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Chemical Engineering 2 (2014) 2280 – 2288 Contents lists available at ScienceDirect Journal of

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/je c e

journal homepage: www.elsevier.com/locate/je c e Comparative cadmium adsorption study on activated carbon

Comparative cadmium adsorption study on activated carbon prepared from aguaje ( Mauritia exuosa ) and olive fruit stones ( Olea europaea L.)

Daniel Obregón-Valencia a , María del Rosario Sun-Kou b , *

a Instituto de Corrosión y Protección, Ponticia Universidad Católica del Perú, Av. Universitaria 1801, Lima 32, Peru b Sección Química, Departamento de Ciencias, Ponticia Universidad Católica del Perú, Av. Universitaria 1801, Lima 32, Peru

Católica del Perú, Av. Universitaria 1801, Lima 32, Peru A R T I C L E

A R T I C L E

I N F O

Article history:

Received 5 June 2014 Accepted 5 October 2014

Keywords:

Adsorption Cadmium Aguaje stones Activated carbons Olive stones Adsorption of heavy metals

A B S T R A C T

This study assesses the capacity of activated carbons, prepared from Mauritia exuosa (AG series) and Olea europaea L. (OL series) fruit stones, to adsorb cadmium ions. These carbons were activated chemically through phosphoric acid solution, using impregnation ratios of 0.75, 1.0, and 1 : 5g H 3 PO 4 = g precursor . The impregnated precursor material was subsequently activated at 400, 500 and 600 C. The physicochemical characteristics of precursors and activated carbons were analyzed by thermogravimetric analysis (TGA), nitrogen adsorption desorption isotherm ( S BET ), Boehm s titration, and scanning electron microscopy (SEM). Kinetic assays were evaluated from solutions containing 10 ppm of cadmium (Cd(II)). Within each series, the activated carbons with higher adsorption capacity turned out to be AG0.75_600 and OL1_600 with 8.14 and 9.01 mg g 1 , respectively at pH 2. Among 26.33 and 24.83 mg g 1 , respectively at pH 5. Both activated carbons were characterized by the highest mesoporous area and acidic surface functional group compared to other activated carbons (of each series). The obtained isotherm correlations t better according to a Langmuir model and this was con rmed with a Redlich Peterson model (with G values close to 1). The adsorption process of cadmium ions took place mostly in adsorption sites of uniform energies. ã 2014 Elsevier Ltd. All rights reserved.

Introduction

Cadmium is one of the most prevailing heavy metals with one of the highest environmental toxicities [1] . Cadmium enters soil, water, and air from mining, industry, and burning coal and household waste. Fish, plants, and animals take up cadmium from the environment [2] . Among the techniques that can currently be applied to remove heavy metals from aqueous solutions, there are chemical precipita- tion, conventional coagulation, reverse osmosis, ion-exchange, ultraltration, and adsorption, among others [3] . In industry, the adsorption process is widely adopted for water purication because of its efciency, versatility, and ease of implementation. Activated carbon (AC) is a carbonaceous material and it is one of the most applied adsorption materials due to its high surface area and chemical reactivity [4] . It can be prepared from renewable and low cost sources (precursors) such as lignocellulosic materials which can be obtained from agroindustrial waste (fruit stones and peels) [510]. The main object of this study is to analyze and compare theAC adsorption capacity prepared from two different precursors: aguaje

* Corresponding author. Tel.: +51 1 626 2000; fax: +51 1 6262853. E-mail address: msun@pucp.edu.pe (M.d.R. Sun-Kou).

2213-3437/ ã 2014 Elsevier Ltd. All rights reserved.

(Mauritia exuosa ) and olive ( Olea europaea L.) fruit stones in order to set the in uence of precursor nature and preparation conditions on the adsorbent properties of the activated carbons.

