ahmad. Jung.73 mg/g of 2.H. Legrouri. Dyes Pigments 75 (2007) 143–149. [26] C ¸. Martin. Velan. Analysis of adsorption characteristics of 2. Adsorption of basic dye (methylene blue) onto activated carbon prepared from rattan sawdust. Shivakamy. 142 (2007) 138–143. Adsorptive removal of chlorophenols from aqueous solution by low cost adsorbent-Kinetics and isotherm analysis. Ahmad.H. Adsorption of methylene blue onto bamboo-based activated carbon: Kinetics and equilibrium studies. Sarıcı-Ozdemir. A. Rio. K. X. Various functional groups on the prepared activated carbon were determined from the FTIR results. P.4-dichlorophenol from aqueous solutions by activated carbon fiber. M. L. Karacan. J. M.H.6-TCP uptake whereas activation temperature showed the most significant effect on activated carbon yield. [3] M.H. Hazard. Hameed. 144 (2007) 200–207. Carbon 39 (2001) 425–432. [16] G. Production of activated carbon from Luscar char: Experimental and modelling studies.4. Erdo˘ gan. S. K. Akmil-Bas ¸ar. M. Mater. [5] C.6-TCP uptake. 294 (2006) 21–30. H. Park. [29] F. J.A. Preparation and characterization of activated carbons by one-step steam pyrolysis/activation from apricot stones. Adsorption study for the removal of basic dye: experimental and modeling.6TCP uptake and carbon yield were found to agree satisfactorily with the values predicted by the models. Sarıcı. [14] I. B138 (2006) 116–124. D. Mater. Ahn. Manju. A. 88 (2006) 126–134. Water Res.B. J. Mater. Bas ¸ar. K. Bioresour. T. Mesopor. Chem. Hannache.29 h activation time and 2. J. Chem.6-TCP References [1] M. Chemosphere 58 (2005) 1079–1086. 115 (2006) 213–218. Eng. Appendix A. S. 70 (2001) 123–131. J. Phan. R. B135 (2006) 232–241. J.T. Acknowledgment The authors acknowledge the research grant provided by the University Science Malaysia under The Fundamental Research Grant Scheme (Project No: 6070015).H. Hazard.A.4.N. N. resulting in 20. ¨ ¨ [8] Y. Ahmad.G. Kamaruddin. Lu. Chen. Optimization of manufacturing conditions for activated carbon from Turkish lignite by chemical activation using response surface methodology. New York. 85 (2005) 219–225. Wang.4. Onal. Micropor. Hazard. 2001. Sheng. [19] F. Design and analysis of experiments.J. Sep. Stavropoulos. R. 94 (2003) 231–239.D. Nguyen. 137 (2008) 462–470. Cloirec. C ¸ . High surface area activated carbon prepared from cassava peel by chemical activation. J. [6] M. Sudaryanto. J. Hazard. J. Wang. Ismadji.F. USA. T. Artok. fifth ed. Purif.B. Eng. Sunando. [15] I.C.A. J. KOH:char impregnation ratio was found to have the most significant effect on 2. Adsorption characteristics of phenol and chlorophenols on granular activated carbon (GAC). Ozden. Bennouna. [13] B. Karacan. Hameed. 2.L. S. Rhee. F. Carbon 44 (2006) 2569–2577. Yaacoubi. Removal of 3-chlorophenol from water using rice-straw-based carbon. [2] R. . Chem.M.W. [24] N.W. Production and characterization of activated carbons from olive-seed waste residue. Micropor. Tan. Sourja. B.G. Technol. [22] E. Tzou. Denoyel. Prakash Kumar. Yang. Wang. 141 (2007) 819–825.H. [4] J. T. Sirshendu. Hazard. Jayanta. Optimization of conditions for the preparation of activated carbons from olive-waste cakes. J.M. S. [11] S. Maldonado-Hodar. Mesopor. A. K. C. [17] J. C. Tay.G. Yu. 127 (2007) 111–119. H. Naslain.91 KOH:char impregnation ratio. Mesopor. S. C. John Wiley and Sons. Bhatia.P.M. [10] B. J. Faur.H. Optimising the preparation of activated carbon from digested sewage sludge and coconut husk. [12] B. 97 (2006) 734–739. Ultrasound-assisted preparation of activated carbon from alkaline impregnated hazelnut shell: An optimization study on removal of Cu2+ from aqueous solution.K. Mater.

Textural and chemical characterisations of activated carbon prepared from oil-palm stone with H2 SO4 and KOH impregnation. Mesopor.C. Preparation and characterization of activated carbon from palm shell by chemical activation with K2 CO3 . A. 252 (2006) 5980–5983. Process effects of activated carbon with large specific surface area from corn cob. V. C. Mesopor. Mater.. [35] J. Xie. C.R. [33] R. [31] D. Aroua.W.K. Micropor. K. Comparisons of pore properties and adsorption performance of KOH-activated and steam-activated carbons. Characterization of adsorbent prepared from oil-palm shell by CO2 activation for removal of gaseous pollutants.4.M.L. Lett. Bao. [32] J.6-trichlorophenol adsorption onto activated clay. Preparation of activated carbons from cherry stones by activation with potassium hydroxide. J. Mac ´ ıas-Garc´ ıa. 97 (2006) 110–115. Mater.C.C. Colloid Interface Sci. Olivares-Mar´ ın.A. W. Guo.C. Colloids Surf. Hu. Bioresour. 98 (2007) 145–149. Hameed. Y.A. Bioresour. 32 (1999) 111–117. Lua. . Surf. Technol.W. 55 (2002) 334–339. W. Micropor. Technol. Cao. Aspects 307 (2007) 45–52. Tseng. A: Physicochem. Wu. Tseng. R. Lua. 80 (2005) 95–106. G´ omezSerrano. Daud. Guo. Fern´ andez-Gonz´ alez. Tan et al. M. Mater. Equilibrium and kinetics studies of 2. 717 [34] F.K.K.I.H.C. / Journal of Hazardous Materials 153 (2008) 709–717 [30] Q. Sci. 287 (2005) 428–437. [36] B.L. [37] M. S. Tseng. A. Pore structure and adsorption performance of the KOH-activated carbons prepared from corncob. Appl. Lv. A. Eng. Adinata.