Journal of Colloid and Interface Science 359 (2011) 499504

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Adsorption of benzoic acid from aqueous solution by three kinds of modied bentonites
Xiaodong Xin a, Wei Si a, Zhenxing Yao a, Rui Feng a, Bin Du a,b,, Liangguo Yan a,, Qin Wei b,
a b

School of Resources and Environment, University of Jinan, Jinan 250022, China School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China

a r t i c l e

i n f o

a b s t r a c t
Benzoic acid removal is important for the water treatment, and adsorption is an efcient treatment process. Three kinds of modied bentonites, hydroxy-aluminum pillared bentonite (Al(OH)-Bent), octadecyl trimethyl ammonium chloride modied bentonite (OTMAC-Bent), and both octadecyl trimethyl ammonium chloride and hydroxy-aluminum modied bentonite (Al(OH)-OTMAC-Bent) were prepared and characterized by XRD, FTIR, and BET analysis. Experiments were conducted on the adsorption of benzoic acid by the prepared modied bentonites at different temperatures in batch experiments. The results show benzoic acid adsorption capabilities of Na-Bent and Al(OH)-Bent are even low, but high for OTMAC-Bent and Al(OH)-OTMAC-Bent. Optimal conditions for the adsorption of benzoic acid on OTMAC-Bent and Al(OH)-OTMAC-Bent were as follows: pH of 3.5, 0.04 g/mL adsorbent, and contact time of 90 min. Increased adsorption with temperature indicates that the adsorptions of benzoic acid onto Al(OH)-OTMAC-Bent and OTMAC-Bent are spontaneous and endothermic. The adsorption data could be well interpreted by the Langmuir model and Temkin Equation. The adsorption efciency was higher than 85%, suggesting that OTMAC-Bent and Al(OH)-OTMAC-Bent are excellent adsorbents for effective benzoic acid removal from water. Crown Copyright 2011 Published by Elsevier Inc. All rights reserved.

Article history: Received 10 December 2010 Accepted 11 April 2011 Available online 18 April 2011 Keywords: Modied Bentonite Benzoic acid Adsorption isotherm Adsorption thermodynamics Octadecyl trimethyl ammonium chloride

1. Introduction Industrial wastewater contains many organic and inorganic matters, such as aromatic compounds, heavy metals, and dyes. Many organic compounds have been classied as hazardous pollutants due to their potential toxicity to human health. Nowadays, the excessive and uncontrolled use of chemical preservatives which are mainly composed of organic compounds become a major problem. Benzoic acid, as a major kind of chemical preservatives, is one of the most important additives in the food industry. Because of the toxicity, its usage has been prohibited as food additive in many countries, such as in China, Japan, and the European Union. But now, benzoic acid could still be detectable in industrial sewage, which could affect the human health. Therefore, the removal of benzoic acid in water brings much public attention [1,2], and there is currently an urgent demand for improved chemical preservatives emoval methods. There are many methods for the removal of organic pollutants from aqueous solutions, such as adsorption, chemical precipitation, ion exchange, membrane processes, biological degradation, chem Corresponding authors. Address: School of Resources and Environment, University of Jinan, Jinan 250022, China (B. Du). Fax: +86 531 82767370. E-mail addresses: bindu0720@gmail.com (B. Du), yanyu-33@163.com (L. Yan), weiqin61@gmail.com (Q. Wei).

ical oxidation, and solvent extraction. Adsorption is the most popular method. There are many studies for the adsorption of benzoic acid from aqueous solutions [36]. Activated carbons have the advantages of high adsorption capacity for benzoic acid [5,6]. However, because of its relatively high cost, there have been attempts to utilize low cost, naturally occurring adsorbents, to remove contaminants from wastewater [4,7,8]. Recently, the usage of natural mineral adsorbents for wastewater treatment is increasing due to their abundance and low price. One type of clay minerals is bentonite, the main component of which is montmorillonite. Simple ion-exchange reactions can signicantly modify the surface properties of natural bentonite. The cations of bentonite (Na+, Ca2+) can be replaced by inorganic hydroxyl-metal polycations acting as pillars, which increase the interlayer spacing of bentonite. Moreover, when organic cations (such as cationic surfactants) occupy the exchange sites of bentonite clay, the surface properties transform from hydrophilic to hydrophobic. There has been much interest in the use of modied bentonites as adsorbents to prevent and remediate environmental contamination. Previous studies show that inorganic pillared bentonite and organic modied bentonite have been widely used to adsorb heavy metals [9], dyes [1012], gases [13], organic pollutants such as benzoic acids [3,4], catechol [14], chlorobenzene [15], phenol [16,17] and other environmental pollutants [1821].