Materials and methods

Activated carbon preparation

Aguaje and olive fruit stones from the Peruvian provinces of Ucayali and Arequipa were used as precursor materials. These materials were previously washed until all organic residues were eliminated, oven-dried at 80 C and grounded until less than 10 mm particles were obtained. The sample (50 g) was mixed with a particular concentration of phosphoric acid solution (initial concentration H 3 PO 4 85%, Merck) in order to obtain three impregnation ratios of 0.75, 1.0, and 1.5 calculated as gram weight ratio of phosphoric acid per gram of precursor. First, this mixture was vacuum dried and then oven-dried at 85 C for 24 h. The impregnated and dried material was later carbonized in a stainless steel tubular reactor, which was placed in an oven at a heating speed of 10 C min 1 until the set activation temperature was reached. Three different activation temperatures (400 C,

D. Obregón-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 2280 2288

2281

500 C, and 600 C) were considered and these were maintained for 60 min. During the activation process, a 100 cm 3 min 1 nitrogen ow was used through the reactor to create an inert atmosphere and to remove the formed vapor by entrainment. In this study the sample nomenclature assigned is as follows:

AG = aguaje stones and OL = olive stones, follow by the impregna- tion ratio, and the activation temperature in Celsius degree ( C). For example, the sample AG0.75_600 was prepared from aguaje stones, with an acid impregnation ratio of 0 : 75g H 3 PO 4 = g precursor , and an activation temperature of 600 C.

Characterization

Thermogravimetric analyses (TGA) and differential thermal analyses (DTA) of starting materials (precursor material) were performed in a thermogravimetric analyzer (LINSEIS STA-PT model 1600) under an argon ow. For this analysis 25 mg of each material were weighted. They were heated at a rate of 5 C min 1 until 550 C were reached in an argon atmosphere with 4 L h 1 ow. The textural properties were studied by N 2 adsorption measurements at liquid nitrogen temperature using Micromeritics GEMINI VII, model 2390t equipment. Prior to adsorption experi- ments, samples were degassed in vacuum at 250 C for 2 h. The range of relative pressures used was from 0.013 to 0.99. The speci c surface area was calculated according to the BET method. Microporous surface was calculated by the t -plot method. Mesoporous area was evaluated by the difference of the total area and microporous area. The quantitative determination of the acidic surface groups was done according to Boehm s method. About 25 mg of activated carbon was added to 50 mL solutions of NaOH 0.1 N standard and was shaken at room temperature for 24 h. Then, the activated carbon samples were separated by ltration. The quantity of acidic surface group on AC samples was determined by back titration of ltered solutions with HCl 0.1 N standard. The activated carbons were characterized with an electronic microscope of scanning (SEM) Phillips model 505DX. In order to appreciate the morphology with more clarity all samples were re-

covered with a gold lm to provide the sample of electrical conductivity.

Adsorption measurements

Adsorption equilibrium information is the most important to understand an adsorption process. Kinetics tests were conducted at room temperature (20 C) with a cadmium solution with an initial concentration of 10 ppm and pH 2 (which was adjusted using 0.1 N HCl and 0.1 N NaOH). About 15 mg of activated carbon were added to different vials with 20 mL of the aqueous solution and kept under agitation. The contact time in each vial was different (between 5 min and 180 min). The amount of cadmium ions adsorbed increases sharply during the rst 30 min., and it reaches its equilibrium value within 1 h. The activated carbons prepared with an activation temperature of 600 C reach their highest adsorption capacity within each series.

Adsorption isotherms were determined using a series of solutions of cadmium in which the initial concentration was increased from

2 to 80 ppm using the activated carbons prepared with an activation temperature of 600 C. The adsorbentadsorbate time of contact was

4 h in order to ensure stationary conditions. The adsorption capacity

is the amount of cadmium ions adsorbed at equilibrium, q e (mg g 1 ),

and it was calculated according to Eq. (1) :

q e ¼ ð C o C e Þ V

(1)

W

where C o and C e are the respective initial and equilibrium concentration of cadmium ions (mg L 1 ); V is the volume of aqueous phase (L); and W is the weight of the activated carbon (g). The cadmium ion concentration was analyzed using a PerkinElmer model 3110 spectrophotometer with acetylene ame at a wavelength of 228.8 nm.

