641

Performance of Poly(StyreneDivinylbenzene) Magnetic Porous Microspheres Prepared by Suspension Polymerization for the Adsorption of 2, 4-Dichlorophenol and 2, 6-Dichlorophenol from Aqueous Solutions
Ping Yu1,2, Qilong Sun3,*, Jianming Pan2, Zhenjiang Tan1,*, Jiangdong Dai4, Yongsheng Yan2 and Feng Cheng1 (1) School of Computer Science, Jilin Normal University, 1301 Haifeng Street, Siping
136000, China. (2) School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China. (3) School of Management, Jilin Normal University, 1301 Haifeng Street, Siping 136000, China. (4) School of Materials, Jiangsu University, Zhenjiang 212013, China. (Received 14 May 2013; revised form accepted 2 July 2013)

ABSTRACT: Poly(styrenedivinylbenzene)/Fe3O4 (Fe3O4@StDVB) magnetic porous polymer microspheres based on suspension polymerization were prepared for adsorption of 2, 4-dichlorophenol (2, 4-DCP) and 2, 6-dichlorophenol (2, 6-DCP) from aqueous solution. The as-prepared product was characterized by Fourier transform infrared spectroscopy, Raman, X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and elemental analysis. The results showed that the composite material has both porous and magnetic characteristics, which aid in faster separation and increase in adsorption capacity. The adsorption performance of the Fe3O4@(StDVB) magnetic porous microspheres was manifested by batch mode adsorption experiments with respect to pH, initial concentration, contact time and temperature. The adsorbent was found to be sensitive to changes in pH, and the adsorption capacity of 2, 4-DCP is higher than that of 2, 6-DCP. The kinetics experimental data fitted well with the pseudo-second-order model, as three steps belonged to the pseudo-secondorder adsorption process. The adsorption isotherms were also described by the Langmuir and Freundlich isotherm models, respectively. It was found that the Langmuir isotherm model fitted the equilibrium data superior to the Freundlich model. Thermodynamic parameters were calculated by the Gibbs free energy function, confirming that adsorption process was spontaneous and endothermic. In addition, the reusability performance of the Fe3O4@(StDVB) magnetic porous microspheres was demonstrated by four repeated cycles.

1. INTRODUCTION Chlorophenols, such as 2, 4-dichlorophenol (2, 4-DCP) and 2, 6-dichlorophenol (2, 6-DCP) are multi-duty raw materials in chemical industries and are widely used in many areas such as petroleum, chemical, petrochemical, coal gasification and carbonization, pharmaceutical, wood, plastic, paper, textile, rubber, photographic, dye, disinfectant and pesticide industries (An et al. 2012). However, the Environmental Protection Agency has listed chlorophenols and its derivatives as toxic pollutants because they are highly toxic and harmful to different biological processes. Chlorophenols give an unpleasant taste and odour to drinking water, and even small amounts of the chemical in water will greatly harm aquatic life and peoples health. Chlorophenols
*Author to whom all correspondence should be addressed. E-mail: jlsdyp@126.com (Q. Sun).