0021-9797/$ - see front matter Crown Copyright 2011 Published by Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2011.04.044

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The objective of this study is to examine the feasibility of using differernt kinds of bentonites as adsorbents for benzoic acid removal. In the present study, three different bentonites, hydroxyaluminum pillared bentonite (Al(OH)-Bent), octadecyl trimethyl ammonium chloride modied bentonite (OTMAC-Bent), and both octadecyl trimethyl ammonium chloride and hydroxy-aluminum modied bentonite (Al(OH)-OTMAC-Bent) were synthesized. The synthesized bentonites were characterized by FTIR, XRD, and BET analysis. The benzoic acid adsorption properties (effect of operating variables, adsorption isotherms, and adsorption thermodynamics) were also evaluated utilizing batch experimental methods.

2.2.4. Preparation of Al(OH)-OTMAC-Bent The pillaring solution of hydroxy-aluminum oligomeric cations and the OTMAC solution were drop-wise added into stirred bentonite suspension. The Na-Bent was reacted with OTMAC solution equivalent to the CEC. And the pillaring solution of hydroxy-aluminum oligomeric cations was the same as that of Al(OH)-Bent. The products were washed with deionized water until chloride free (as judged by the silver nitrate test) and collected by centrifugation. Finally, the product dried at 80 C, ground in an agate mortar to pass through a 200 mesh sieve, and kept in a sealed bottle. The inorganicorganic modied bentonites were designated as Al(OH)-OTMAC-Bent. 2.3. Characterization methods XRD patterns of the prepared samples were acquired with a Rigaku D/MAX 2200 X-ray diffractometer (Tokyo, Japan). BET analysis was performed on Micromeritics ASAP 2020 surface area and porosity analyzer (Quantachrome, United States). Pore distributions and pore volume were calculated using the adsorption branch of the N2 isotherms based on the BJH model. Specic surface area was calculated on the basis of the BET equation. FTIR spectra were recorded in the spectral range of 4000 $ 400 cm1 on a PerkinElmer Spectrum One FTIR spectrometer (Perkin Elmer, United States). 2.4. General batch adsorption procedure Benzoic acid stock solution of 15 mmol/L was prepared by dissolving benzoic acid in deionized water, and dilutions of the stock solution were used in subsequent experiments. In the isotherm experiments, 0.4 g of modied bentonite (OTMAC-Bent, Al(OH)OTMAC-Bent) and 10 mL 212 mmol/L benzoic acid solution were mixed in a series of Teon centrifuge tubes. The pH was adjusted to the optimum pH by adding a few drops of 1 mol/L HCl or 1 mol/ L NaOH. The tubes were capped and placed on an orbital shaker at 170 rpm for 90 min to ensure equilibrium. The suspension was separated by lter. The residual concentration of benzoic acid was determined by Lambda 35 UVvis spectrophotometer (Perkin Elmer, United States) at a wavelength of 227 nm. Each experiment was duplicated under identical conditions. Blank samples (containing only deionized water and corresponding modied bentonites) were prepared and monitored for the duration of the experiment as a control. These blank samples indicated insignicant benzoic acid volatilization or adsorption losses on the glassware for the duration of the experiment. 3. Results and discussion 3.1. Characterization of bentonites X-ray diffraction (XRD) was performed on dried natural bentonite, Na-Bent, OTMAC-Bent, Al(OH)-Bent, and Al(OH)-OTMAC-Bent, as shown in Table 1. For natural bentonite, the main compensating cations were calcium and magnesium, which was in agreement with the observed d001 distance of 14.73 . The d001 value decreased to 12.17 when Ca2+ and Mg2+ ions were fully exchanged by Na+ ions for their lower radii in the layer of bentonite. After hydroxyaluminum polycations exchange, the d001 value increased to 18.97 . After OTMAC cation exchange, the d001 value increased to 20.22 . For the Al(OH)-OTMAC-Bent, the d001 value is 20.73 , which is larger than that of OTMAC-Bent and Al(OH)-Bent, and is also larger than that of Zhu and Zhu [23], who reported the 19.11 basal spacing for the CTMAB-Al-Bent. The result may be due to OTMAC molecule is larger than CTMAB molecule.