Results and discussion

TGA and DTA curves for both precursors show four different stages of weight loss ( Fig. 1 ). For both precursors, the rst stage

100 155 307 TGA 100 155 257 333 TGA 380 380 80 80 AGUAJE OLIVE
100
155
307
TGA
100
155
257 333
TGA
380
380
80
80
AGUAJE
OLIVE
60
60
STONE
STONE
40
40
20
20
0
0
0
150
300
450
600
0
150
300
450
600
T (ºC)
T (ºC)
Mass loss (%)
Mass loss (%)
0 155 307 DTA 380 -20 -40 -60 AGUAJE -80 STONE -100 0 150 300
0
155
307
DTA
380
-20
-40
-60
AGUAJE
-80
STONE
-100
0
150
300
450
600
dm/dt

T (ºC)

0 155 257 333 DTA 380 -20 -40 -60 OLIVE -80 STONE -100 0 150
0
155
257 333
DTA
380
-20
-40
-60
OLIVE
-80
STONE
-100
0
150
300
450
600
dm/dt

T (ºC)

Fig. 1. Thermogravimetric analysis and differential thermal analysis of aguaje and olive stones.

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appears by 40 163 C, with a weight loss about of 12% of the initial weight. This stage is associated with the loss of water physisorbed on the precursors. The second stage for the aguaje stones extends by 163 307 C with a weight loss of about 47%, due mainly to hemicelluloses degradation ( Fig. 1 left). The olive stones ( Fig. 1 right) showed consecutive weight losses by 155 257 C and 257 333 C of about 11 and 22%, respectively, attributed to hemicelluloses and lignin degradation. In DTA curves for olive stones, the in exion point at 257 C shows a sharp exothermic peak due to volatile evolution (CO 2 , CH 4 and some hydrocarbon) from biopolymer degradation of hemicelluloses and lignin. These values are signi cantly higher compared to aguaje stones, which indicates that there is a high content of these biopolymers in the o lives stones. The third stage for the aguaje stones shows up by 307 377 C with a weight loss of about 12%. At this stage the cellulose is mainly degraded. The olive stones were degraded at 334 380 C with a weight loss of about 7%. Lignin degradation occurred in a wide temperature range (100 900 C) due to its structure. The last stage is attributed to lignin degradation. The aguaje stones showed a weight loss by 391 570 C of about 13.83% with a remainder weight of 14.36%, and the olive stones showed a weight loss by 380 570 C of about 14% with a remainder weight of 31%. This difference is due to the higher lignin content in olive stones, a fact which agrees with the lignin content of 6.5% for aguaje stone and 19.5% for olive stone, as determined by adapting the analysis method from ASTM D1106-96 (2007) [11] . The thermogravimetric results were compared with Yang et al. [12] who made a thermogravimetric study of the cellulose, hemicelluloses and lignin, and establishing thereby the temperature degradation range for each biopolymer. The results for the surface area, mesoporous distribution, surface acidity, and adsorption capacity are shown in Table 1 [13] . In both series, the surface area decreases as the pyrolysis temperature is increased, due to a thermal contraction effect on the porous structure. The same behavior was observed by others authors [14 16] . This contraction is more evident in the AG series and it affects its micro and mesoporous areas as well. Both series of activated carbons with an activation temperature of 600 C show that while the surface area increases with the impregnation ratio, its mesoporous area decreases. This holds true for both series and especially for the AG series. As for the OL series, an exception is found for sample OL0.75, given that its mesoporous area is lower than that of the rest of the OL series. The increase in surface area is attributed to phosphoric acid decomposition (Eq. (2) ) [14 17] which favors the formation of water and enhances the formation of various gaseous compounds, such as CO 2(g) , CO (g) , H 2(g) (Eqs. (3) and (4) . These compounds are released from the precursor forming the porous structure of the activated carbon [17] .

H 3 PO 4 ! P 2 O 5(S) + 3H 2 O (g) (2)

C (S) + H 2 O (g) ! H 2 (g) + CO (g) (3)

(2)

(3)

(4)

