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Chemical Engineering Journal 181–182 (2012) 467–478

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Chemical Engineering Journal
journal homepage: www.elsevier.com/locate/cej

Comparison of activated carbon and iron impregnated activated carbon derived ¸ ı lignite to remove cyanide from water from Gölbas
Tolga Depci ∗
Yuzuncu Yil University, Faculty of Engineering – Architecture, Department of Mining Engineering, 65080 Van, Turkey

a r t i c l e

i n f o

a b s t r a c t
The ability of lignite-activated carbon (LAC) and iron-impregnated activated carbon (FeAC) obtained from Gölbas ¸ ı lignite to remove cyanide ions from aqueous solution by adsorption was researched and compared with each other. The same process was applied also with commercial activated carbons which are in both granular (CAC-1) and powder forms (CAC-2). The morphologies, structures and properties of the activated carbons were determined by BET, XRD, XRF, SEM, zeta meter and magnetometer, respectively. The effects of various experimental parameters, such as initial cyanide concentration, pH, adsorbent type and particle size were researched in a batch adsorption technique at a temperature of 25 ◦ C. BET surface area of LAC is determined as 921 m2 /g. The obtained magnetic activated carbon has high surface area of 667 m2 /g with 19 wt.% Fe3 O4 coated and perfect magnetic separation performance. Langmuir model was found to be the best representative for cyanide-adsorption. The maximum monolayer adsorption capacities of LAC and FeAC are 60.18 mg/g and 67.82 mg/g at pH values of 7–7.5 and 64.10 mg/g and 68.02 mg/g at pH values of 10–10.5, respectively. Kinetic evaluation indicated that the cyanide adsorption onto the obtained activated carbons followed the pseudo-second order rate reaction. The diffusion-controlled kinetic models on the cyanide-adsorbent system showed that the removal rate was controlled not only by intraparticle diffusion but also by film diffusion. All experimental results point out that the LAC and FeAC are viable candidates for the removal of cyanide from water and wastewater. © 2011 Elsevier B.V. All rights reserved.

Article history: Received 3 October 2011 Received in revised form 1 December 2011 Accepted 1 December 2011 Keywords: Cyanide Magnetic activated carbon Non-linear regression Turkish lignite

1. Introduction In gold and silver leaching operation, cyanide is mostly used for extracting gold and silver from finely disseminated ores owing to its potential applicability and low cost [1]. Turkey has epithermal type gold deposits and it is not economically feasible to operate this type of ores without using cyanide in today’s conditions. Therefore, gold has been extracted by cyanide (cyanidation) [2,3]. However, over the past decades, with the rising awareness of environmental consciousness and growing fear because of its extremely toxic character, cyanide has become a matter of considerable debates in Turkey. Therefore, there has been a great pressure on producers of gold and silver for the disposal of cyanide wastes from gold and silver plants. Moreover, cyanide is not only employed for gold and silver discharge but also for the discharge of plating and surface finishing [4,5]. Removal of cyanide from aqueous solution is required when human health and protection of ecosystems are considered. Especially, at last decade, various researches have been carried out for the removal of cyanide using activated carbon [5–9]. Activated

∗ Tel.: +90 432 225 10 24; fax: +90 432 225 17 32. E-mail address: tdepci@gmail.com 1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.cej.2011.12.003

carbon (AC), one of the most commonly used adsorbent all over the globe due to the great specific surface area and pore structure, has a potential for adsorption of molecules from both the liquid and gas phase. Recently, granular activated carbon was impregnated with metallic compounds such as nickel [7], copper [8–10] and silver [7,8,11] to increase the removal efficiency of activated carbon. In the literature, however, there is no scientific investigation about removal of cyanide using iron impregnated activated carbon. Productions of iron impregnated activated carbons for the removal of inorganic compounds from aqueous solution have attracted great attention since separation from the medium is executed by a simple magnetic process [12–15]. Especially, in recent years, studies regarding synthesis and characterization of coal based magnetic activated carbon show rapidly increasing trend [16–18]. The aim of this research is to focus on the removal of cyanide from aqueous solution at different pH range using Gölbas ¸ ı lignite based activated carbon and iron-impregnated coal based activated carbon as adsorbent materials and is to compare the results with commercial activated carbon. As carbonaceous raw material, Gölbas ¸ ı lignite, was selected to prepare coal based activated carbon and magnetic activated carbon due to its readily availability and low cost. Proven reserve of Gölbas ¸ ı lignite (Harmanlı field) is 51,325,000 ton, and it has high ash and high moisture content with

