Chemical Engineering Journal 181182 (2012) 467478

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Chemical Engineering Journal

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Comparison of activated carbon and iron impregnated activated carbon derived lignite to remove cyanide from water from Glbas
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 Glbas 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 77.5 and 64.10 mg/g and 68.02 mg/g at pH values of 1010.5, 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 lm 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 nely 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 todays 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 nishing [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 [59]. 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 specic 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 [810] and silver [7,8,11] to increase the removal efciency of activated carbon. In the literature, however, there is no scientic 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 [1215]. Especially, in recent years, studies regarding synthesis and characterization of coal based magnetic activated carbon show rapidly increasing trend [1618]. The aim of this research is to focus on the removal of cyanide from aqueous solution at different pH range using Glbas 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, Glbas lignite, was selected to prepare coal based activated carbon and magnetic activated carbon due to its readily availability and low cost. Proven reserve of Glbas lignite (Harmanl eld) is 51,325,000 ton, and it has high ash and high moisture content with

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Table 1 Proximate and ultimate analysis of the air-dried lignite sample [20]. Proximate analysis Moisture (%) Volatile matter (%) Fixed carbon (%) Ash (%) Low caloric value (kcal/kg) High caloric value (kcal/kg) 20.50 18.10 31.69 29.71 3063 3248 Ultimate analysis (d.a.f) C H N S O (diff.) H/C 55.10 5.49 2.06 3.02 34.33 1.20

2.2. Characterization methods Surface area, pore size distribution and pore volume of the activated carbons were measured from nitrogen adsorption isotherms at 77 K in the range of 106 to 1 relative pressures by a Tri Star 3000 (Micromeritics, USA) surface analyzer. BET equation was used to calculate total surface area and average pore-diameter. Pore size distribution and the features of pore structure were determined using BJH methods and t-plot, respectively. Prior to the measurement, the sample was degassed at 400 C for 2 h. X-ray powder diffraction (XRD) was used to characterize and identify the phase compositions and crystallinity of the samples. The XRD patterns were recorded by using Rigaku Miniex Diffractometer with An iron content of FeAC was Cu Ka (30 kV, 10 mA, k = 1.54050 A). determined using X-ray uorescence (XRF Spectro IQ). In order to investigate the morphology of the samples, LeO EVO 40 scanning electron microscope was used. The zeta potential of the activated carbon was measured by a Zeta Meter 3.0 (Malvern Inc.) equipped with a microprocessor unit. The pH of the test solution was adjusted to the desired value by drop-wise addition of dilute NaOH (0.5%) or HCl (0.1 N). Magnetic measurements of the LAC and FeAC were performed with a vibrating sample magnetometer (VSM; Lake Shore 7407). 2.3. Adsorption experiments

low caloric value [19]. Moreover, the adsorption isotherm data were tted to well known two-parameter models Langmuir and Freundlich isotherms as well as three parameter isotherm model (RedlichPeterson). The results were also considered on the basis of kinetic models, the pseudo rst-order, second-order and diffusioncontrolled kinetic models. To nd out the best tting kinetic and isotherm models, error analysis was also conducted. Average relative error (ARE) and nonlinear Chi-square test (X2 ) for kinetic models were applied in addition to correlation coefcient (R2 ).

2. Materials and methods 2.1. Preparation of activated carbons 2.1.1. Preparation of activated carbon (LAC) Activated carbon was prepared using Glbas Adyaman (Turkey) lignite which was chosen for the precursor due to its availability and low cost. Proximate and ultimate analyses of the air-dried lignite sample are given in Table 1 [20]. 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. Then, this mixture was dried at 105 C in furnace to obtain an impregnated sample. The impregnated sample was heated to the activation temperature of 500 C for 1 h under N2 ow (100 ml/min) at the rate of 10 C min1 . After the activation process, the obtain product was cooled down under N2 ow and then 0.5 N HCl was added on it. This mixture was ltered and washed with distilled water at several times to remove residual chemicals and chlorine until ltrated solution did not give any reaction with AgNO3 . Finally, the samples were dried at 105 C for 24 h and ground and sieved under 200 mesh sizes. 2.1.2. Preparation of iron-impregnated activated carbon (FeAC) The experimental procedure is based on the study conducted lignite by Yang et al. [21]. Activated carbon derived from Glbas (LAC) was modied with nitric acid for 3 h at 80 C. Then, being prepared it was modied with 20 ml aqueous solution containing 4 g Fe(NO3 )3 9H2 O and 0.5 g of the LAC was put into solution and the mixture was placed into ultrasonic bath for dispersion. The mixture was ltered and the solid dried. Finally, the solid was heated in tube furnace at 750 C for 3 h in the presence of nitrogen. The obtained material was denoted as FeAC. 2.1.3. 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, commercial activated carbon was used in the same experimental condition and the obtained results were compared to the results of LAC and FeAC. The commercial activated carbon, which is derived from coconut shell by physical activation, was supplied by Calgon Corporation (Calgon GRC 22). It was used in granular form (7 + 12 mesh) and powder form (200 mesh) and they were called as CAC-1 and CAC-2, respectively.