Acidic surface groups were determined by Boehm s method. The increase in activation temperature generated the increase in surface acidity ( Table 1 ); this property is closely related to absorbent adsorbate interactions that take place on the carbon surface. Puziy et al. [18] found that, as the activation temperature is increased, the surface enrichment with oxygen progressively expands to deeper layers of carbon due to the action of phosphoric acid as an oxidizing agent. In both series, the sample with higher impregnation ratio (AG1.5_600 and OL1.5_600) showed a low acidic surface. Thus, although phosphoric acid favors the formation of carbon oxygen bonds, in large quantity the phosphorous compounds avoid the formation of oxygen-containing functional groups on the carbon surface. This behavior was observed in studies on AC prepared from cellulose, hemicelluloses, and lignin [19 21] . For OL series the surface acidity is very similar between OL1_600 and OL0.75_600 decreasing signi cantly in OL1.5_600. Fig. 2 shows the SEM micrographs of the four activated carbons with higher adsorption capacity at a magni cation of 1010X. In AG series, the sample AG0.75_600 ( Fig. 2 top-left) shows pores with an average size of 8 m m on the surface of the activated carbon. Sample AG1_600 ( Fig. 2 top-right) shows pores with an average size of 5 m m. OL series show more compact bers, furthermore, the porous structure is not so developed as in AG series. The sample OL0.75_600 ( Fig. 2 bottom-left) shows pores with an average size of 3.5 m m. Finally, the sample AC1_600 ( Fig. 2 top-right) shows an irregular surface with pore sizes from 2 to 0.5 m m.

CO (g) + H 2 O (g) ! H 2(g) + CO 2(g) (4)

Adsorption capacity

For both series of activated carbons, the capacity for cadmium ion adsorption increases with higher activation temperature, as shown in Table 1. Furthermore, the adsorption capacity decreases with the increase of impregnation ratio. The higher adsorption capacities in samples AG0.75_600 and OL1_600 were associated to their high surface acidity and high mesoporous area ( Table 1 ). Both AC samples with high adsorption capacity (AG0.75_600 and OL1_600) differ in their impregnation ratio. This fact is attributed to differences in their precursor source. The higher lignin content and compact bers in olive stones required a high ratio of impregnation in order to get a high super cial acidity and suitable mesoporous structures in favor of cadmium ion adsorption.

Table 1 Characterization and adsorption capacities of the activated carbon.

Sample

Surface area (m 2 g 1 )

Surface acidity (mmol H + g 1 )

Adsorption capacity (mg g 1 )

Removal ef ciency (%)

Total

Mesoporous

AG1_400

1202

109

1.42

0.60

5

AG1_500

1077

36

1.98

2.92

22

AG1_600

1014

77

2.24

7.28

55

AG0.75_600

906

140

2.43

8.14

61

AG1.5_600

1623

32

1.40

4.11

31

OL1_400

1283

145

1.44

0.68

5

OL1_500

1242

135

1.80

3.03

23

OL1_600

1169

125

2.37

9.01

68

OL0.75_600

800

10

2.36

3.00

23

OL1.5_600

1565

75

0.54

2.66

20

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Chemical Engineering 2 (2014) 2280 – 2288 2283 Fig. 2. SEM micrographs of activated carbons at

Fig. 2. SEM micrographs of activated carbons at a magni cation of 1010X.

On the other hand, while sample OL0.75_600 shows a similar surface acidity as OL1_600, its surface area was not completely developed and its low mesoporous area was unfavorable to the adsorption capacity (3 mg g 1 ).

In accordance with the results, the surface acidity and the surface area developed (high mesoporous structure) were the main important factors in the adsorption capacity of cadmium.

important factors in the adsorption capacity of cadmium. Fig. 3. Effect of contact time on the

Fig. 3. Effect of contact time on the removal of cadmium ion from different AC prepared with an activation temperature of 600 C.

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Table 2 Pseudo rst order, pseudo second order and Elovich parameters.

Sample

Pseudo rst order

 

Pseudo second order

 

Elovich s model

q

e

k

1

r 2

q e (mg g 1 )

k

2

r 2

D q e (%)

(1/ b ) ln ( ab ) (mg g 1 )

1/ b (mg g 1 )

r

2

(mg g 1 )

(min 1 )

(g mg 1 min 1 )

   