In respect to the result of pH. Then.001 M) in the presence of p-dimethylaminobenzylrhodanine (0.2 L plastic reactor provided with temperature control and shaker. determined using X-ray fluorescence (XRF Spectro IQ). Kinetic experiments were also carried out under similar conditions (four selected solutions with different cyanide concentrations. (1). Preparation of activated carbons 2. Average relative error (ARE) and nonlinear Chi-square test (X2 ) for kinetic models were applied in addition to correlation coefficient (R2 ). Magnetic measurements of the LAC and FeAC were performed with a vibrating sample magnetometer (VSM. The amount of cyanide q (mg/g) adsorbed on activated carbons was calculated by the mass balance Eq. 100.5 and 10–10.2.) equipped with a microprocessor unit.06 3. being prepared it was modified with 20 ml aqueous solution containing 4 g Fe(NO3 )3 ·9H2 O and 0.20 2.468 T.5 g of the LAC was put into solution and the mixture was placed into ultrasonic bath for dispersion. second-order and diffusioncontrolled kinetic models. 200. The commercial activated carbon. commercial activated carbon was used in the same experimental condition and the obtained results were compared to the results of LAC and FeAC.0 (Malvern Inc. respectively. It was used in granular form (−7 + 12 mesh) and powder form (−200 mesh) and they were called as CAC-1 and CAC-2. the obtain product was cooled down under N2 flow and then 0. the samples were dried at 105 ◦ C for 24 h and ground and sieved under 200 mesh sizes. Materials and methods 2. Preparation of activated carbon (LAC) Activated carbon was prepared using Gölbas ¸ ı – Adıyaman (Turkey) lignite which was chosen for the precursor due to its availability and low cost.71 3063 3248 Ultimate analysis (d. was supplied by Calgon Corporation (Calgon GRC 22). pore size distribution and pore volume of the activated carbons were measured from nitrogen adsorption isotherms at 77 K in the range of 10−6 to 1 relative pressures by a Tri Star 3000 (Micromeritics. This process is very dangerous due to the HCN. Adsorption studies were conducted in routine manner by batch technique. the sample was degassed at 400 ◦ C for 2 h.1. The impregnated sample was heated to the activation temperature of 500 ◦ C for 1 h under N2 flow (100 ml/min) at the rate of 10 ◦ C min−1 .02% w/w in acetone) as indicator [8.54050 A). USA) surface analyzer. Nine solutions with different cyanide concentrations were prepared (i. 50. Moreover. the reactors were sealed immediately and all the experiments were done under fume hood. the effect of pH on the cyanide adsorption on the activated carbon was investigated. 7–7. Therefore. The obtained material was denoted as FeAC. this mixture was dried at 105 ◦ C in furnace to obtain an impregnated sample. The mixture was filtered and the solid dried. especially at low pH values.10 5.5%) or HCl (0.5 g adsorbent dosage at 25 ◦ C for 72 h at a constant stirring speed of 100 rpm. 350.1. The results were also considered on the basis of kinetic models.3.49 2.) H/C 55.33 1. Cyanide equilibrium concentration was determined by titrating against standardized silver nitrate solution (0. First.5 N HCl was added on it.23]. The pH values were adjusted in the range of 5–11.50 18. 10 mA. To find out the best fitting kinetic and isotherm models. q = (C0 − C ) × V W (1) where C0 (mg/l) is the initial cyanide concentration and C (mg/l) is unadsorbed cyanide concentration in solution at time t.1 N). The pH of the test solution was adjusted to the desired value by drop-wise addition of dilute NaOH (0. Finally. error analysis was also conducted. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 Table 1 Proximate and ultimate analysis of the air-dried lignite sample [20]. In order to investigate the morphology of the samples.1. The zeta potential of the activated carbon was measured by a Zeta Meter 3. 300 and 400 mg/L) and equilibrium concentration was found at different time intervals. respectively. 2. respectively.5.1. . Prior to the measurement. 200. The lignite sample (−60 + 40 mesh) was mixed with ZnCl2 (lignite/ZnCl2 weight ratio of 1:1) and the required amount of distilled water was added to this mixture. 100.f) C H N S O (diff. The XRD patterns were recorded by using Rigaku Miniflex Diffractometer with ˚ An iron content of FeAC was Cu Ka (30 kV. Pore size distribution and the features of pore structure were determined using BJH methods and t-plot. Proximate analysis Moisture (%) Volatile matter (%) Fixed carbon (%) Ash (%) Low calorific value (kcal/kg) High calorific value (kcal/kg) 20. X-ray powder diffraction (XRD) was used to characterize and identify the phase compositions and crystallinity of the samples.e. the solid was heated in tube furnace at 750 ◦ C for 3 h in the presence of nitrogen. Adsorption of cyanide onto activated carbons with respect to initial cyanide concentration was determined by equilibrating 1. [21]. 300.69 29. V (L) and W (g) is the volume of the solution and the weight of the dry activated carbons used respectively. 2. Preparation of iron-impregnated activated carbon (FeAC) The experimental procedure is based on the study conducted ¸ ı lignite by Yang et al. k = 1.10 31. The adsorption experiments were conducted at room temperature and samples were put in shaker at 100 rpm for 72 h. the samples of 5 ml were taken by micropipette and stored in vials. all experiments were conducted at two different pH ranges. This mixture was filtered and washed with distilled water at several times to remove residual chemicals and chlorine until filtrated solution did not give any reaction with AgNO3 . BET equation was used to calculate total surface area and average pore-diameter. LeO EVO 40 scanning electron microscope was used. Each time.3. the pseudo first-order. 2. 2. Experiment was carried out at 500 ml of 100 mg/L initial cyanide concentration with 1.02 34. Lake Shore 7407). Then. After the activation process. which is derived from coconut shell by physical activation.5 g of activated carbon samples with 500 ml of cyanide solution at the selected pH ranges in a 1. Adsorption experiments low calorific value [19]. Proximate and ultimate analyses of the air-dried lignite sample are given in Table 1 [20].2. Finally. the adsorption isotherm data were fitted to well known two-parameter models Langmuir and Freundlich isotherms as well as three parameter isotherm model (Redlich–Peterson). Commercial activated carbon (CAC) In order to evaluate and give a better decision about the applicability of LAC and FeAC for removal of cyanide from aqueous solution. The experimental procedure was based on the study published by Behnamfard and Salarirad [22]. 150. 250. Characterization methods Surface area. Activated carbon derived from Gölbas (LAC) was modified with nitric acid for 3 h at 80 ◦ C. 400 and 450 mg/L) by using the cyanide stock solution (2000 mg/l).1..a.