Adsorption studies were conducted in routine manner by batch technique. First, the effect of pH on the cyanide adsorption on the activated carbon was investigated. Experiment was carried out at 500 ml of 100 mg/L initial cyanide concentration with 1.5 g adsorbent dosage at 25 C for 72 h at a constant stirring speed of 100 rpm. The pH values were adjusted in the range of 511. This process is very dangerous due to the HCN. Therefore, especially at low pH values, the reactors were sealed immediately and all the experiments were done under fume hood. In respect to the result of pH, all experiments were conducted at two different pH ranges, 77.5 and 1010.5, respectively. Adsorption of cyanide onto activated carbons with respect to initial cyanide concentration was determined by equilibrating 1.5 g of activated carbon samples with 500 ml of cyanide solution at the selected pH ranges in a 1.2 L plastic reactor provided with temperature control and shaker. The adsorption experiments were conducted at room temperature and samples were put in shaker at 100 rpm for 72 h. The experimental procedure was based on the study published by Behnamfard and Salarirad [22]. Nine solutions with different cyanide concentrations were prepared (i.e., 50, 100, 150, 200, 250, 300, 350, 400 and 450 mg/L) by using the cyanide stock solution (2000 mg/l). Kinetic experiments were also carried out under similar conditions (four selected solutions with different cyanide concentrations; 100, 200, 300 and 400 mg/L) and equilibrium concentration was found at different time intervals. Each time, the samples of 5 ml were taken by micropipette and stored in vials. Cyanide equilibrium concentration was determined by titrating against standardized silver nitrate solution (0.001 M) in the presence of p-dimethylaminobenzylrhodanine (0.02% w/w in acetone) as indicator [8,23]. The amount of cyanide q (mg/g) adsorbed on activated carbons was calculated by the mass balance Eq. (1). 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, V (L) and W (g) is the volume of the solution and the weight of the dry activated carbons used respectively.

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469

350

Vol. Adsorbed (cm/g)

250 200 150 100 50 0 0 0.2 0.4 0.6 0.8 1

LAC FeAC CAC

Intensity (a.u.)

300

FeAC (220) (400) (511)

AC

P/Po
Fig. 1. Adsorption isotherm of nitrogen on the activated carbons at 77 K.

15

25

35

(311)

400

45

55

2 (Degree)
Fig. 2. Powder X-ray diffraction patterns of activated and magnetic activated carbon.

In the present study, 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 Microsofts spreadsheet, Microsoft Excel. 2.4. 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 coefcient (R2 ). The expressions of the error functions are given below: ARE, 100 N
N N

i =1

qeexp qecal qeexp

exp 2

(2)
i

X2,
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, respectively. N is the number of observations in the regression model.

3. Results and discussion 3.1. Characterization of the activated carbons The N2 adsorption isotherms of the activated carbons are given in Fig. 1. They can be classied as Type 1 characteristic of micropore solids [24]. The isotherms plots exhibit a round knee, indicating a high adsorption capacity and wider micropores in microporous solids [25,26]. Besides, Fig. 1 shows that the volume of nitrogen gas adsorption of FeAC is lower than that of others. Surface area and porosity values of the activated carbons are presented in Table 2. It was found out that the activated carbons had a remarkable BET surface area, which was primarily contributed by micropores. The average pore diameters were between 2.08 nm and 2.16 nm, indicative of its micropores character. It appeared that