AG1_400

0.25

0.03

0.69

0.63

0.20

0.99

11.08

0.09

0.11

0.84

AG1_500

0.52

0.01

0.64

2.88

0.10

0.99

12.91

2.12

0.13

0.64

AG1_600

1.45

0.03

0.78

7.38

0.06

1.00

2.53

4.21

0.19

0.83

AG0.75_600

2.58

0.03

0.91

8.35

0.03

1.00

2.29

3.77

0.97

0.89

AG1.5_600

0.56

0.05

0.80

4.15

0.21

1.00

2.27

3.06

0.24

0.77

OL1_400

0.20

0.02

0.87

0.70

0.36

0.99

3.68

0.32

0.08

0.89

OL1_500

0.82

0.02

0.86

3.04

0.07

0.99

13.85

1.90

0.20

0.84

OL1_600

3.53

0.07

0.98

9.22

0.04

1.00

17.70

5.67

0.75

0.97

OL0.75_600

0.93

0.02

0.94

3.06

0.08

0.99

23.75

1.52

0.31

0.95

OL1.5_600

1.60

0.06

0.84

2.84

0.05

0.99

14.84

0.45

0.51

0.92

Kinetic studies

The adsorption kinetic describes the rate at which Cd(II) is adsorbed onto the activated carbon surface and the time required to reach its equilibrium. The results were assessed with pseudo rst and second order models, and the Elovich equation described by:

Pseudo rst order [22] :

log ð

q

e

q

t

Þ ¼ log ð q Þ

e

k

1

2

: 303

t

(5)

Pseudo second order [23] :

t

1

1

t

t

k 2 q 2

e

q

e

(6)

q

where k 1 (min 1 ) and k 2 (g mg 1 min 1 ) are the rst and second rate constant of adsorption respectively, q e and q t (mg g 1 ) are the amount adsorbed at equilibrium and the amount adsorbed at time t . A linear plot of log( q e q t ) vs. t and t / q t vs. t is used to calculated k 1 and 1/ q e (slops) and log ( q e ) and 1/ kq e 2 (intercepts), respectively. Elovich s model [24] :

¼

þ

q t ¼

1

b

ln ð ab Þ þ 1 b ln ð t Þ

(7)

where a is considered the initial adsorption rate (mg g 1 min 1 ) and b is related to the area of surface coverage and activation energy for chemisorptions (g mg 1 ). A linear plot of q t vs. ln ( t ) is used to calculated 1/ b (slope) and (1/ b )ln ( ab ) (intercept). The 1/ b values are related to the vacancy sites available on the AC surface and (1/ b )ln ( ab ) values are related to the adsorption amount at zero time. All kinetics curves of activated carbon with an activation temperature of 600 C are shown in Fig. 3 . The equilibrium state was reached within the rst hour. The kinetic model parameters

Table 3 Comparison of intraparticle diffusion constants from activated carbon.

are shown in Table 2 . The kinetic curves tted better with pseudo second order model with r 2 values as 0.99 which means that adsorption occurred by two mechanisms: physical and chemical absorption over the activated carbon surface. A similar behavior was established by other authors [2527]. The rate constant, k 2 , is lower in the AC with higher adsorption capacity. It can be established that if the diffusion rate is higher in other AC, it does determine the adsorption capacity. Furthermore, the Elovich parameters show that adsorption capacity is proportional to the available areas according to 1/b (mg g 1 ) values.

Adsorption mechanism

The intraparticle diffusion model was also evaluated to identify the mechanism of adsorption based on Weber and Morris s theory [28] . They established that the adsorption mechanism depends on the physicochemical characteristics of the adsorbents as well as on the mass transport or diffusion. The intraparticle diffusion coef cient, k diff , is given by:

(8)

where q t (mg g 1 ) is the adsorption capacity at time t (min), k diff (mg g 1 min 0.5 ) is the intraparticle diffusion constant and C (mg g 1 ) is related to the thickness of boundary layer. The intraparticle parameters are shown in Table 3 . The intraparticle diffusion constant values decrease from the rst stage, or external surface adsorption, to the second stage where intraparticle diffusion is the limiting rate. Comparing the parameters on the second stage, in both series the higher values were found in AG0.75_600, AG1_600 and OL1_600. None linear portion of second and third stage are extrapolated through the origin, this indicates that particle diffusion is involved but is not the only limiting rate mechanism ( Fig. 4 ). In brief, kinetic curves tted in pseudo second order model with major in uence of intraparticle diffusion, which leads to establish

q t ¼ k diff t 0 :5 þ C

Sample

Intraparticle diffusion model

 

k

diff1

k

diff2

k

diff3

C 1

C 2

C 3

r 1 2

r 2 2

r 3 2

(mg g 1 min 0.5 )

(mg g 1 min 0.5 )

(mg g 1 min 0.5 )