642

Ping Yu et al./Adsorption Science & Technology Vol. 31 No. 7 2013

can encroach the nerve centre, causing different degree of headache, vomiting and other adverse symptoms. Most of these compounds are known or suspected to be human carcinogens (Kieth and Telliard 1979). Therefore, removal of chlorophenols from aqueous solution is a crucial theme in the field of environmental protection. Various techniques and methods can be used to remove chlorophenols from aqueous solution, such as biodegradation (Stehlickova et al. 2009), photocatalytic degradation (Deshpande and Madras 2010), chemical oxidation (Zazo et al. 2009), membrane separation (Ng et al. 2010) and adsorption (Matynia et al. 2003). Among these methods, adsorption is an economic and effective method. Recently, a variety of adsorbents have received increased attention for their application in the removal of chlorophenols. For example, functional chitosan (Kumar et al. 2010) and fly ash (Andini et al. 2008) have been used as sorbents for the adsorption of chlorophenols from aqueous solutions. However, common adsorbents have to face the problems of low adsorption capacity and it is difficult to reuse them. Therefore, searching for reproducible adsorbents that have comparable capacity and simple separation process is highly desired (Matynia et al. 2003). Recently, porous polymer adsorbents were synthesized and widely applied to remove chlorophenols from aqueous solution (Zeng et al. 2010), due to their characteristic properties such as low density, high porosity and easy functionalization. The methods of synthesis of porous polymer microspheres commonly included suspension polymerization, emulsion polymerization, dispersion polymerization, etc. Of all these methods, suspension polymerization has been proved to be the most simple yet powerful method. Suspension polymerization not only has the advantage of simple operation, but also the purity of the product is high. In addition, the porous polymer adsorbents prepared by suspension polymerization, as a kind of special surface morphology modification method, have large specific surface area and increased adsorption ability. To the best of our knowledge, there were no studies about the adsorptive removal of chlorophenols by porous polymer adsorbents prepared by suspension polymerization. In order to solve the difficulty in collecting adsorbents from their dispersing media, special attention has been directed to the combination of iron oxide magnetic nanoparticles and conventional adsorbents (Pan et al. 2011). A series of absorbents composed of magnetic particles and inorganic matters has been prepared. For example, -Fe2O3 and cerium atomic composite magnetic nanoparticles (Haviv et al. 2010) and the Fe2O3 nanoparticles have been introduced into the multi-walled carbon nanotubes to synthesize magnetic adsorption material (Qu et al. 2008). The magnetic particles showed significant advantages in the separation process, easy to separate and no longer required additional centrifugal separators or filters. However, the aforementioned magnetic particles are very limited due to the lack of high magnetic leakage and difference in acid resistance. Use of functional polymer-coated magnetic particle preparation of a magnetic adsorbent is a useful method to improve this limitation, by which we can use the polymer-coated layer to bind pollutants and using polymer layer internal magnetic particles to realize the response of the magnetic field. The preparation of magnetic porous polymer microspheres by suspension polymerization not only has high specific surface and excellent adsorption performance, but also can be realized by simple separation in additional magnetic field. Inspired by these works, we herein report the synthesis of magnetic porous polymer microspheres based on suspension polymerization of styrene (St) and divinylbenzene (DVB) with Fe3O4 coated by oleic acid. The Fe3O4@(StDVB) magnetic porous polymer microspheres were then used for the absorption of 2, 4-DCP and 2, 6-DCP from aqueous solution. The adsorption properties such as adsorption equilibrium, kinetics, thermodynamics and regeneration performance were manifested by batch mode adsorption experiments.