activated carbons were dominantly micropores. 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 specic surface area because of highly developed internal pore structure. Besides, 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. Especially, the decrease in micropore volume and micropore area were 28.45% and 46.13%, respectively, due to the iron impregnation process. It may be attributed to the formation of iron oxide inside the pores [17,21,27,28]. Fig. 2 shows the XRD pattern of the activated carbon and FeAC. An analysis of the powder XRD data proved that the main structures of activated carbons are amorphous and the broader reections in the range of 1030 . The reections on FeAC could be assigned to the iron oxide. Yang et al. [21] claimed that the peaks that were indexed in Fig. 2 show the face-centered cubic (fcc) structure of Fe3 O4 which is magnetic nanoparticles. By comparison with the patterns and d values of the FeAC and those of standard magnetite (JCPDS Card No: 19-629), it can be found that all peaks correspond to magnetite (Fe3 O4 partially oxidized at the surface of activated carbon), and no characteristic peaks belonging on other iron oxides or iron forms are detected in the XRD pattern. The average crystallite size of Fe3 O4 particles are calculated by DebyeScherrer equation (D = 0.9 / cos ) and found as 17 nm. Fig. 3 shows the SEM images of LAC and FeAC. As observed within gure, LAC has a highly porous structure with a uniform distribution of the pores. On the other hand, SEM image of FeAC reects the morphological changes. 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. The coated iron oxide content was determined as 19 wt.%. The hysteresis loops of LAC and FeAC are given in Fig. 4. The results indicated that the activated carbon gained magnetic property as a result of the impregnation process. The saturation magnetization of LAC (Ms = 0.16 emu/g) showed nearly 656% increase after the impregnation process. The saturation magnetization of FeAC was obtained as 1.05 emu/g. According to hysteresis

Table 2 Surface area and porosity values of the activated carbons. 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) 0.49 0.504 0.476 0.27 Vmic (cm3 /g) 0.42 0.44 0.427 0.23 Vmeso (cm3 /g) 0.07 0.064 0.049 0.05 Dp (nm) 2.16 2.17 2.11 2.08

Dp denotes the average pore diameter (4 V/A by BET); Vt denotes the total pore volume.

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Fig. 3. SEM images of LAC and FeAC.

Fig. 4. The hysteresis loops of LAC and FeAC and picture of FeAC with magnet.

loop, FeAC is a magnetic material and it can be removed from solution by magnetic separator. Besides, remanent magnetization of FeAC was found to be 0.069 emu/g. This value is very close to zero indicating that FeAC shows super-paramagnetic behaviors at room temperature [29]. It means that FeAC can be easily separated from solution by a magnet which is seen in Fig. 4. The obtained results are compatible with the literature data [16,17,21]. In order to test the magnetic separability of the FeAC from solution, a magnet is also put near the glass bottle. As seen in Fig. 4, FeAC stick on the surface of glass bottle near the magnet demonstrating the magnetic sensitivity of FeAC. 3.2. Effect of pH on removal of cyanide and adsorption mechanism The effect of pH of solution on cyanide adsorption is shown in Figure 5. The lower limit of pH value was selected as 5 to keep the magnetic properties of iron impregnated activated carbon stable [13]. Fig. 5 indicates that the shape of the removal curve of FeAC is different from the others. It has a strict pHdependent character. 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. This observation is very compatible with the study published by Noroozifar et al. [30] and Cornell and Schwertmann [31] who used zeoliteiron oxyhydroxide to remove cyanide from wastewater. They mentioned that Fe oxides enter the zeolite channels or covers the surface of zeolite and they cause additional active sites ( Fe OH). In addition, Noroozifar et al. [30] claimed that

maximum retention which was obtained at a pH of 7.5 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. Furthermore, Adams [6] declared that maximum retention of cyanide (HCN form) is obtained at pH value of 7. At high pH values (higher than 9), literature survey indicates that when activated carbon is impregnated with transitional metal such as copper and silver, the adsorption properties of the obtained adsorbant increase due to chemisorption and the catalytic oxidation of cyanide [7,8,32]. At
75
CAC-1 CAC-2

CN Removal (%)

65

LAC FeAC

55

45

35 4 6 8 10 12

pH
Fig. 5. Effect of solution pH on adsorption of CN on CAC-1, CAC-2, LAC and FEAC (cyanide concentration of 100 mg/L).

T. Depci / Chemical Engineering Journal 181182 (2012) 467478

471

20

Zeta Potential (mV)

0 0 2 4 6 8 10 12

-20

LAC FeAC CAC

-40

-60

Equilibrium pH
Fig. 6. Zeta potentials of the activated carbons.

pH values of 1010.5, cyanide could be removed by forming iron 3 4 cyanide complexes in the form Fe(CN) 6 and Fe(CN)6 . In order to check the suggestion of Noroozifar et al. [30] and Cornell and Schwertmann [31] about the effect of electrostatic forces on adsorption mechanism of cyanide, zeta potential is taken into account. The zeta () potential variation of the activated carbon was estimated considering the pH of solution and this variation is given in Fig. 6. The zeta potential of FeAC increase in the negative direction with increasing pH and isoelectrical points (IEP) is approximately 7 for FeAC. FeAC has positive charge until the pH of 7. HCN and CN present in the aqueous solution at the pH values in the range of 68. It can be said that electrostatic attraction may take place between cyanide species and FeAC due to different charge. As the pH of the solution increases, the surface of the activated carbon has negative charge due to the successive deprotonation of positive charged groups on the surface of activated carbon, and negative charge density on the surface increases. Therefore, electrostatic