2 show the face-centered cubic (fcc) structure of Fe3 O4 which is magnetic nanoparticles. Besides. 3.504 0. 4. Fig.28]. 2. In the present study. Code CAC-1 CAC-2 LAC FeAC SBET (m2 /g) 906 928 921 667 Smic (m2 /g) 794 807 812 581 Smezo (m2 /g) 112 121 109 86 Vt (cm3 /g) 0.08 Dp denotes the average pore diameter (4 V/A by BET). According to hysteresis Table 2 Surface area and porosity values of the activated carbons. N is the number of observations in the regression model. As observed within figure. 2. 5 15 25 35 (311) 400 45 55 2 Θ (Degree) Fig. It may be attributed to the formation of iron oxide inside the pores [17. The expressions of the error functions are given below: ARE.26].05 Dp (nm) 2. An analysis of the powder XRD data proved that the main structures of activated carbons are amorphous and the broader reflections in the range of 10–30◦ .11 2.16 emu/g) showed nearly 656% increase after the impregnation process.08 nm and 2. Especially.9 /ˇ cos ) and found as 17 nm. it can be found that all peaks correspond to magnetite (Fe3 O4 – partially oxidized at the surface of activated carbon). LAC has a highly porous structure with a uniform distribution of the pores. which was primarily contributed by micropores. Characterization of the activated carbons The N2 adsorption isotherms of the activated carbons are given in Fig.44 0. By comparison with the patterns and d values of the FeAC and those of standard magnetite (JCPDS Card No: 19-629).476 0.17 2. 100 N N N i =1 qeexp − qecal qeexp exp 2 (2) i X2. Yang et al. Fig.4 0. Adsorption isotherm of nitrogen on the activated carbons at 77 K. indicative of its micropores character.8 1 LAC FeAC CAC Intensity (a. indicating a high adsorption capacity and wider micropores in microporous solids [25.05 emu/g. The coated iron oxide content was determined as 19 wt.07 0.049 0. Fig. Validity of adsorption isotherm and kinetic model Average relative error (ARE) and nonlinear Chi-square test (X2 ) to control consistency of adsorption isotherms and kinetic models were applied in addition to determination coefficient (R2 ).27.2 0.1.13%.16 nm.49 0. respectively.42 0. respectively. The reflections on FeAC could be assigned to the iron oxide.4. Powder X-ray diffraction patterns of activated and magnetic activated carbon. Vt denotes the total pore volume.%. 1. The saturation magnetization of LAC (Ms = 0.427 0. The results indicated that the activated carbon gained magnetic property as a result of the impregnation process.27 Vmic (cm3 /g) 0. On the other hand.T. Microsoft Excel. They can be classified as Type 1 – characteristic of micropore solids [24]. Surface area and porosity values of the activated carbons are presented in Table 2. The comparison of pore structure of CAC-1 and CAC-2 indicated that particle size of activated carbon had only a very small effect on the specific surface area because of highly developed internal pore structure. and no characteristic peaks belonging on other iron oxides or iron forms are detected in the XRD pattern.16 2. The average pore diameters were between 2. It can be seen that the iron oxide particles (brighter and small aggregates form) are inside the porous structure and cover the surface of activated carbon due to the impregnation process.23 Vmeso (cm3 /g) 0. The hysteresis loops of LAC and FeAC are given in Fig.6 0. adsorption isotherms and kinetics studies were explained using linear least squares methods and non-linear method which were determined using the solver add-in with Microsoft’s spreadsheet.064 0. The saturation magnetization of FeAC was obtained as 1. due to the iron impregnation process. 1. the comparison of surface area and porosity values of LAC and FeAC showed that the surface area of FeAC reduced from 921 m2 /g to 667 m2 /g. Besides.u. It appeared that activated carbons were dominantly micropores. [21] claimed that the peaks that were indexed in Fig. Adsorbed (cm/g) 3 250 200 150 100 50 0 0 0. It was found out that the activated carbons had a remarkable BET surface area. 1 shows that the volume of nitrogen gas adsorption of FeAC is lower than that of others. SEM image of FeAC reflects the morphological changes.) 300 FeAC (220) (400) (511) AC P/Po Fig. 2 shows the XRD pattern of the activated carbon and FeAC. 3 shows the SEM images of LAC and FeAC. The isotherms plots exhibit a round knee. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 469 350 Vol. The average crystallite size of Fe3 O4 particles are calculated by Debye–Scherrer equation (D = 0. Results and discussion 3. i=1 cal − qe (qei i ) qei exp exp (3) cal represent the amount of cyanide (mg/g) on where qei and qei the activated carbon which are experimentally found and calculated results.45% and 46.21. the decrease in micropore volume and micropore area were 28. .

Effect of pH on removal of cyanide and adsorption mechanism The effect of pH of solution on cyanide adsorption is shown in Figure 5. .5 and adsorption mechanism of cyanide could be explained using electrostatic attraction/repulsion “Fes –OH+ + CN− ↔ Fes –OH+ · · ·CN− ” or direct 2 2 − + exchange mechanism “Fes –OH2 + CN ↔ Fes − CN + H2 O”. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 Fig. At 75 CAC-1 CAC-2 CN Removal (%) 65 LAC FeAC 55 45 35 4 6 8 10 12 pH Fig.32]. 5. Effect of solution pH on adsorption of CN on CAC-1. The percentage removal of cyanide increased with increasing the pH and maximum retention was obtained at pH values between 6 and 8 and then decreased drastically until pH 11. [30] claimed that maximum retention which was obtained at a pH of 7. At high pH values (higher than 9). 5 indicates that the shape of the removal curve of FeAC is different from the others.21]. This observation is very compatible with the study published by Noroozifar et al. Noroozifar et al. The obtained results are compatible with the literature data [16. It means that FeAC can be easily separated from solution by a magnet which is seen in Fig. In order to test the magnetic separability of the FeAC from solution.2. It has a strict pHdependent character.470 T. The hysteresis loops of LAC and FeAC and picture of FeAC with magnet. They mentioned that Fe oxides enter the zeolite channels or covers the surface of zeolite and they cause additional active sites ( Fe OH). the adsorption properties of the obtained adsorbant increase due to chemisorption and the catalytic oxidation of cyanide [7. 4. loop. 4. 3. literature survey indicates that when activated carbon is impregnated with transitional metal such as copper and silver. remanent magnetization of FeAC was found to be 0. Fig. FeAC is a magnetic material and it can be removed from solution by magnetic separator. a magnet is also put near the glass bottle. Adams [6] declared that maximum retention of cyanide (HCN form) is obtained at pH value of 7. FeAC stick on the surface of glass bottle near the magnet demonstrating the magnetic sensitivity of FeAC. LAC and FEAC (cyanide concentration of 100 mg/L). [30] and Cornell and Schwertmann [31] who used zeolite–iron oxyhydroxide to remove cyanide from wastewater.069 emu/g. Besides. 4.17. This value is very close to zero indicating that FeAC shows super-paramagnetic behaviors at room temperature [29]. Fig. SEM images of LAC and FeAC. As seen in Fig. The lower limit of pH value was selected as 5 to keep the magnetic properties of iron impregnated activated carbon stable [13]. 3.8. Furthermore. CAC-2. In addition.