Magnetic Porous Microspheres for DCP Adsorption

643

2. EXPERIMENTAL SECTION 2.1. Materials All solvents used in this work were of analytical or high-performance liquid chromatography grade. St, toluene, sodium chloride, sodium acetate, ethanol, acetone, methylene dichloride and methyl alcohol were supplied by Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). The 2,4-DCP and 2,6-DCP were purchased from Tianda Chemical Reagent Factory (Tianjin, China). Azodiisobutyronitrile (AIBN), DVB, cyclohexanol, iron(III) chloride and ethylene glycol were obtained from Aladdin Reagent Co., Ltd. (Shanghai, China). Hydroxyethyl cellulose (HEC) was supplied by Shanghai Hualing Resin Co., Ltd (China Shanghai). 2.2. Equipment Fourier transmission infrared spectra (FTIR) of the Fe3O4@(StDVB) magnetic porous polymer microspheres were recorded on a Nicolet NEXUS-470 FTIR apparatus. The shape and the surface morphology of the magnetic porous polymer microspheres were obtained using a scanning electron microscope (XL-30ESEM, Philips). An elemental analyzer (Elementary, Hanau, Germany) was used to investigate the surface elemental composition of the Fe3O4@(StDVB) magnetic porous microspheres. Magnetic measurements were carried out using a vibrating sample magnetometer (VSM) (7300, Lakeshore) under a magnetic field up to 10 kOe. The thermogravimetric analysis (TGA) and DSC of the samples (powdered form, weighing about 10 mg) were performed using a Diamond TG/DTA instrument (PerkinElmer) under a nitrogen atmosphere up to 800 C with a heating rate of 5 l minute1. The photographs of the magnetic separation were obtained using Canon IXUS125 HS. The identification of crystalline phase was performed using a Rigaku D/max-B X-ray diffractometer with monochromatized Cu-K radiation over a 2 range of 2070 at a scanning rate of 7 minute1, Raman spectroscopy was used to analyze the chemical composition and crystallographic structure of the nanoparticles. 2.3. Preparation of Oleic AcidModified Fe3O4 Magnetic Fluid The oleic acidmodified Fe3O4 nanoparticles were prepared according to our previous work (Laurenti et al. 2011). In brief, 1.35 g of FeCl36H2O and 7.2 g sodium acetate were dissolved in 40 ml of ethylene glycol under nitrogen gas protection with vigorous stirring at 160 C for 1 hour. Thereafter the mixture was transferred into a 50-ml reaction flask and heated to 200 C for 10 hours. After cooling the mixture to room temperature, the suspension was washed three times with ethyl alcohol. Subsequently, the products obtained were dried under vacuum at 60 C and finely ground in a mortar. Finally, 4 ml oleic acid was added to 0.1 g of Fe3O4 particles and the mixture was continuously stirred for 1 hour to obtain the magnetic fluid. 2.4. Preparation of Fe3O4@(StDVB) Magnetic Porous Microspheres The preparation of Fe3O4@(StDVB) magnetic porous microsphere was followed according to a previously described procedure (Li et al. 2006) with a few modifications. The microspheres were mainly used to adsorb phenol from aqueous solution. In order to achieve the optimal morphology and performance of the microspheres, the dosage of the porogen and surfactant was varied. Table 1 shows the characterization data of Fe3O4@StDVB microspheres. In this work, Sample 3 was

644

Ping Yu et al./Adsorption Science & Technology Vol. 31 No. 7 2013

TABLE 1. Characterization Data of Poly(StyreneDivinylbenzene)@Fe3O4 Microspheres Organic phase NaCl (m mol) Sample 1 Sample 2 Sample 3 Sample 4 25.67 17.11 25.67 17.11 Deionized HEC (g) water (ml) 0.9 0.6 0.9 0.6 80 80 80 80 Water phase AIBN St (ml) DVB (ml) (m mol) 5 5 5 5 7.5 7.5 7.5 7.5 1.52 1.52 1.52 1.52 Cyclohexanol Toluene (ml) (ml) 4.165 4.165 4.165 4.165 8.33 8.33 6.25 6.25