repulsion between the negatively charged sites of FeAC and cyanide occurred. Depending on the incompatible surface interactions, the adsorption of the cyanide on FeAC decreased with increasing the pH of the solution. On the other hand, the adsorption of cyanide on CAC-1, CAC-2 and LAC showed the same trend and rose by increasing the pH of the solution. The pKa of HCN is 9.0 and this shows that HCN is completely dissociated to CN at a solution pH of 10 [33]. Fig. 6 shows that the CAC and LAC particle surfaces are negatively charged for a pH over 2.8 and 4 (pHzpc), respectively. Despite the same charge of the CAC and LAC particles and the dominant specify of cyanide (CN ) in the solution, maximum cyanide retention was obtained at pH value over 10. It proves that adsorption mechanism not only depends on the surface charge of adsorbate and adsorbent. As known that physical, 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]. In the literature, adsorption of cyanide ion at pH values over than 10 is explained with the properties of chemical ion exchange mechanism and physical adsorption. Dash et al. [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]. 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. In addition, Garg et al. [38] mentioned that maximum cyanide adsorption at pH 11 related with complexation of CN with functional groups, and physical adsorption due to the precipitations. 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 911 [7,8,22,30,39,40]. With respect to the above-mentioned information and also due to the pH values of 1011 of gold cyanide disposals, in the present study, the adsorption isotherm parameters and kinetic data were determined at two different pH ranges (77.5 and 1010.5).

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

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

Contact Time (h)

Contact Time (h)

Fig. 7. Effect of cyanide concentration on the adsorption of the activated carbons at pH 77.5.

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T. Depci / Chemical Engineering Journal 181182 (2012) 467478

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

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

20 40 60 Contact Time (h)

80

20 40 60 Contact Time (h)

80

Fig. 8. Effect of cyanide concentration on the adsorption of the activated carbons at pH 1010.5.

3.3. Effect of initial cyanide concentration The effect of cyanide concentration onto adsorbents (CAC-1, CAC-2, LAC and FeAC) was investigated at two different pH ranges of 77.5 and 1010.5 and their plots are illustrated in Figs. 7 and 8, respectively. Figs. 7 and 8 indicate that 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 for all cases. This may indicate that the adsorption is limited by number of the available active sites which are not sufcient for the high initial concentration of the cyanide. The obtained results are consistent with the available scientic data [8,22,36]. Besides, it can be seen that the shape of the curves of all adsorbents keep almost constant, showing an activated carbon type-independent character. Literature survey shows that the cyanide adsorption capacities of activated carbons increases with the impregnation of them with silver, copper, and nickel at high pH level [68]. On the contrary of the literature, it was found that iron impregnation did not enhance the percentage of the removal of cyanide from aqueous solution at pH values of 1010.5 (in Fig. 8). On the other hand, by comparing the percentage of cyanide removal using FeAC depending on the initial pH of solution (Figs. 7 and 8), it was dened that the removal of cyanide increased with decreasing the pH values from 10 to 7 for FeAC (Fig. 8). The results indicate that iron impregnation enhanced the removal of cyanide depending on the pH of the solution. This result also supports the previous conclusion which was obtained the effect of pH section. However, according to Fig. 8b at normal pH conditions (77.5) the adsorption of cyanide onto FeAC is only 3050% higher than on LAC. As mentioned before, the obtained magnetic activated carbon (FeAC) shows super-paramagnetic behaviors at room temperature, so it can be removed easily by a magnetic separator, as opposed to the traditional screening technology. Although iron impregnation does not signicantly affect the removal of cyanide, considering the

magnetic property of FeAC, it can be said that it is a viable candidate for the removal of cyanide from water and wastewater. 3.4. Adsorption isotherms The adsorption isotherm data were tted with well-known two-parameter models, Langmuir [41] and Freundlich [42] as well as three-parameter isotherm model, RedlichPeterson [43]. Literature data show that these isotherm models have been found applicable to cyanide sorption processes [6,8,30], so they were chosen in the present study. To nd out the best tting kinetic and isotherm models, average relative error (ARE) and nonlinear Chi-square test (X2 ) for kinetic models were applied in addition to correlation coefcient (R2 ). The isotherm expressions are given below: Langmuir, qe = Q0 bCe 1 + bCe (4) (5) ARP Ce
g

Freundlich, qe = kf (Ce )1/n RedlichPeterson, qe = 1 + BRP Ce

(6)

where Ce is the equilibrium cyanide concentration in the liquid phase (mg/L), qe is the adsorption capacity (mg/g), b (L/mg) and Q0 (mg/g) are Langmuir isotherm constants, where Q0 signies the theoretical monolayer capacity, kf (L/g) is the Freundlich constant and 1/n (dimensionless) is the heterogeneity factor, ARP (L/g), BRP (L/mg)g and g are the RedlichPeterson isotherm constants. 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 Microsofts spreadsheet, Microsoft Excel. The calculated parameters for two different pH range (77.5 and 1010.5), the correlation coefcient and error functions were summarized in Tables 3 and 4, respectively.