electrostatic repulsion between the negatively charged sites of FeAC and cyanide occurred.22.8 and 4 (pHzpc). maximum cyanide retention was obtained at pH value over 10. the surface of the activated carbon has negative charge due to the successive deprotonation of positive charged groups on the surface of activated carbon. FeAC has positive charge until the pH of 7. Therefore. The zeta (␨) potential variation of the activated carbon was estimated considering the pH of solution and this variation is given in Fig.5). [38] mentioned that maximum cyanide adsorption at pH 11 related with complexation of CN− with functional groups. [36] declared that CN− ion is a nucleophilic ion and it could be bind with the negatively charged adsorbent surface due to the anionic functional groups present on the adsorbent surface which occur due to the deprotonation on the activated carbon surface at pH values over than 10 [37]. Depending on the incompatible surface interactions. 7. pH values of 10–10. zeta potential is taken into account. .30. As the pH of the solution increases. 6. the adsorption isotherm parameters and kinetic data were determined at two different pH ranges (7–7. The pKa of HCN is 9. In the literature. chemical and exchange adsorptions are three general types of adsorption [34] and the adsorbents surface chemistry and aqueous phase chemistry affect an adsorption mechanism [35].T. [30] and Cornell and Schwertmann [31] about the effect of electrostatic forces on adsorption mechanism of cyanide. adsorption of cyanide ion at pH values over than 10 is explained with the properties of chemical ion exchange mechanism and physical adsorption.0 and this shows that HCN is completely dissociated to CN− at a solution pH of 10 [33]. The results obtained in the present study are also compatible with recent publications which indicates that maximum cyanide adsorption onto different adsorbents occurs in the pH range of 9–11 [7. Dash et al. In addition. respectively. the adsorption of the cyanide on FeAC decreased with increasing the pH of the solution. With respect to the above-mentioned information and also due to the pH values of 10–11 of gold cyanide disposals. 6. Fig.8. in the present study. On the other hand. Despite the same charge of the CAC and LAC particles and the dominant specify of cyanide (CN− ) in the solution.5. In order to check the suggestion of Noroozifar et al. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 471 20 Zeta Potential (mV) 0 0 2 4 6 8 10 12 -20 LAC FeAC CAC -40 -60 Equilibrium pH Fig. CAC-2 and LAC showed the same trend and rose by increasing the pH of the solution. HCN and CN− present in the aqueous solution at the pH values in the range of 6–8. and negative charge density on the surface increases. It proves that adsorption mechanism not only depends on the surface charge of adsorbate and adsorbent. and physical adsorption due to the precipitations.40]. Zeta potentials of the activated carbons. It can be said that electrostatic attraction may take place between cyanide species and FeAC due to different charge. the adsorption of cyanide on CAC-1. 6 shows that the CAC and LAC particle surfaces are negatively charged for a pH over 2.5 and 10–10. Garg et al. The prevailing mechanism for the adsorption of cyanide ions onto CAC and LAC may be explained by chemical ion exchange and this mechanism improves the cyanide adsorption. As known that physical.39. Effect of cyanide concentration on the adsorption of the activated carbons at pH 7–7. cyanide could be removed by forming iron 3 −4 cyanide complexes in the form Fe(CN)− 6 and Fe(CN)6 . The zeta potential of FeAC increase in the negative direction with increasing pH and isoelectrical points (IEP) is approximately 7 for FeAC.5. CAC-1 60 60 CAC-2 CN Removal (%) CN Removal (%) 40 40 100 ppm 20 100 ppm 20 200 ppm 300 ppm 400 ppm 0 20 40 60 80 200 ppm 300 ppm 400 ppm 0 20 40 60 80 0 0 Contact Time (h) Contact Time (h) LAC 60 80 FeAC CN Removal (%) 60 40 20 0 0 20 40 60 CN Removal (%) 40 100 ppm 20 100 ppm 200 ppm 300 ppm 400 ppm 80 200 ppm 300 ppm 400 ppm 0 20 40 60 80 0 Contact Time (h) Contact Time (h) Fig.