2. Materials and methods 2.1. Materials The bentonite used in this study was purchased from the Fangzi bentonite plant (Weifang, Shandong Province, China). Octadecyl trimethyl ammonium chloride (OTMAC), NaCl, Na2CO3, AlCl3, NaOH, KH2PO4 were all of analytical grade, obtained from Sinopharm Chemical Reagent Beijing Co., Ltd., China. All of the reagents were used as received.

2.2. Preparation of modied bentonites 2.2.1. Preparation of sodium bentonite The natural bentonite was converted to sodium bentonite (NaBent) before the synthesis of modied bentonites. Firstly, 100 g of the natural bentonite was dispersed in 2.0 L of deionized water by intense shaking for about 6 h. The <2 lm fraction of the bentonite was collected. Then, the bentonite was dispersed in 500 mL 0.5 mol/L NaCl solution and stirred for 24 h. The supernatant was removed after settling. This procedure was repeated 2 times. After complete exchange, Na-Bent was washed with deionized water repeatedly until free of chloride ions as indicated by AgNO3 solution. The product was dried at 80 C, gently ground in an agate mortar to 200 mesh, and kept in a sealed bottle. The cation exchange capacity (CEC) of this Na-Bent is 0.835 mmol/g.

2.2.2. Preparation of OTMAC-Bent Twenty grams of Na-Bent was reacted with OTMAC solution equivalent to the CEC, shaken for 24 h, and the clear supernatant was discarded. The nal organic modied bentonite mixture was washed several times with deionized water until free of chloride ions in the supernatant. The samples were dried at 80 C, activated for 1 h at 105 C, ground in an agate mortar to pass through a 200 mesh sieve, and kept in a sealed bottle. The organic modied bentonites were designated as OTMAC-Bent.

2.2.3. Preparation of Al(OH)-Bent According to the method described by Yan et al. [22], the pillaring solution of hydroxy-aluminum oligomeric cations was prepared by slowly adding 0.48 mol/L NaOH solution to 0.2 mol/L AlCl3 solution under vigorous stirring at 60 C, until the OH/Al3+ molar ratio reached 2.4. The solution was stored at 60 C for 24 h. The resulting pillaring solutions were added drop-wise to a 1% (by weight) Na-Bent suspension by stirring for 12 h at the ratio of 10 mmol oligomeric cations per gram of Na-Bent. The slurry was stirred for 24 h at room temperature and washed repeatedly with deionized water until there was no chloride. The solid was dried at 80 C, ground in an agate mortar to pass through a 200 mesh sieve, and kept in a sealed bottle. The inorganic pillared bentonites were designated as Al(OH)-Bent.

X. Xin et al. / Journal of Colloid and Interface Science 359 (2011) 499504 Table 1 The BET surface area, total pore volume, and average pore diameter for natural bentonites, Na-Bent, Al(OH)-Bent, OTMAC-Bent, and Al(OH)-OTMAC-Bent. Adsorbent Natural bentonites Na-Bent Al(OH)-Bent OTMAC-Bent Al(OH)-OTMAC-Bent d001 () 14.73 12.17 18.97 20.22 20.73 BET surface area (m2/g) 10.15 31.67 167.3 26.70 71.54 Pore volume (cm3/g) 0.03071 0.06075 0.1215 0.08663 0.1005

501

Average pore diameter (nm) 3.515 7.672 8.794 10.53 9.261

Table 1 also showed the BET surface area, pore volume, and average pore diameter for the different samples. The BET surface area of Al(OH)-Bent was far larger than that of OTMAC-Bent and Al(OH)-OTMAC-Bent. FTIR has been widely used to probe the aggregating situations of the adsorbed organic cations on clay minerals. The FTIR spectra of natural bentonite, Na-Bent, OTMAC-Bent, and Al(OH)-OTMACBent in the range of 4000300 cm1 were shown in Fig. 1. A band at 3435 cm1 in the spectra showed HOH hydrogen bonded water. The intensive band at around 1040 cm1 can be assigned to SiO stretching vibrations. The SiOAl and SiOSi bending vibrations appeared at 525 and 465 cm1, respectively. The small band at 1635 cm1 corresponded to the dSiOH deformation vibration [24]. From Fig. 1C and D, it can be seen that the bands at 2920 and 2850 cm1 were correspond to the CH2 asymmetric stretching mode (ms(CH2)) and the symmetric stretching mode (ms(CH2)), respectively. The splitting of the methylene scissoring mode at 1490 cm1 in FTIR was considered to be diagnostic of the packing density increase in the intercalated surfactants within the clay gallery. The results indicated that the OTMAC molecules were impregnated into the interlayer space of the bentonite.