T. Depci / Chemical Engineering Journal 181182 (2012) 467478 Table 3 Isotherms parameters for the sorption of cyanide on the activated carbons (cyanide concentration of 100 mg/L, pH values in the range of 77.5). Linearized form CAC-1 Langmuir isotherm Q0 (mg/g) b 103 (L/mg) R2 ARE X2 Freundlich isotherm kf (L/g) n R2 ARE X2 RedlichPeterson isotherm ARP (L/g) BRP (L/mg)g g R2 ARE X2 61.23 8.32 0.99 2.16 0.24 1.77 1.73 0.96 5.45 0.91 0.62 0.013 0.91 0.99 2.94 0.5 CAC-2 60.6 7.92 0.99 2.33 0.34 1.68 1.72 0.96 4.23 0.78 0.52 0.002 1.21 0.99 2.92 0.42 LAC 59.17 8.32 0.99 2.40 0.28 1.82 1.76 0.95 5.73 0.8 0.52 0.002 1.32 0.99 3.19 0.52 FeAC 66.24 5.49 0.99 2.05 0.27 5.75 2.41 0.92 3.23 0.68 2.34 0.923 0.52 0.99 2.12 0.42 Non-linearized form CAC-1 62.12 8.11 0.99 2.37 0.21 2.43 1.92 0.95 6.72 0.94 0.57 0.007 1 0.99 3.12 0.21 CAC-2 61.35 7.24 0.99 1.92 0.12 2.04 1.85 0.97 4.72 0.81 0.48 0.006 1 0.99 1.85 0.12 LAC 60.18 7.93 0.99 2.32 0.13 2.13 1.92 0.97 5.12 0.7 0.46 0.006 1 0.99 2.92 0.11 FeAC

473

67.82 5.33 0.99 1.38 0.17 6.12 2.73 0.95 4.12 0.39 1.71 0.032 0.99 0.99 1.41 0.07

From Tables 3 and 4, it can be inferred that, 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, the deviation very large for both cases. Adsorption of cyanide on all the activated carbons at two different pH ranges is quite well consistent with the Langmuir and RedlichPeterson models. Especially, Langmuir model has lowest level of the values of error function. 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. Therefore, only the plots of linear and non-linear Langmuir isotherms for both pH values are depicted in Fig. 9. Since Langmuir model is one of the best tting isotherm models which is also applied in this study, RL named as dimensionless separation factor was calculated to determine whether the adsorption system is favorable or not [44]. It is dened by the following equation: RL = 1 1 + bCo (7)

where RL is a dimensionless separation factor, Co is the initial dye concentration and b is Langmuir constant. The feasibility of the reactions are explained using the value of RL (RL > 1 unfavorable, RL = 1 linear, 0 <RL < 1 favorable, RL = 0 irreversible). The values of RL were found in the range of 0.070.8, indicating that the adsorption is favorable. The results of RedlichPeterson isotherm also support the suitability of Langmuir model. This model is related with three parameters empirical equation and is a hybrid isotherm featuring both Langmuir and Freundlich isotherms [45]. It can be used to understand adsorption mechanism of homogeneous or heterogeneous systems due to its versatility [46]. In this model, g is the exponent varying between 0 and 1. Tables 3 and 4 show that g values are close to one, and especially they calculated as one using non-linear form. This indicates that Langmuir condition is ideal one for the adsorption mechanism [47]. Based on the adsorption capacities (Langmuir (Q0 ) and Freundlich (kf ) constants) of the activated carbons at both pH range (in Tables 3 and 4), the adsorption capacities of CAC-1, CAC-2 and