where Q0 signifies the theoretical monolayer capacity.3. qe is the adsorption capacity (mg/g). kf (L/g) is the Freundlich constant and 1/n (dimensionless) is the heterogeneity factor.5). 7 and 8 indicate that the percentage of cyanide removal at the adsorption equilibrium shows a concentration-dependent character. On the other hand. Figs. and nickel at high pH level [6–8]. b (L/mg) and Q0 (mg/g) are Langmuir isotherm constants. Effect of initial cyanide concentration The effect of cyanide concentration onto adsorbents (CAC-1. The isotherm expressions are given below: Langmuir. 3.5) the adsorption of cyanide onto FeAC is only 30–50% higher than on LAC. considering the magnetic property of FeAC.472 T. However.4. LAC and FeAC) was investigated at two different pH ranges of 7–7. The results indicate that iron impregnation enhanced the removal of cyanide depending on the pH of the solution. Adsorption isotherms The adsorption isotherm data were fitted with well-known two-parameter models. it was found that iron impregnation did not enhance the percentage of the removal of cyanide from aqueous solution at pH values of 10–10. so they were chosen in the present study.5 (in Fig. ARP (L/g). Literature survey shows that the cyanide adsorption capacities of activated carbons increases with the impregnation of them with silver. showing an activated carbon type-independent character. Literature data show that these isotherm models have been found applicable to cyanide sorption processes [6.22. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 60 CAC-1 60 CAC-2 CN Removal (%) CN Removal (%) 40 40 100 ppm 20 100 ppm 20 200 ppm 300 ppm 400 ppm 0 20 40 60 80 200 ppm 300 ppm 400 ppm 0 20 40 60 80 0 0 Contact Time (h) 60 Contact Time (h) LAC CN Removal (%) FeAC 60 CN Removal (%) 40 40 100 ppm 100 ppm 20 200 ppm 300 ppm 400 ppm 20 200 ppm 300 ppm 400 ppm 0 0 0 20 40 60 Contact Time (h) 80 0 20 40 60 Contact Time (h) 80 Fig. as opposed to the traditional screening technology. 7 and 8). 8). the obtained magnetic activated carbon (FeAC) shows super-paramagnetic behaviors at room temperature. To find out the best fitting kinetic and isotherm models. 8). 8b at normal pH conditions (7–7. BRP (L/mg)g and g are the Redlich–Peterson isotherm constants. respectively. 7 and 8. The calculated parameters for two different pH range (7–7. it can be seen that the shape of the curves of all adsorbents keep almost constant. The obtained results are consistent with the available scientific data [8.36].5 and 10–10.8. On the contrary of the literature. so it can be removed easily by a magnetic separator. The linearized isotherm parameters were calculated by applying the linear regression procedure and also non-linear isotherm parameters were determined using the solver add-in with Microsoft’s spreadsheet. Effect of cyanide concentration on the adsorption of the activated carbons at pH 10–10. it was defined that the removal of cyanide increased with decreasing the pH values from 10 to 7 for FeAC (Fig. Besides.30]. Redlich–Peterson [43].5 and 10–10.5. qe = Q0 bCe 1 + bCe (4) (5) ARP Ce g Freundlich.5 and their plots are illustrated in Figs. Langmuir [41] and Freundlich [42] as well as three-parameter isotherm model. the correlation coefficient and error functions were summarized in Tables 3 and 4. it can be said that it is a viable candidate for the removal of cyanide from water and wastewater. Although iron impregnation does not significantly affect the removal of cyanide. respectively. As mentioned before. CAC-2. qe = kf (Ce )1/n Redlich–Peterson. This may indicate that the adsorption is limited by number of the available active sites which are not sufficient for the high initial concentration of the cyanide. The adsorption capacity of the activated carbons decreases with increasing the cyanide concentration for all cases. This result also supports the previous conclusion which was obtained the effect of pH section. . by comparing the percentage of cyanide removal using FeAC depending on the initial pH of solution (Figs. qe = 1 + BRP Ce (6) where Ce is the equilibrium cyanide concentration in the liquid phase (mg/L). 8. Microsoft Excel. according to Fig. 3. average relative error (ARE) and nonlinear Chi-square test (X2 ) for kinetic models were applied in addition to correlation coefficient (R2 ). copper.

81 0.73 0.25 0.35 8. In this model. CAC-2 and Table 4 Isotherms parameters for the sorption of cyanide on the activated carbons (cyanide concentration of 100 mg/L. Since Langmuir model is one of the best fitting isotherm models which is also applied in this study.8 1.99 2. it can be inferred that.18 7.21 0.006 1 0.97 4.17 0.006 1 0.3 0.71 2.48 0.20 9.16 0.52 0.32 0.62 0.73 0.18 0.12 1.82 1.42 0.96 6. 0 <RL < 1 – favorable.34 8.99 2.95 2.18 0.99 3.32 0.78 0.51 0.24 5.31 2. Especially.99 1.74 0.21 0.007 1 0.5).32 0.23 8.99 1.37 0.52 0.82 1.T.77 1.51 0.82 2.25 0.78 0.45 0.52 LAC 64.92 0.97 7.26 2.16 0.12 0. Linearized form CAC-1 Langmuir isotherm Q0 (mg/g) b × 10−3 (L/mg) R2 ARE X2 Freundlich isotherm kf (L/g) n R2 ARE X2 Redlich–Peterson isotherm ARP (L/g) BRP (L/mg)g g R2 ARE X2 64.52 0.10 9.23 0.5).97 4.96 5.13 0.57 0.95 5.88 0.40 0.33 0.68 1.96 6.7 0.49 0.67 CAC-2 63.92 0.23 0.73 0.013 0.72 0.05 0.95 0.42 Non-linearized form CAC-1 62.95 0.41 LAC 64.85 0.99 3.81 0.97 5.96 7.52 FeAC 66.72 0.34 0.96 4. RL = 1 – linear.29 9.13 2.92 0.99 2.23 0.99 2.21 2.99 1.95 8.81 0. This model is related with three parameters empirical equation and is a hybrid isotherm featuring both Langmuir and Freundlich isotherms [45].86 0.99 2.28 0.7 0.37 0.27 FeAC 68.13 1.91 0.95 6.44 0.02 8.45 0.25 CAC-2 63.12 0. the adsorption capacities of CAC-1.95 6.12 8.99 2.21 CAC-2 61.96 5.009 1 0.52 0. It is defined by the following equation: RL = 1 1 + bCo (7) where RL is a dimensionless separation factor.8.71 0.74 FeAC 68.17 8. The results of Redlich–Peterson isotherm also support the suitability of Langmuir model.23 0. Langmuir model has lowest level of the values of error function. It can be used to understand adsorption mechanism of homogeneous or heterogeneous systems due to its versatility [46].34 0.002 1.923 0.12 2. It means that cyanide ions cover the surface of all activated carbons as monolayer and each cyanide ion has equal sorption activation energy at both pH values.32 0.82 5.79 0.81 0.86 0.99 2.95 4.99 3. and especially they calculated as one using non-linear form.11 FeAC 473 67.99 0.91 0.42 LAC 59.99 3.6 7.51 0.41 0.93 8.99 2. two parameter linear isotherm and non-linear isotherm data are very close with each other and have the minimal deviation. but not in the case of Freundlich isotherm.95 5.92 0.67 0.12 0.13 0.46 0. Co is the initial dye concentration and b is Langmuir constant.49 1.99 3.68 2.38 2.51 0.67 0.88 2. indicating that the adsorption is favorable.28 1.72 0.002 1.75 2.49 0.45 0.24 1.41 0.96 6.75 1.12 0.95 0.98 3.99 2.76 0.99 3. Tables 3 and 4 show that “g” values are close to one.57 0.12 0.74 0.92 0.52 0.17 6.85 0.96 5. “g” is the exponent varying between 0 and 1.68 0.93 0.94 0.99 2.5 CAC-2 60.43 1.12 2.41 0. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 Table 3 Isotherms parameters for the sorption of cyanide on the activated carbons (cyanide concentration of 100 mg/L.19 0.21 .98 1.99 1. Adsorption of cyanide on all the activated carbons at two different pH ranges is quite well consistent with the Langmuir and Redlich–Peterson models.07–0. Therefore.8 0.07 2. The values of RL were found in the range of 0.13 0.96 1.45 0.4 0. pH values in the range of 7–7.98 0.01 1.92 3.48 0.45 0.006 1 0.2 0. pH values in the range of 10–10.92 0.32 2.99 2.04 1. The feasibility of the reactions are explained using the value of RL (RL > 1 – unfavorable.24 0.53 1.63 0.99 3.07 From Tables 3 and 4.72 Non-linearized form CAC-1 64.38 0.11 0.34 1.27 5. 9. RL = 0 – irreversible).35 7.33 0. the deviation very large for both cases.47 0.99 2. Based on the adsorption capacities (Langmuir (Q0 ) and Freundlich (kf ) constants) of the activated carbons at both pH range (in Tables 3 and 4).008 1 0.94 0.12 LAC 60.29 1.32 0.98 2.99 2.93 0.16 0. ‘RL ’ named as dimensionless separation factor was calculated to determine whether the adsorption system is favorable or not [44].39 1.14 1 0.99 2.42 0.97 4.22 9. This indicates that Langmuir condition is ideal one for the adsorption mechanism [47].032 0.99 2.81 1. Linearized form CAC-1 Langmuir isotherm Q0 (mg/g) b × 10−3 (L/mg) R2 ARE X2 Freundlich isotherm kf (L/g) n R2 ARE X2 Redlich–Peterson isotherm ARP (L/g) BRP (L/mg)g g R2 ARE X2 61. only the plots of linear and non-linear Langmuir isotherms for both pH values are depicted in Fig.97 1.