3.2. Effect of operating variables on the adsorption of benzoic acid onto Al(OH)-Bent, OTMAC-Bent, and Al(OH)-OTMAC-Bent To understand the adsorption of benzoic acid by OTMAC-Bent, Al(OH)-Bent, and Al(OH)-OTMAC-Bent, the inuences of initial pH, adsorbent concentration, contact time, adsorption isotherms, and adsorption thermodynamics on benzoic acid adsorption were studied at room temperature (298 K). The removal efciency and the amount of benzoic acid adsorbed q (mg/g) were given according to the formula:

Removal efficiency% c0 ct M V m

c0 c t 100% c0

qt

Where ct (mmol/L) is the concentration of adsorbates by adsorbent at time t (min), V (L) is the volume of adsorbates, m (g) is the mass of adsorbents. qe (mg/g) is the adsorbed amount at equilibrium. qt (mg/g) is the adsorbed amount at time t (min). 3.2.1. Effect of initial pH on adsorption The pH value of the solution was an important controlling parameter in the adsorption process. The adsorptions of benzoic

(A) 1.0
0.9

(B)
Transmission
4000 3500 3000 2500 2000 1500 1000 500

1.1 1.0

Transmittance

0.9 0.8 0.7 0.6 0.5 0.4 4000 3500 3000 2500 2000 1500 1000 500

0.8 0.7 0.6 0.5

Wavenumber (cm -1)

Wavenumber (cm )

-1

(C)
Transmittance

1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 4000 3500 3000 2500 2000 1500 1000 500
-1

(D) 1.05
1.00

Transmittance

0.95 0.90 0.85 0.80 0.75 4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm )

Wavenumber (cm )

-1

Fig. 1. FTIR spectra of natural bentonite (A), Na-Bent (B), OTMAC-Bent (C), and Al(OH)-OTMAC-Bent (D).

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acid onto natural bentonites, Al(OH)-Bent, OTMAC-Bent, and Al(OH)-OTMAC-Bent were carried out with a xed 10 mL, 5.0 mmol/L benzoic acid solution at various pH values to examine the effect of pH. The amounts of benzoic acid adsorbed onto natural bentonite, Al(OH)-Bent, OTMAC-Bent, and Al(OH)-OTMAC-Bent at various pH values are illustrated in Fig. 2A. Benzoic acid was hardly adsorbed by Na-Bent and Al(OH)-Bent, so the adsorption properties of Na-Bent and Al(OH)-Bent were not discussed further. As presented in Fig. 2A, pH exerts a signicant impact on OTMAC-Bent and Al(OH)-OTMAC-Bent, which affects the surface charge of the adsorbent and the degree of ionization of organic compounds. Both OTMAC-Bent and Al(OH)-OTMAC-Bent have a high removal efciency of benzoic acid at pH 34, while the uptake of benzoic acid decreased with increasing pH (pH > pKa,benzoic acid = 4.19).

Generally, benzoic acid is mostly present in neutral form when pH is less than its pKa. At pKa, 50% of benzoic acid is present as anion, and at pH > pKa, anions are predominated. Lower adsorption at higher pH may be due to the abundance of OH- ions competing with anion of organic compounds for the adsorption sites and the ionic electrostatic repulsion between the negatively charged bentonite surface and the ionic organic compounds. Similar behaviors have been reported by Yldz et al. [4] for benzoic acid adsorption by organobentonites, and by Banat et al. [25] for the adsorption of phenol by bentonite. According to Banat et al. [25], ionization increases as the pH value increased and organic solutes will be adsorbed to lower extent at higher pH values due to the repulsive forces prevailing at higher pH values. And other authors were reported similar results [26]. Hence, the amount of benzoic acid adsorbed to OTMAC-Bent and Al(OH)-OTMAC-Bent should be pH dependent. 3.2.2. Effect of adsorbent concentration Different concentrations of OTMAC-Bent and Al(OH)-OTMACBent were combined with a xed 10 mL, 5.0 mmol/L benzoic acid solution at the optimum pH, respectively. As shown in Fig. 2B, the adsorption of benzoic acid increased with the increase in adsorbent concentration at lower concentration, and reached to a plateau at the appropriate concentration of adsorbent of 0.04 g/mL. This trend was expected because more adsorbates will naturally attach to an increased number of adsorbent particles surrounding the adsorbates. 3.2.3. Effect of contact time on adsorption The adsorption of benzoic acid increased with contact time and reached equilibrium at about 90 min with a xed 10 mL, 5.0 mmol/L benzoic acid solution, and 0.04 g/mL of adsorbent (Fig. 2C). The nal adsorption efciency was both higher than 85%, and qe in the batch system are 12.89 mg/g and 13.28 mg/g for the adsorption of benzoic acid onto OTMAC-Bent and Al(OH)-OTMAC-Bent, suggesting that OTMAC-Bent and Al(OH)-OTMAC-Bent are excellent adsorbents for effective benzoic acid removal from water. 3.3. Adsorption isotherms