used. St, DVB, AIBN, toluene and cyclohexanol were mixed with oleic acidmodified Fe3O4 magnetic fluid to form the organic phase. Pre-specified concentrations of sodium chloride and HEC were dissolved in 80 ml of deionized water to form the water phase. After complete stirring, the two phases were mixed together by ultrasonic treatment (t = 1530 minutes) in order to form an emulsion. This emulsion was then transferred into a 250-ml three-necked flask equipped with a condenser, a N2 inlet and stirred for 1 hour under nitrogen gas protection. Thereafter, the temperature was increased to 70 C and the reaction was carried out with a stirring rate of 800 rpm for 24 hours. Finally, the brown magnetic emulsion was obtained and the magnetic porous microspheres were separated by an additional magnetic field. The obtained polymer microspheres were filtrated and washed with deionized water, ethanol and acetone to remove water-soluble impurities, followed by extraction with methylene dichloride in a Soxhlet extractor to remove the linear polystyrene porogen and organic impurities. The purified beads were washed three times with deionized water and methanol and dried under vacuum for 24 hours (Li et al. 2006; Tai et al. 2011). 2.5. Effect of Solution pH on 2,4-DCP and 2,6-DCP Adsorption Fe3O4@(StDVB) microspheres (10 mg) were added to eight centrifuge tubes containing 10 ml of 100 mg l1 2, 4-DCP or 2, 6-DCP solution. The solution pH was adjusted to 2, 3, 4, 5, 6, 7, 8, 9 by adding 1 mol l1 HCl or NH3H2O solutions. After stewing in a thermostatic water bath for 12 hours at 298 K, the supernatant fluid was obtained by centrifuging the solution at high speeds. Ultraviolet spectroscopy was used to analyze the remnant concentrations of 2, 4-DCP and 2, 6-DCP. 2.6. Equilibrium Studies Equilibrium experiments were carried out by treating 5 mg Fe3O4@(StDVB) microspheres with 10 ml of 2, 4-DCP (pH = 2) or 2, 6-DCP (pH = 2) solution of different initial concentrations (10, 30, 50, 80, 100, 150, 200, 250, 300 and 400 mg l1). Several samples of the mixture were added to 10-ml centrifuge tubes and stewed in a thermostatic water bath for 12 hours at 298 K. The equilibrium adsorption capacity of (Qe, mg g_1) was calculated according to equation (1) Qe = (c0 ce )V W (1)

where C0 (mg l1) is the initial concentration and Ce (mg l1) is the equilibrium concentration of the adsorbate (2,4-DCP or 2,6-DCP); V (l) is the solution volume and W (g) is the weight of the adsorbent.

Magnetic Porous Microspheres for DCP Adsorption

645

2.7. Adsorption Kinetics Adsorption kinetics experiment was studied over a reaction time of 10720 minutes. Approximately 5 mg of Fe3O4@(StDVB) microspheres were added into various centrifuge tubes containing 10 ml of 2, 4-DCP or 2, 6-DCP solution (solution pH = 2 for both 2, 4-DCP and 2, 6-DCP; concentration = 100 mg l1). The solutions were stewed in a thermostatic water bath and the reaction time was varied from 10 to 720 minutes. The mixtures were centrifuged and using ultraviolet spectroscopy the residual concentrations of 2, 4-DCP and 2, 6-DCP were analyzed. 2.8. Desorption and Regeneration Desorption and regeneration experiments of the adsorbent were carried out to verify the regeneration capability of the magnetic porous microsphere. Desorption of the adsorbed 2, 4-DCP and 2, 6-DCP from Fe3O4@(StDVB) was also studied by batch experiment, using acetic acid and methyl alcohol solution as eluent. The Fe3O4@(StDVB)-adsorbed 2, 4-DCP and 2, 6-DCP were placed in the eluent and the remnant concentrations of 2, 4-DCP and 2, 6-DCP were studied using ultraviolet spectroscopy, after drying under vacuum for 12 hours. The Fe3O4@(StDVB) microspheres[CE1] were once again added to 100 mg l1 2, 4-DCP (pH = 2) and 2, 6-DCP (pH = 2) solutions. The mixture was allowed to react for 12 hours. This adsorptiondesorption cycle was repeated four times in order to evaluate the regeneration performance of the microspheres.

3. RESULTS AND DISCUSSION 3.1. Characterization of Fe3O4@(StDVB) FTIR spectra of the porous polymer microsphere StDVB and magnetic porous polymer microsphere Fe3O4@(StDVB) were measured and are shown in Figures 1(a and b), respectively.
100
(a)

Transmittance (%)

80

(b)

60
1610 1489 755 1453 694 599

40

3029 3065 3090

3000

2500

2000

1500

1000

500

Wave number

(cm1)

Figure 1. FTIR spectra of the (a) porous microsphere St-DVB and (b) magnetic porous microsphere Fe3O4@(St-DVB).