Table 4 Isotherms parameters for the sorption of cyanide on the activated carbons (cyanide concentration of 100 mg/L, pH values in the range of 1010.5). Linearized form CAC-1 Langmuir isotherm Q0 (mg/g) b 103 (L/mg) R2 ARE X2 Freundlich isotherm kf (L/g) n R2 ARE X2 RedlichPeterson isotherm ARP (L/g) BRP (L/mg)g g R2 ARE X2 64.93 8.13 0.99 2.45 0.29 1.81 1.74 0.97 7.25 0.88 2.17 0.79 0.45 0.95 5.45 0.67 CAC-2 63.29 9.4 0.99 2.68 0.31 2.12 1.78 0.96 6.42 0.97 1.98 0.47 0.52 0.97 4.18 0.52 LAC 64.10 9.37 0.99 2.44 0.38 2.01 1.74 0.95 8.63 0.98 1.95 0.81 0.51 0.96 5.67 0.74 FeAC 68.02 8.16 0.98 3.32 0.8 1.82 1.67 0.96 6.88 0.82 2.18 0.57 0.49 0.97 4.86 0.72 Non-linearized form CAC-1 64.34 8.23 0.99 2.23 0.26 2.49 1.95 0.96 7.13 0.81 0.51 0.006 1 0.99 3.25 0.25 CAC-2 63.22 9.3 0.99 2.41 0.07 2.95 2.12 0.96 5.51 0.75 1.48 0.14 1 0.99 3.93 0.41 LAC 64.20 9.2 0.98 2.34 0.32 2.53 1.95 0.95 6.42 0.81 0.51 0.008 1 0.99 3.45 0.27 FeAC 68.35 8.21 0.99 3.28 0.71 2.96 1.86 0.96 6.13 0.7 0.52 0.009 1 0.99 3.16 0.21

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Linear isotherm plots (pH 7 - 7.5)

8 6 60 45 30 15 0 0 100 200
Ce (mg/L)

Non-linear isotherm plots (pH 7 - 7.5)

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

100

200
Ce (mg/L)

300

400

Linear isotherm plots (pH 10 - 10.5)

7

Non-linear isotherm plots (pH 10 - 10.5)

45

Ce /qe (mg/g)

qe (mg/g)

5
CAC-1

30
CAC-1 CAC-2 LAC FeAC Langmuir non-linear

CAC-2 LAC FeAC

15

1 0 100 200 300

400

0 0 100 200 300 400

Ce (mg/L)

Ce (mg/L)

Fig. 9. 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).

LAC are very close with each other at the same pH range and their capacities increases by increasing the pH of the solution. 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. On the other hand, the adsorption capacity of FeAC shows different trend. FeAC has the highest adsorption capacity at pH 77.5 and its capacity decreases with increasing the pH of the solution. It indicates that the adsorption capacities of the activated carbons for cyanide, especially FeAC, have a strict pH-dependent character. The result conrms the previous results which were obtained in this study. Moreover, the ultimate carbon-adsorption capacities of CAC-1, 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. It was found that LAC and FeAC exhibited nearly same cyanide removal efciency with the commercial activated carbons. In order to compare the adsorption capacities of LAC and FeAC, the adsorption capacities of some adsorbents for cyanide adsorption are given in Table 5. It seems that LAC and FeAC have also greater removal efciency than lots of the adsorbents which are given in Table 5. Therefore, it seems that LAC and FeAC are attractive candidates for removal of cyanide from aqueous solution.

3.5. Adsorption kinetics The pseudo-rst 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 (77.5 and 1010.5). The accuracy and applicability of the kinetics model were checked using ARE and X2 error function model. In addition, intraparticle diffusion model [50] was also applied for all conditions. The kinetic equations are given below: Pseudo-rst order, qt = qe [1 exp(k1 t )] qt = k2 qe 2 t 1 + k2 qe t (8) (9) (10)

Pseudo-second order, Intraparticle diffusion,

qt = kint t 1/2 + C

Table 5 Comparison of the adsorption capacities of cyanide onto some adsorbents. Adsorbents Ag-imregnated AC Ni-impregnated AC Cu-impregnated AC Ativated carbon Modied zeolite with iron Pistachio hull wastes Pyrophylite Adsorption capacity (mg/g) 45.7 15.4 19.7 47.62 6.21 156.2 72.4 pH 11 >11 10.511 1011 77.5 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), respectively, k1 is the rate constant of the pseudo-rst-order adsorption (min1 ), k2 is the rate constant of the pseudo-second-order adsorption (g/mg min), C is the intercept and kint is the intraparticle diffusion rate constant (mg/g min1/2 ). 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 tted kinetic models for two pH ranges, 77.5 and 1010.5, are given in Tables 6 and 7, respectively. It can be concluded that the adsorption of cyanide onto the activated carbons did not follow the pseudo rst order model. The pseudo second order kinetic model with high correlation coefcient, low ARE and X2 describes the system much better than the pseudo rst order kinetic models. Similar results were found by Deveci et al. [8] and Behnamfard and Salarirad [22]. 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, at room temperature (25 C) are given in Fig. 10. From Fig. 10, it can be concluded that pseudo-second order kinetic model with linear and non