(A)
Removal efficiency %

90 80 70 60 50 40 30 20 10 0 2 3 4 5

OTMAC-Bent Al(OH)-OTMAC-Bent Al(OH)-Bent Na-Bent

pH

(B)
Removel efficiency %

90 80 70 60 50 40 30 20 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08

OTMAC-Bent Al(OH)-OTMAC-Bent

Based on the above optimized conditions, the adsorption isotherms of benzoic acid by the two modied bentonites were studied at room temperature (298 K) and the results are shown in Fig. 3. The Henry, Langmuir, Freundlich, DubininRadushkevich, and Temkin equations expressed in Eqs. (3)(7) were used for modeling these adsorption isotherm data.

Concentrations of adsorbents (g/mL)

qe kce qe bqm ce 1 bce 1 1 1 1 qe bqm c qm ln qe ln K F 1 ln ce n

3 4

(C)
Removal efficiency %

90 85 80 75 70 65 60 0 50 100 150 200 250 300

1=n qe K F ce

5 6 7

ln qe ln qm be2 qe RT RT ln ce ln AT bT bT

OTMAC-Bent Al(OH)-OTMAC-Bent

t (min)
Fig. 2. Effect of pH (A), concentrations of adsorbents (B), and contact time (C) for the adsorption of benzoic acid onto OTMAC-Bent and Al(OH)-OTMAC-Bent.

The tted constants along with regression coefcients (R2) are summarized in Table 2. The R2 values obtained for the Langmuir isotherms were both above 0.99, indicating a very good mathematical t by both models. Langmuir model is based on three following assumptions: (1) the adsorption of molecule is a monolayer adsorption; (2) the adsorption of adsorbent surface is uniform; (3) there is no interaction between adsorbed molecules. The R2

X. Xin et al. / Journal of Colloid and Interface Science 359 (2011) 499504

503

(A)
qe (mgg )
-1

25 20 15 10
OTMAC-Bent Al(OH)-OTMAC-Bent

(B) 0.225
0.200 0.175 0.150
OTMAC-Bent Al(OH)-OTMAC-Bent

(C) 3.2
3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

OTMAC-Bent Al(OH)-OTMAC-Bent

1 / qe

0.125 0.100 0.075 0.050 0.025

5 0 1 2 3
-1

lnqe

ce(mmol L )

-1.5 -1.0 -0.5

0.0

0.5

1.0

1.5

1 / ce

lnce
24 22 20 18 16 14 12 10 8 6 4 -1.0
OTMAC-Bent Al(OH)-OTMAC-Bent

(D) 3.2
3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 0 2 4
OTMAC-Bent Al(OH)-OTMAC-Bent

(E)

lnqe

10 12 14 16

qe

-0.5

0.0

0.5

1.0

1.5

lnce

Fig. 3. Henry (A), Langmuir (B), Freundlich (C), DubininRadushkevich (D), and Temkin (E) adsorption isotherm t of benzoic acid adsorption onto Al(OH)-OTMAC-Bent and OTMAC-Bent.