646

Ping Yu et al./Adsorption Science & Technology Vol. 31 No. 7 2013

The main functional groups of the predicted structure can be observed with the corresponding infrared absorption peaks (Pan et al. 2011). In Figure 1(b), compared with StDVB particles, Fe3O4@(StDVB) microspheres showed new absorption bonds at 599 cm1 corresponding to the FeO groups. The absorption peaks at 3090, 3065 and 3029 cm1 were attributed to the stretching vibration of the CH bond of the benzene ring in polystyrene (Li et al. 2006), whereas the absorption peaks at 1453 and 1489 cm1 were attributed to the skeletal vibration of the benzene ring. A sharp peak was observed at 694 and 755 cm1, which indicates the presence of polystyrene in the polymer (Torres et al. 2012). In addition, the strong peaks at 1610 cm1 were assigned to the C = C groups of DVB monomer (Tai et al. 2011). Raman spectrum of the Fe3O4@(StDVB) composites was shown in Figure 2. There were two peaks at 621 and 642 cm1 in the wavelength range of 200800 cm1, and these peaks could prove the existence of Fe3O4.

40

30

Intersity

20

621 642

10

200

300

400

500

600

700

800

Wave

number/cm1

Figure 2. Raman spectrum of Fe3O4@(StDVB) magnetic porous polymer microspheres.

Figure 3 shows the X-ray diffraction (XRD) patterns of Fe3O4 and Fe3O4@(StDVB) microspheres. In the 2 range of 2565, six characteristic peaks corresponding to maghemite (2 = 30.00, 35.45, 42.98, 53.41, 57.03 and 62.55) were observed in the Fe3O4 XRD pattern, and the peak positions could be indexed to (2, 2, 0), (3, 1, 1), (4, 0, 0), (4, 2, 2), (5, 1, 1) and (4, 4, 0) (Zhu et al. 2010). Moreover, the corresponding peaks also appeared in the pattern suggestive of Fe3O4@(StDVB), but presented in slightly lower wave numbers than those of Fe3O4. The results showed that Fe3O4 was introduced into StDVB without changing its crystal structure. The detailed morphologies of Fe3O4@(StDVB) microspheres and regenerated microspheres were obtained using scanning electron microscope and the images are shown in Figure 4. As can be seen from Figure 4(a), the microspheres were spherical with a rough surface, with particle-size distribution value of approximately 20 m. Figure 4(b) shows that there are many pores on the surface of the magnetic composite microspheres. Furthermore, the spectral image in Figure 4(c) further confirms the presence of magnetic materials in the microspheres. Figure 4(d) shows the morphologies of the microspheres after four repeated uses. The surface of the microspheres

Magnetic Porous Microspheres for DCP Adsorption

647

Intensity

(311) 35.45 (220) 30.00 (400) 42.98 (422) 53.41 (511) 57.03 (440) 62.55 (a) (b)

25

35

45

55

65

2 (degree) Figure 3. XRD patterns of (a) Fe3O4 and (b) Fe3O4@(StDVB) magnetic porous polymer microspheres.

100 nm

120 100 80 60 40 20 0

c
Fe Fe Fe 1 m

0 1 2 3 4 5 6 7 8

1 m

1 m

Figure 4. Scanning electron microscopic images of (a) Fe3O4@(StDVB) microspheres, (b) surface detail, (c) energy spectrum diagram, (d) after adsorption of microspheres and (e) surface detail.

appeared peeled owing to the effect of eluent acidity, but as can be seen from Figure 4(e), their surface still has many cavities, ensuring that the microspheres still have good adsorption capacity even after recycling several times. The TGA and differential thermal analysis (DTA) curves were obtained to determine the thermal stability and the magnetic content of the Fe3O4@(StDVB) polymer microspheres. As can be seen from Figure 5(a), in the temperature range of approximately 350460 C, the TGA curve exhibited one weight-loss step, which was accompanied with an endothermic peak at approximately 430 C in the DTA curve due to the decomposition of organic polymer. Moreover, when the temperature reached 480 C, there was an exothermic peak in the DTA curve, which can be ascribed to the rapid decomposition of the polymer. At temperatures above 550 C, no weight loss was noted, and therefore, it was very easy to determine the content of magnetic