T. Depci / Chemical Engineering Journal 181182 (2012) 467478 Table 6 Kinetic parameters for the effect of the activated carbon types on the adsorption of cyanide (pH values: 77.5; cyanide concentration: 100 mg/L). Pseudo-rst-order CAC-1 Linearized form qe (cal) (mg/g) k1 (min1 ) R2 ARE X2 13.08 0.072 0.97 26.67 13.16 CAC-2 20.32 0.14 0.94 29.95 11.03 LAC 12.16 0.10 0.98 24.84 12.55 FeAC 20.37 0.13 0.95 23.22 19.56 CAC-1 CAC-2 Non-linearized form 16.45 0.08 0.995 4.48 0.28 17.32 0.11 0.99 5.85 0.58 LAC 14.44 0.14 0.99 4.49 0.34

475

FeAC 24.70 0.15 0.99 6.29 2.32

Pseudo-second-order CAC-1 Linearized form qe (cal) (mg/g) k2 (g/mg min) h (mg/g min) R2 ARE X2 19.80 0.00 1.74 0.99 5.04 0.46 CAC-2 19.19 0.01 2.86 0.99 7.94 1.23 LAC 16.10 0.01 3.03 1.00 6.57 0.47 FeAC 26.53 0.01 6.56 1.00 8.66 2.10 CAC-1 CAC-2 Non-linearized form 19.93 0.004 1.75 0.99 3.2 0.25 20.10 0.007 2.63 0.98 4.82 1.03 LAC 16.32 0.011 3.06 1.00 4.34 0.25 FeAC 27.71 0.007 5.66 0.99 5.23 1.89

Table 7 Kinetic parameters for the effect of the activated carbon types on the adsorption of cyanide (pH values: 1010.5; cyanide concentration: 100 mg/L). Pseudo-rst-order CAC-1 Linearized form qe (cal) (mg/g) k1 (min1 ) R2 ARE X2 14.87 0.07 0.98 22.10 8.52 CAC-2 19.31 0.14 0.97 12.39 2.61 LAC 19.08 0.14 0.97 7.18 1.38 FeAC 18.36 0.10 0.98 7.63 1.02 CAC-1 CAC-2 Non-linearized form 16.86 0.09 0.99 4.78 0.42 18.20 0.12 0.99 6.87 1.26 LAC 18.46 0.12 0.99 6.39 0.83 FeAC 16.94 0.11 0.99 4.72 0.48

Pseudo-second-order CAC-1 Linearized form qe (cal) (mg/g) k2 (g/mg min) h (mg/g min) R2 ARE X2 19.72 0.01 2.09 1.00 4.93 0.39 CAC-2 19.96 0.01 3.51 0.99 7.58 1.11 LAC 18.20 0.01 3.63 1.00 9.48 2.87 FeAC 18.90 0.01 2.72 0.99 9.02 1.37 CAC-1 CAC-2 Non-linearized form 20.06 0.005 2.05 1.00 4.96 0.36 20.85 0.007 3.09 0.99 7.00 0.97 LAC 21.05 0.007 3.32 1.00 6.02 0.94 FeAC 19.68 0.007 2.59 0.99 8.39 1.19

linear forms showing good correlation between experimental and predicted values. In the present study, to understand the adsorption mechanism of cyanide on the activated carbons, intraparticle diffusion model was also applied for all conditions. 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 (77.5 and 1010.5) are given in Tables 8 and 9,

respectively. Their plots are shown in Figs. 11 and 12 which indicate that the adsorption mechanism of cyanide onto the activated carbons for all conditions follows two steps. The rst one covering the time interval between 1 and 21 h (more than 21 h for high cyanide concentration), which has a very sharp, is attributed to the diffusion of cyanide through the solution lm to the external surface of the activated carbons (mass transfer). 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: 77.5). 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 1.48 4.71 0.76 200 3.69 2.65 0.84 300 5.19 2.46 0.86 400 5.19 5.61 0.86 FeAC 100 2.35 9.17 0.70 200 3.86 15.42 0.82 300 4.43 21.19 0.79 400 5.42 14.13 0.89 100 2.05 1.99 0.88 200 3.72 2.79 0.85 300 5.1 2.8 0.86 400 5.7 3.9 0.88 CAC-2 100 1.92 4.06 0.77 200 3.66 4.54 0.85 300 5.2 4.36 0.86 400 5.17 7.52 0.85

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T. Depci / Chemical Engineering Journal 181182 (2012) 467478

6.4

Linear forms (pH 7 - 7.5)

CAC-1

30

Non-linear forms (pH 7 - 7.5)

4.8

CAC-2

t/q t

3.2

FeAC

qt (mg/g)

LAC

20

CAC-1

1.6

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 - 10.5)