Table 2 Constants and correlation coefcients of adsorption isotherms for the adsorption of benzoic acid onto Al(OH)-OTMAC-Bent and OTMAC-Bent. Model Temkin Equation Parameter bT AT R2 b (g2/kJ2) qm (mg/g) R2 Kh R2 Kf n R2 qm (m/g) b (L/mg) R2 OTMACBent 207.3 7.2469 0.9906 0.1055 19.05 0.8840 3.527 0.7608 10.79 1.942 0.9223 20.80 1.337 0.9954 Al(OH)-OTMACBent 193.4 7.463 0.9895 0.1021 20.08 0.9076 4.012 0.7750 11.53 1.900 0.9165 22.03 1.374 0.9936

The thermodynamic equilibrium constants (Kd) of the adsorption process, i.e. the constants for benzoic acid distribution between the solid and liquid phases at equilibrium, were computed according to Lyubchik et al. [27] by plotting ln(qe/ce) versus qe and extrapolating qe to zero. The change in DG was then calculated with Eq. (8). DH and DS were calculated from the slope and intercept of the plot of lnKd versus 1/T using Eq. (9).

DubininRadushkevich Equation Henry equation Freundlich equation

DG RT ln K d
ln K d

DS DH R RT

Langmuir equation

values obtained for the Temkin equation were above 0.98, indicating also a good mathematical t by both models. Temkin equation is the correction of Langmuir equation, which is based on Langmuir equation and introduces the inuence of temperature on the adsorption. Therefore, the adsorptions of benzoic acid onto Al(OH)-OTMAC-Bent and OTMAC-Bent are monolayer uniform adsorptions. From Table 2, the calculated qm and Kf followed the order of Al(OH)-OTMAC-Bent > OTMAC-Bent. All the isotherms showed a similar shape and were nonlinear over a wide range of aqueous equilibrium concentrations in Fig. 3. 3.4. Adsorption thermodynamics The inuences of temperature on benzoic acid adsorption onto Al(OH)-OTMAC-Bent and OTMAC-Bent were carried out at temperatures of 293, 303, and 313 K.

The thermodynamic parameters are listed in Table 3. The negative values of DG and positive values of DH indicate that the adsorptions of benzoic acid onto Al(OH)-OTMAC-Bent and OTMAC-Bent are spontaneous and endothermic. The values of DG decreased from 3.501 kJ/mol to 3.992 kJ/mol (Al(OH)-OTMACBent), and 3.452 kJ/mol to 3.968 kJ/mol (OTMAC-Bent) in the temperature range of 293313 K, which indicates the endothermic adsorptions of benzoic acid onto Al(OH)-OTMAC-Bent and OTMACBent were enhanced by an increase in temperature. The values of DH are high enough to ensure strong interaction between the adsorbates and adsorbents. The positive values of DS state clearly

Table 3 Thermodynamic data for the adsorption of benzoic acid onto Al(OH)-OTMAC-Bent and OTMAC-Bent. Adsorbates OTMAC-Bent T (K) 293 303 313 293 303 313 Kd 4.123 4.336 4.491 4.206 4.444 4.637

DG (kJ/ mol)
3.452 3.716 3.968 3.501 3.749 3.992

DS (J/ mol)
27.06

DH (kJ/ mol)
4.490

Al(OH)-OTMACBent

25.68

4.032

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that the randomness increased at the solidsolution interface during the benzoic acid adsorption onto the modied bentonites. The increased adsorption capacity of Al(OH)-OTMAC-Bent and OTMACBent at higher temperatures may be caused by the enlargement of pore size and/or activation of the adsorbent surface [28]. 4. Conclusions In this study, three prepared modied bentonites, Al(OH)-Bent, OTMAC-Bent, and Al(OH)-OTMAC-Bent, were applied to remove benzoic acid from aqueous solution. The benzoic acid adsorption capability of Al(OH)-Bent is low, but high for OTMAC-Bent and Al(OH)-OTMAC-Bent. The pH effect, adsorbents concentration, contact time, adsorption isotherms, and adsorption thermodynamics were also examined. Optimal conditions for the adsorption of 5.0 mmol/L benzoic acid on OTMAC-Bent and Al(OH)-OTMAC-Bent were as follows: pH of 3.5, 0.04 g/mL adsorbent, and contact time of 90 min. The data agree well with the Langmuir adsorption isotherm model. Adsorption thermodynamics indicate the adsorptions of benzoic acid onto Al(OH)-OTMAC-Bent and OTMAC-Bent are spontaneous and endothermic. Aqueous benzoic acid solution with concentration of 5.0 mmol/L was adsorbed by OTMAC-Bent and Al(OH)-OTMAC-Bent, respectively, and the nal adsorption efciency was both higher than 85%, suggesting that OTMAC-Bent and Al(OH)-OTMAC-Bent are excellent adsorbents for effective benzoic acid removal from water. Acknowledgments This study was supported by the Natural Science Foundation of China (No. 21075052), the Natural Science Foundation of Shandong Province (No. ZR2010BM030, ZR2010EM063), the Project of Shandong Province Higher Educational Science and Technology Program (J08LC06), the Science and Technology Key Plan Project of