 

AG1_400

0.09

0.07

0.02

0

0.11

0.41

1.00

0.69

0.71

AG1_500

1.05

0.04

0.07

0

2.29

2.04

1.00

0.41

0.74

AG1_600

2.15

0.51

0.07

0

4.11

6.52

1.00

0.78

0.99

AG0.75_600

2.14

0.61

0.15

0

3.95

6.52

1.00

0.77

0.91

AG1.5_600

1.43

0.17

0.02

0

3.04

3.94

1.00

0.68

0.65

OL1_400

0.18

0.05

0.01

0

0.35

0.52

1.00

0.75

0.96

OL1_500

1.03

0.06

 

0.11

0

2.18

1.82

1.00

0.98

0.94

OL1_600

3.06

0.44

0.07

0

5.90

8.27

1.00

1.00

0.67

OL0.75_600

0.85

0.17

0.08

0

1.67

2.16

1.00

0.80

1.00

OL1.5_600

0.49

0.33

0.04

0

0.48

2.26

1.00

0.91

0.61

D. Obregón-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 2280 2288

2285

12 12 AG1_600 AG0.75_600 OL1_600 OL0.75_600 AG1_500 AG1.5_600 OL1_500 OL1.5_600 AG1_400 OL1_400 9 9
12
12
AG1_600
AG0.75_600
OL1_600
OL0.75_600
AG1_500
AG1.5_600
OL1_500
OL1.5_600
AG1_400
OL1_400
9
9
k
k
k
diff1
diff2
diff3
k diff1
k diff2
k diff3
6
6
3
3
0
0
0
2
4
6
8
10
12
0
2
4
6
8
10
12
t 1/2 (min 1/2 )
t 1/2 (min 1/2 )
q t (mg g -1 )
q t (mg g -1 )

Fig. 4. Intraparticle diffusion model plot for the adsorption of cadmium ion from different activated carbons.

that ion cadmium adsorption is governed by two types of interactions, physical and chemical, over the activated carbon surface.

Adsorption isotherms

An adsorption isotherm curve describes the phenomenon governing the retention or mobility of a substance from the aqueous solution to a solid-phase at a constant temperature (20 C) and pH 2. The experimental values are related to the following equilibrium isotherm models: Langmuir, Freundlich, Redlich Peterson, Dubinin Radushkevich and Temkin [29] . Langmuir isotherm model can be represented as:

C

(9)

q

e

e

¼

1

c

e

K L q max

q

max

þ

Freundlich isotherm model can be represented as:

1

log q e ¼ log K F þ n log C e

(10)

where q e (mg g 1 ) is the adsorption capacity at equilibrium and C e (mg L 1 ) is the solute concentration in the solution at equilibrium. The K L (L mg 1 ) constant is related to the adsorption heat and the K F (mg 1 1/ n L 1/ n g 1 ) constant is a parameter related to the adsorption capacity. The maximum capacity value is represented by q max (mg g 1 ) and 1/ n value (dimensionless) represents the adsorption intensity.

The Redlich Peterson isotherm [30] is an empirical isotherm. It combines elements from both the Langmuir and Freundlich equations and the mechanism of adsorption is a hybrid. Therefore it can be applied either to homogeneous or heterogeneous systems. The linearized equation is expressed as:

ln

A RP C e

e

q

1 ¼ G ln ð C e Þþ ln ð B RP Þ

(11)

where q e (mg g 1 ) is the adsorption capacity at equilibrium, C e (mg L 1 ) is the solute concentration present in the solution at equilibrium; A RP , B RP and G (heterogeneity grade) are Redlich Peterson parameters. In the limit, it approaches Freundlich isotherms model at high concentration (as G values tend to 0) and is in accordance with the low concentration limit of the ideal Langmuir condition (as G values are all close to 1). Dubinin Radushkevich (D R) isotherm assumes that there is a surface area in which the adsorption energy is homogeneous. The D R isotherm is expressed as:

ln ð q e Þ ¼ ln ð q s Þ K ad e 2

where e = RTln [1 + 1/ C e ], q s is the theoretical isotherm saturation capacity (mg g 1 ), K ad is related to the mean free energy of sorption per mole of the adsorbate when it is transferred to the surface of the solid from the solution and this energy can be computed using the following relationship:

(12)

1

E ¼ p ffiffiffiffiffiffiffiffiffiffiffi 2 K ad

(13)

14 OL1_600 12 10 8 OL0.75_600 6 OL1.5_600 4 2 0 20 40 60 80
14
OL1_600
12
10
8
OL0.75_600
6
OL1.5_600
4
2
0
20
40
60
80
-1
C (mg L )
e
q e (mg g -1 )
q e (mg g -1 )
14 AG0.75_600 12 10 8 AG1_600 6 AG1.5_600 4 2 0 20 40 60 80
14
AG0.75_600
12
10
8
AG1_600
6
AG1.5_600
4
2
0
20
40
60
80
-1
C (mg L )
e

Fig. 5. Adsorption isotherms of cadmium ion from different activated carbons prepared with an activation temperature of 600 C.

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D. Obregón-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 2280 2288

Table 4 Comparison of Frendlich, Langmuir, Redlich Peterson, Dubinin Radushkevich, and Temkin model adsorption parameters at pH 2.

Model

Sample

AG0.75_600

AG1_600

AG1.5_600

OL0.75_600

OL1_600

OL1.5_600

Freundlich K F (mg g 1 ) 1/ n r 2 D q e (%)

6.08

3.83

1.90

1.70

5.78

2.29

0.18

0.23

0.32

0.30

0.20

0.22

0.81

0.80

0.88

0.98

0.76

0.92

1.52

5.92

2.94

158.24

17.03

3.69

Langmuir q max (mg g 1 ) K L (L mg 1 ) r 2 D q e (%)

11.87

9.47

6.76

6.87

11.86

6.57

0.74

0.48

0.23

0.14

0.83

0.11

1.00

0.99

1.00

0.99

0.99

0.97

0.03

3.56

0.76

3.87

10.40

1.39

Redlich Peterson B RP (L mg 1 ) G G r 2 D q e (%)

0.77

0.98

0.98

0.43

2.34

0.25

0.99

0.97

0.95

0.96

0.98

0.97

1.00

0.99

0.99

0.99

1.00

0.99

0.03

0.72

0.39

1.08

5.36

0.62

Dubinin Radushkevich

m (mg g 1 )

Q

11.1

8.1

5.2

4.7

10.0

5.1

K ad

0.29

0.15

0.52

0.53

0.05

3.62

E

(kJ mol 1 )

1.32

1.80

0.98

0.97

3.06

0.37

r 2 D q e (%)

0.96

0.95

0.90

0.80

0.96

0.61

0.03

0.72

0.39

1.08

5.36

0.62

Temkin

A (L g 1 )

69.79

31.73

4.56

3.54

142.84

4.10

B (kJ mol 1 )

1.67

1.98

2.12

2.32

1.83

2.41

r 2 D q e (%)

0.87

0.93

0.98

0.97

0.90

0.88

1.13

4.39

1.07

0.50

5.98

0.39

The Temkin isotherm assumes that the decrease in the heat of adsorption is linear rather than logarithmic, as implied in the Freundlich equation. It is expressed as:

q e ¼ RT

(14)

b

ð ln A T Þ þ RT ð ln C e Þ

b

where constant RT/ b is related to the heat of adsorption, R the universal gas constant (J mol 1 K 1 ), T the temperature (K), b the variation of adsorption energy (J mol 1 ) and A T is the equilibrium binding constant (L mg 1 ) corresponding to the maximum binding energy. The isotherms curves are shown in Fig. 5 . All activated carbons, except for AG1_600 and OL1_600, are concave type and are similar to curve L type according to Giles s classi cation [31] , meanwhile, AG1_600 and OL1_600 are similar to H type curve. This type of curve represents a strong adsorption of the adsorbate which is re ected in the high initial slope. In all cases, except for AG0.75_600, there is a progressive increase of adsorption capacity as the equilibrium concentration increases.