CAC-1 CAC-2 LAC FeAC

40

60

80

t (hours)
20

4.8

Non-linear form (ph 10 - 10.5)

q t (mg/g)

3.2

t/q t

10

CAC-1 CAC-2 LAC FeAC pseudo second order non-linear

1.6

0 0 20 40 60 80

0 0 20 40 60 80

t (hours)

t (hours)

Fig. 10. The pseudo-second order adsorption kinetics for cyanide adsorption onto the activated carbons at two pH values at cyanide concentration of 100 mg/L.

the liquid contained in pores of adsorbent particles and along the pores walls (intraparticle diffusion) [51]. Besides, the adsorption kinetics reaches the equilibrium at a different time depending on the initial cyanide concentration. Fast equilibrium obtained at low initial cyanide concentration. This observation is supported with the data published by Behnamfard and Salarirad [22] and Dash et al. [36] who explained that cyanide ions at low cyanide concentration could be adsorbed by more readily available sorption sites. At high cyanide concentration, diffusion of cyanide through the solution

lm to the external surface of the activated carbons are very fast and then decreases depending on the equilibrium time. 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. It means that the pores show resistance against the diffusion of cyanide ion into inner adsorption sites. Briey it can be concluded that the intraparticle diffusion step controls the cyanide adsorption on CAC-1, CAC-2, LAC and FeAC for all conditions. Moreover, 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

10

10

t
60
100 ppm

1/2

(h

1/2

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

6
1/2

10

10

(h

1/2

1/2

(h

1/2

Fig. 11. Plots of intraparticle diffusion for adsorption of cyanide onto the activated carbons at various initial concentration of cyanide (pH values: 77.5).

T. Depci / Chemical Engineering Journal 181182 (2012) 467478 Table 9 Intraparticle diffusion parameters for the effect of the activated carbon types and cyanide concentration on adsorption (pH values: 1010.5). 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 1.94 5.32 0.76 200 3.69 5.99 0.84 300 5.19 5.80 0.86 400 5.19 8.94 0.86 FeAC 100 1.90 3.93 0.77 200 3.64 4.56 0.84 300 5.09 5.33 0.85 100 2.02 2.74 0.88 200 3.73 4.13 0.85 300 5.17 4.47 0.87 400 5.48 5.57 0.87 CAC-2 100 1.93 5.04 0.78 200 3.68 5.54 0.82 300 5.19 5.37 0.86

477

400 5.19 8.52 0.86

400 5.19 8.23 0.86

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

10

10

t
60
100 ppm

1/2

(h

1/2

)
60
100 ppm

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

10

10

1/2

(h

1/2

1/2

(h

1/2

Fig. 12. Plots of intraparticle diffusion for adsorption of cyanide onto the activated carbons at various initial concentration of cyanide (pH values: 1010.5).

[52] suggested that the boundary layer thicknesses, C should be considered to give a better decision. Tables 8 and 9 show that C values are positive indicating that cyanide adsorption controls with not only the intraparticle diffusion but also the lm diffusion. Besides C values increase with increasing cyanide concentration for all activated carbons. It means that the lm diffusion is involved in controlling cyanide adsorption onto the activated carbons at higher cyanide concentrations [52]. 4. Conclusion In this study, a plain activated carbon and iron impregnated activated carbon were prepared from Glbas lignite. BET surface area of LAC is determined as 921 m2 /g. FeAC has also high surface area of 667 m2 /g with 19 wt.% Fe3 O4 coated and perfect magnetic separation performance. Adsorption of cyanide on the activated carbons is quite well consistent with the Langmuir models. The ultimate carboncyanide adsorption capacities of the activated carbons are virtually independent of particle size, pore structure and the activated carbon types. The maximum monolayer adsorption capacities of LAC and FeAC are 60.18 mg/g and 67.82 mg/g

at pH values of 77.5 and 64.10 mg/g and 68.02 mg/g at pH values of 1010.5, respectively. They are much higher than some of the maximum values reported in the literature. 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. Solution pH plays a major role in cyanide adsorption onto FeAC and maximum retention was obtained at pH 77.5 due to the electrostatic attraction and exchange mechanism. The experimental results best tted to the second-order kinetic equation. Intraparticle diffusion model shows that the removal rate is controlled by not only intraparticle diffusion but also the lm diffusion. Finally, it is possible to afrm that LAC and FeAC are promising adsorbents, which were obtained from natural resource, for the removal of cyanide from aqueous solution. Acknowledgements Thanks are due to Askale Van Cement Factory for their contributions in performing experiments. Also special thanks to

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Dr. Yunus Onal for helping to carry out some extra experiments in the laboratory of Chemical Engineering in Inonu University after the earthquake in Van. References
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