Moreover.21 156. It indicates that the adsorption capacities of the activated carbons for cyanide.5) 45 Ce /qe (mg/g) qe (mg/g) 5 CAC-1 30 CAC-1 CAC-2 LAC FeAC Langmuir non-linear 3 CAC-2 LAC FeAC 15 1 0 100 200 300 400 0 0 100 200 300 400 Ce (mg/L) Ce (mg/L) Fig. it can be concluded that pseudo-second order kinetic model with linear and non .2 72.5) 7 Non-linear isotherm plots (pH 10 . [8] and Behnamfard and Salarirad [22]. C is the intercept and kint is the intraparticle diffusion rate constant (mg/g min1/2 ).4 19.5. it seems that LAC and FeAC are attractive candidates for removal of cyanide from aqueous solution. Adsorption kinetics The pseudo-first order kinetic model [48] and pseudo-second order kinetic model [49] were used to predict the mechanism involved in the adsorption process of cyanide at two different pH ranges (7–7. It seems that LAC and FeAC have also greater removal efficiency than lots of the adsorbents which are given in Table 5. 9.5 and 10–10. the adsorption capacity of FeAC shows different trend. Adsorbents Ag-imregnated AC Ni-impregnated AC Cu-impregnated AC Ativated carbon Modified zeolite with iron Pistachio hull wastes Pyrophylite Adsorption capacity (mg/g) 45. The result confirms the previous results which were obtained in this study. 3. k1 is the rate constant of the pseudo-first-order adsorption (min−1 ).5. 10.5) C e /q e (mg/g) qe (mg/g) 4 2 0 300 CAC-1 CAC-2 LAC FeAC CAC-1 CAC-2 LAC FeAC 400 0 100 200 Ce (mg/L) 300 400 Linear isotherm plots (pH 10 .5) 8 6 60 45 30 15 0 0 100 200 Ce (mg/L) Non-linear isotherm plots (pH 7 . It was found that LAC and FeAC exhibited nearly same cyanide removal efficiency with the commercial activated carbons.62 6. 10. CAC-2 and LAC at both pH ranges show that the adsorption of cyanide onto them is virtually independent of particle size and the activated carbon types.5–11 10–11 7–7. LAC are very close with each other at the same pH range and their capacities increases by increasing the pH of the solution. On the other hand. Therefore only the plots validating the pseudo-second order kinetic model for linear and non-linearized kinetic models (between t/qt vs t and qt vs t) at different pH range of the cyanide of 100 mg/L. the adsorption capacities of some adsorbents for cyanide adsorption are given in Table 5. k2 is the rate constant of the pseudo-second-order adsorption (g/mg min). Intraparticle diffusion. It can be concluded that the adsorption of cyanide onto the activated carbons did not follow the pseudo first order model. From Fig. The plots of linear and non-linear isotherm Langmuir model for the removal of cyanide at two different pH values (cyanide concentration of 100 mg/L). qt = kint t 1/2 + C Table 5 Comparison of the adsorption capacities of cyanide onto some adsorbents. are given in Tables 6 and 7. at room temperature (25 ◦ C) are given in Fig.10. The pseudo second order kinetic model with high correlation coefficient.5 and 10–10. FeAC has the highest adsorption capacity at pH 7–7.5). Therefore. The kinetic linearized and non-linearized model studies were carried out at initial cyanide concentration of 100 mg/l and the calculated kinetic parameters of the fitted kinetic models for two pH ranges. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 Linear isotherm plots (pH 7 . 7–7. low ARE and X2 describes the system much better than the pseudo first order kinetic models. intraparticle diffusion model [50] was also applied for all conditions. Equilibrium adsorption between the activated carbons and cyanide indicated that the extent of adsorption was not dependent on the pore structure of the activated carbons.10. respectively. especially FeAC. qt = qe [1 − exp(−k1 t )] qt = k2 qe 2 t 1 + k2 qe t (8) (9) (10) Pseudo-second order.5 and its capacity decreases with increasing the pH of the solution. respectively.5 10 7 References [7] [7] [8] [22] [30] [39] [40] where qe and qt are the amounts (mg/g) of solute bound at the interface at the equilibrium and after time t (min). have a strict pH-dependent character.4 pH 11 >11 10. Similar results were found by Deveci et al. In order to compare the adsorption capacities of LAC and FeAC.7 15.7.474 T. In addition.7. The accuracy and applicability of the kinetics model were checked using ARE and X2 error function model. The kinetic equations are given below: Pseudo-first order. the ultimate carbon-adsorption capacities of CAC-1.7 47.