The correlationof the experimental valueswith themathematical isotherm models are shown in Table 4 . The isotherm constants for RedlichPeterson were evaluated using a trial-and-error optimiza- tion method to calculate the isotherm constants through maximiza- tion of the coef cient of determination ( r 2 ). Both activated carbon series (AG and OL) isotherm curves t the Langmuir and Redlich Peterson isotherm models ( r 2 0.99 for all the tested samples. The normalized standard deviation values were calculated by [32] :

D q e ð % Þ ¼ 100 X

s

ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

½ð q e ð exp Þ q e ð pred Þ Þ = q e ð pred Þ 2

N

(15)

where q e(exp) is the experimental q e and q e(pred) is the correspond- ing predicted q e according to the equation under study with best tted parameters, N is the number of measurements.

The G value close to 1 in Redlich Peterson model con rms that the adsorption process corresponds to a Langmuir model. The Langmuir isotherm model shows that the monolayer adsorption value ( q max ) decreases with high impregnation rates. In AG series, these values decrease from 11.87 to 6.76 mg g 1 . In OL series, the maximum adsorption capacity is obtained for OL1_600 and the least for OL1.5_600 with 11.86 and 6.57 mg g 1 , respectively. Furthermore, the adsorption constant, K L , is higher in the activated carbons with higher adsorption capacities in both series; this means that adsorption process requires a high energy to retain the cadmium ion over the carbon surface. This can be explained by pH solution condition (pH 2) which can produce a competitive effect between cadmium ions and protons H + in the solution.

Table 5 Comparison of Frendlich, Langmuir, Redlich Peterson, Dubinin Radushkevich, and Temkin model adsorption parameters at pH 5.

Model

Sample

AG0.75_600

OL1_600

Freundlich K F (mg g 1 ) 1/ n r 2 D q e (%)

12.03

12.59

0.19

0.18

0.95

0.91

0.73

1.85

Langmuir q max (mg g 1 ) K L (L mg 1 ) r 2 D q e (%)

26.33

24.83

0.46

0.78

0.99

1.00

8.27

14.50

Redlich Peterson B RP (L mg 1 ) G G r 2 D q e (%)

1.69

3.17

1.00

1.00

1.00

1.00

1.22

76.13

D. Obregón-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 2280 2288

2287

Furthermore, the total surface charge will be on average positive [4] in a solution with pH lower than the point zero charge (pH PZC ) of the adsorbent (in previous work, it was found that pH PZC was on average 2.55) which generates electrostatic repulsion between the AC surface charge and the cadmium ion. The adsorption capacity of Cd increased at pH 5 ( Table 5 ), for example, according with Langmuir model, the sample AG0,75 _600 reached a q max = 26.33 mg g 1 and OL1_600 a q max = 24.83 mg g 1 . These results were compared with Rao et al. [33] which obtained a q max = 19.59 mg g 1 . At this pH, the carbon surface is negatively charged, it gets more nucleophile and this allows a greater attraction of the adsorbate to the surface of the adsorbent. This indicates that the adsorption process would be associated with an electrostatic interaction.

Conclusions

The parameters with greater in uence in the adsorption properties of the activated carbons are the precursor nature, the activation temperature, and the impregnation ratio. Aguaje stones offer a promising raw material for the production of activated carbon for water treatment purposes. The activated carbon chemical and textural characteristics are highly related to the precursor nature and generate different adsorption capacities, although both precursors (aguaje and olive fruit stones) were prepared under the same conditions. The activated carbons with the highest adsorption capacities were: from AG series, AG0.75_600 (26.33 mg g 1 ) and from OL series OL1_600 (24.83 mg g 1 ) at pH 5. Both activated carbons presented a high developed mesoporous area (140 y 125 m 2 g 1 , respectively) and a high super cial acidity (2.43 y 2.37 mmol H + g 1 , respectively). The high lignin content and natural ber compaction in olive stones required a higher impregnation ratio to get a suitable super cial acidity and mesoporous area to increase the cadmium ion adsorption. The kinetic curve tted suitably to pseudo second order model, which allows to establish that the adsorption process is the result of two types of interactions, chemical and physical, between the metal ion and the activated carbon surface. The isotherm model ts suitably to Langmuir model. In accordance with Redlich Petersons G parameter near to 1, the adsorption process mostly takes place in homogeneous active sites over the activated carbon surface.

Con icts of interest

The authors declared that there is no con ict of interest.

Acknowledgement

The authors thank Vicerrectorado de Investigación (VRI-PUCP) for the partial support under Proyecto Interdisciplinario DGI 2010-

0099.

References

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