Shandong Province (No. 2010GSF10628), and the Science and Technology Development Plan Project of Jinan City (No. 201004015). And all the authors express their deep thanks. References
[1] B. Saad, Md.F. Bari, M.I. Saleh, K. Ahmad, M.K.M. Talib, J. Chromatogr. A 1073 (2005) 393. [2] C. Dong, Y. Mei, L. Chen, J. Chromatogr., A 1117 (2006) 109. [3] L.G. Yan, J. Wang, H.Q. Yu, Q. Wei, B. Du, X.Q. Shan, Appl. Clay Sci. 37 (2007) 226. [4] N. Yldz, R. Gnlsen, H. Koyuncu, A. alml, Colloids Surf. A 260 (2005) 8. [5] J.M. Chern, Y.W. Chien, Water Res. 37 (2003) 2347. [6] E. Ayranci, N. Hoda, E. Bayram, J. Colloid Interface Sci. 84 (2005) 83. [7] S. Lagerge, P. Rousset, T. Zoungrana, J.M. Douillard, S. Partyka, Colloids Surf. A 80 (1993) 261. [8] L. Madsen, C. Grn, I. Lind, J. Engell, J. Colloid Interface Sci. 205 (1998) 53. [9] D. Karamanis, P.A. Assimakopoulos, Water Res. 41 (2007) 1897. [10] Z. Bouberka, A. Kheni, N. Benderdouche, Z. Derriche, J. Hazard. Mater. 133 (2006) 154. [11] P. Baskaralingam, M. Pulikesi, D. Elango, V. Ramamurthi, S. Sivanesan, J. Hazard. Mater. B128 (2006) 138. [12] Q.Y. Yue, Q. Li, B.Y. Gao, Y. Wang, Sep. Purif. Technol. 54 (2007) 279. [13] A. Itadani, M. Tanaka, T. Abe, H. Taguchi, M. Nagao, J. Colloid Interface Sci. 313 (2007) 747. [14] K. Shakir, H.F. Ghoneimy, A.F. Elkafrawy, J. Hazard. Mater. 150 (2008) 765. [15] R. Sennour, G. Mimane, A. Benghalem, S. Taleb, Appl. Clay Sci. 43 (2009) 503. [16] S. Yapar, V. zbudak, A. Dias, A. Lopes, J. Hazard. Mater. 121 (2005) 135. [17] Y. Shu, L. Li, Q. Zhang, H. Wu, J. Hazard. Mater. 173 (2010) 47. [18] L. Zhu, J. Ma, Chem. Eng. J. 139 (2008) 503. [19] B. Chen, W. Huang, J. Environ. Sci. 21 (2009) 1044. [20] R. Zhu, L. Zhu, J. Zhu, J. Zhu, F. Ge, T. Wang, J. Hazard. Mater. 168 (2009) 1590. [21] M. Cruz-Guzmn, R. Celis, M.C. Hermosn, W.C. Koskinen, J. Cornejo, J. Agric. Food Chem. 53 (2005) 7502. [22] L. Yan, Y. Xu, H. Yu, X. Xin, Q. Wei, B. Du, J. Hazard. Mater. 179 (2010) 244. [23] L. Zhu, R. Zhu, Sep. Purif. Technol. 54 (2007) 71. [24] X. Huang, S. Xu, M. Zhong, J. Wang, S. Feng, R. Shi, Appl. Clay Sci. 42 (2009) 455. [25] F.A. Banat, B. Al-Bashir, S. Al-Asheh, O. Hayajneh, Environ. Pollut. 107 (2000) 391. [26] K.A. Halhouli, N.A. Darwish, Y. Al-Jahmany, Sep. Sci. Technol. 32 (1997) 3027. [27] S.I. Lyubchik, A.I. Lyubchik, O.L. Galushko, L.P. Tikhonova, J. Vital, I.M. Fonseca, S.B. Lyubchik, Colloids Surf. A 242 (2004) 151. [28] Y. Masue, R.H. Loeppert, T.A. Kramer, Environ. Sci. Technol. 41 (2007) 837.