Pseudo-first-order CAC-1 Linearized form qe (cal) (mg/g) k1 (min−1 ) R2 ARE X2 14.63 0. Intra particle diffusion CAC-1 Initial concentration (ppm) kint (mg/g min1/2 ) C R2 Intra particle diffusion LAC Initial concentration (ppm) kint (mg/g min1/2 ) C R2 100 1.16 CAC-2 20.95 23.39 CAC-2 19. respectively.01 2.00 6. In the present study.48 2.45 0.86 400 5.11 0.43 21.46 0.66 4.19 0.71 0.79 0. 11 and 12 which indicate that the adsorption mechanism of cyanide onto the activated carbons for all conditions follows two steps.32 1.14 0.01 2.96 0.10 0.98 7.70 200 3.007 3.63 1.10 8.8 0.23 LAC 16.99 4.61 LAC 19.52 CAC-2 19.94 FeAC 19.10 0.004 1.42 18.09 1.97 7.70 0.87 0.5).00 1.53 0.42 14.55 FeAC 20.99 5.94 0.78 0.03 1. to understand the adsorption mechanism of cyanide on the activated carbons.36 0.01 2.05 1.09 0.01 3.44 0.99 4.28 17.72 2.17 7.99 4.86 FeAC 100 2.011 3. The first one covering the time interval between 1 and 21 h (more than 21 h for high cyanide concentration).13 0.01 3.39 2.85 300 5.20 0.86 0.T.5) are given in Tables 8 and 9.66 2.80 0.32 0.1 2.88 200 3.95 11.995 4.35 9.00 4.89 100 2. Parameters which are obtained from the general equation of intraparticle diffusion model as a function of different initial cyanide concentrations at two different pH values (7–7.12 0.48 4. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 Table 6 Kinetic parameters for the effect of the activated carbon types on the adsorption of cyanide (pH values: 7–7.005 2.14 0. The second range (after 21 h) is described as the gradual adsorption limited by diffusion of solute in Table 8 Intraparticle diffusion parameters for the effect of the activated carbon types and cyanide concentration on adsorption (pH values: 7–7.67 13.32 0. is attributed to the diffusion of cyanide through the solution film to the external surface of the activated carbons (mass transfer).99 5.94 1.20 0.46 0.63 1.08 0.56 CAC-1 CAC-2 Non-linearized form 16.85 .32 Pseudo-second-order CAC-1 Linearized form qe (cal) (mg/g) k2 (g/mg min) h (mg/g min) R2 ARE X2 19.85 300 5.08 0.99 9.03 LAC 16.86 400 5.68 0.5.93 0.52 0.84 300 5.75 0.99 5.98 24.31 0.54 0.22 19.83 FeAC 16.74 0. which has a very sharp.42 0.00 4.19 0.13 0.7 3.92 4.97 LAC 21. Their plots are shown in Figs.5 and 10–10.99 7.99 8.77 200 3.00 0.99 3.007 5.06 1.00 6.61 0.94 29.19 2.02 1.93 0.04 0.99 6.01 6.9 0.69 2.84 12.86 15.88 CAC-2 100 1.71 0.06 0.72 0.15 0.65 0.99 0.19 linear forms showing good correlation between experimental and predicted values.07 0.99 6.11 LAC 18.14 0.5.89 Table 7 Kinetic parameters for the effect of the activated carbon types on the adsorption of cyanide (pH values: 10–10.38 FeAC 18.82 1.03 LAC 12.02 0.17 0.99 7.29 2.37 0.11 0.97 26.51 0.86 400 5.58 LAC 14.16 0.79 400 5.02 CAC-1 CAC-2 Non-linearized form 16.23 1.01 3.09 0. intraparticle diffusion model was also applied for all conditions.87 FeAC 18.72 0.85 0.37 CAC-1 CAC-2 Non-linearized form 20.06 0.98 22.34 0.90 0.00 8.25 20.86 0.49 0.48 0.26 LAC 18.36 0.25 FeAC 27.56 1.66 0.87 1. cyanide concentration: 100 mg/L).58 1.39 1.34 475 FeAC 24.96 0.72 0.072 0.97 12.05 1.32 0.14 0.00 9.2 0.007 2. cyanide concentration: 100 mg/L).10 0.99 7.18 1.00 4.99 6.05 0.48 Pseudo-second-order CAC-1 Linearized form qe (cal) (mg/g) k2 (g/mg min) h (mg/g min) R2 ARE X2 19.08 0.57 0.10 0.47 FeAC 26.10 CAC-1 CAC-2 Non-linearized form 19.98 4. Pseudo-first-order CAC-1 Linearized form qe (cal) (mg/g) k1 (min−1 ) R2 ARE X2 13.82 300 4.39 0.007 2.2 4.46 CAC-2 19.36 20.85 0.12 0.007 3.19 5.59 0.76 200 3.

Fast equilibrium obtained at low initial cyanide concentration.2 FeAC qt (mg/g) LAC 20 CAC-1 1.7. It means that the pores show resistance against the diffusion of cyanide ion into inner adsorption sites. CAC-2. At high cyanide concentration. . LAC and FeAC for all conditions.10. Besides. diffusion of cyanide through the solution film to the external surface of the activated carbons are very fast and then decreases depending on the equilibrium time.5) CAC-1 30 Non-linear forms (pH 7 .6 10 CAC-2 LAC FeAC 0 0 20 40 60 80 0 0 20 pseudo second order non-linear t (hours) Linear forms (pH 10 . the liquid contained in pores of adsorbent particles and along the pores walls (intraparticle diffusion) [51]. the adsorption kinetics reaches the equilibrium at a different time depending on the initial cyanide concentration. Moreover.5) q t (mg/g) 3. 10.4 Linear forms (pH 7 . This observation is supported with the data published by Behnamfard and Salarirad [22] and Dash et al. 11.6 0 0 20 40 60 80 0 0 20 40 60 80 t (hours) t (hours) Fig. Moussavi and Khosravi [39] and Hameed 60 100 ppm CAC-1 200 ppm 300 ppm 60 100 ppm CAC-2 200 ppm 300 ppm 45 45 qt (mg/g) qt (mg/g) 30 15 0 0 400 ppm 30 15 0 400 ppm 2 4 6 8 10 0 2 4 6 8 10 t 60 100 ppm 1/2 (h 1/2 ) t 1/2 (h 1/2 ) LAC 60 100 ppm 200 ppm FeAC qt (mg/g) 45 200 ppm 300 ppm qt (mg/g) 45 30 15 0 300 ppm 400 ppm 30 15 0 0 400 ppm 2 4 6 1/2 8 10 0 2 4 6 8 10 t (h 1/2 ) t 1/2 (h 1/2 ) Fig.2 t/q t 10 CAC-1 CAC-2 LAC FeAC pseudo second order non-linear 1. Plots of intraparticle diffusion for adsorption of cyanide onto the activated carbons at various initial concentration of cyanide (pH values: 7–7.8 CAC-2 t/q t 3.7. [36] who explained that cyanide ions at low cyanide concentration could be adsorbed by more readily available sorption sites.5).8 Non-linear form (ph 10 . Briefly it can be concluded that the intraparticle diffusion step controls the cyanide adsorption on CAC-1. The pseudo-second order adsorption kinetics for cyanide adsorption onto the activated carbons at two pH values at cyanide concentration of 100 mg/L.10.476 T.5) CAC-1 CAC-2 LAC FeAC 40 60 80 t (hours) 20 4.5) 4. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 6. This shows that available sorption sites of activated carbon are saturated depending on the mass transfer and then high level of cyanide ions in the system try to diffuse in the pores.

[52] suggested that the boundary layer thicknesses.5 and 64.73 4.57 0. Conclusion In this study.37 0. The ultimate carbon–cyanide adsorption capacities of the activated carbons are virtually independent of particle size. Plots of intraparticle diffusion for adsorption of cyanide onto the activated carbons at various initial concentration of cyanide (pH values: 10–10.02 mg/g at pH values of 10–10.13 0.02 2.86 400 5. a plain activated carbon and iron impregnated activated carbon were prepared from Gölbas ¸ ı lignite.94 5.54 0. “C” should be considered to give a better decision.87 400 5.99 0. Depci / Chemical Engineering Journal 181–182 (2012) 467–478 Table 9 Intraparticle diffusion parameters for the effect of the activated carbon types and cyanide concentration on adsorption (pH values: 10–10. respectively. pore structure and the activated carbon types.09 5.32 0.% Fe3 O4 coated and perfect magnetic separation performance.82 mg/g at pH values of 7–7.19 8.85 100 2. FeAC has also high surface area of 667 m2 /g with 19 wt.93 5. Solution pH plays a major role in cyanide adsorption onto FeAC and maximum retention was obtained at pH 7–7. 12.76 200 3.33 0. Intraparticle diffusion model shows that the removal rate is controlled by not only intraparticle diffusion but also the film diffusion.5). Finally.78 200 3.77 200 3. Adsorption of cyanide on the activated carbons is quite well consistent with the Langmuir models. Tables 8 and 9 show that C values are positive indicating that cyanide adsorption controls with not only the intraparticle diffusion but also the film diffusion. They are much higher than some of the maximum values reported in the literature.90 3. 4.84 300 5.17 4.86 477 400 5.5). Besides C values increase with increasing cyanide concentration for all activated carbons.88 200 3. The experimental results best fitted to the second-order kinetic equation. The maximum monolayer adsorption capacities of LAC and FeAC are 60.86 FeAC 100 1.18 mg/g and 67. which were obtained from natural resource.68 5. It means that the film diffusion is involved in controlling cyanide adsorption onto the activated carbons at higher cyanide concentrations [52]. BET surface area of LAC is determined as 921 m2 /g.47 0. for the removal of cyanide from aqueous solution.T. Intra particle diffusion CAC-1 Initial concentration (ppm) kint (mg/g min1/2 ) C R2 Intra particle diffusion LAC Initial concentration (ppm) kint (mg/g min1/2 ) C R2 100 1.04 0.86 400 5.19 8.5 due to the electrostatic attraction and exchange mechanism.80 0.94 0.19 8.74 0.5.87 CAC-2 100 1.69 5.84 300 5. it is possible to affirm that LAC and FeAC are promising adsorbents. The percentage of cyanide removal at the adsorption equilibrium shows a concentration-dependent character. The adsorption capacity of the activated carbons decreases with increasing the cyanide concentration due to the limited available active site of the surface of activated carbons.52 0.19 5.64 4.82 300 5.85 300 5.86 60 100 ppm CAC-1 200 ppm 60 100 ppm CAC-2 200 ppm 300 ppm 45 45 qt (mg/g) 300 ppm qt (mg/g) 30 15 0 0 400 ppm 30 15 0 400 ppm 2 4 6 8 10 0 2 4 6 8 10 t 60 100 ppm 1/2 (h 1/2 ) 60 100 ppm t 1/2 (h 1/2 ) LAC 200 ppm 300 ppm FeAC qt (mg/g) 45 30 15 0 0 45 200 ppm 300 ppm qt (mg/g) 400 ppm 30 15 0 400 ppm 2 4 6 8 10 0 2 4 6 8 10 t 1/2 (h 1/2 ) t 1/2 (h 1/2 ) Fig. Also special thanks to .19 5.23 0.93 0.48 5.10 mg/g and 68.56 0. Acknowledgements Thanks are due to Askale Van Cement Factory for their contributions in performing experiments.

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