648

Ping Yu et al./Adsorption Science & Technology Vol. 31 No. 7 2013

110 100 90 80 70
(a)

DTA (mW/mg)

TG (%)

60 50 40 30 20 10 0 0 100 200 300 400 500 600 700 800 900

86.65588 Carbon Hydrogen Magnetic material 5.402835 7.941285 (b)

10

Temperature (C) Figure 5. The TG/DTA curve of (a) Fe3O4@(StDVB) microspheres and (b) the microspheres element analysis.

materials in the polymer. From Figure 5(a), it can be seen that the magnetic content incorporated in magnetic polymer composites was 5.37%. Figure 5(b) shows the percentage of polymer composition elements, with carbon and hydrogen in the polymer being 86.66% and 7.94%, respectively. The magnetic hysteresis loop of Fe3O4@(StDVB) polymer microspheres was recorded by VSM at room temperature and is shown in Figure 6(a). From the curve, it can be observed that the

1500
(b) (a)

1000

Magnetization (emu/g)

500 0
Magnetic concentration (mg/l) 0.004 0.002 0.000 0.002 0.004 2 3 4 5 6 7 Initial pH

(c)

500 1000 1500 2000 10000

5000

5000

10000

Magnetic field (kOe) Figure 6. (a) Magnetization curve of Fe3O4@(StDVB) microspheres, (b) photographs of microspheres suspended in the presence of an externally placed magnet and (c) curve of magnetic leakage.

Magnetic Porous Microspheres for DCP Adsorption

649

Fe3O4@(StDVB) microspheres were superparamagnetic (Wang et al. 2009). Figure 6(a) also manifested that the magnetic saturation values of Fe3O4@(StDVB) microspheres were 11.19 emu/g, indicating that the microspheres have strong magnetic responsiveness. As shown in Figure 6(b), the magnetic microspheres hybrid solution could be separated by efficiently applying an external magnetic field. Moreover, Figure 6(c) suggests that the magnetic leakage of the Fe3O4@(StDVB) polymer microspheres was feeble. The results further confirmed the magnetic stability of the Fe3O4@(StDVB) magnetic porous microsphere. 3.2. Effect of pH pH is a very important factor in influencing the adsorption of 2, 4-DCP and 2, 6-DCP onto Fe3O4@(StDVB). The pH of the solution affects the degree of ionization that subsequently leads to a change in reaction kinetics and equilibrium characteristics of the adsorption process (Kumar et al. 2010). Figure 7 shows the effect of pH on the absorption of 2, 4-DCP and 2, 6-DCP onto the

9 8 7
2,4-DCP 2,6-DCP

Equilibrium pH

6
90 Adsorption capicity (mg g1)

5 4 3 2 1 2 3 4 5

80 70 60 50 40 30 1 2 3 4 5 6 7

2,4-DCP 2,6-DCP

10

Initial pH

10

Initial pH Figure 7. Effect of pH on adsorptive removal of (a) 2,4-DCP and 2,6-DCP and the (b) effect of initial pH on equilibrium pH.

Fe3O4@(StDVB) polymer microspheres. The solution pH used in the experiments ranged from 2 to 9, and Figure 7 shows that the adsorption capacity reduced with increase in pH. The adsorption performance peak appeared in pH = 2 for two kinds of solutions. One of the reason is hydrophobic interaction, which is the only force between the adsorbent and the adsorbate at low pH (pH = 2); besides, dissociated DCP molecules may decrease the effect of adsorption at a higher pH. As a result, the adsorption capacity of Fe3O4@(StDVB) decreased with the increase in pH (Pan et al. 2011). In addition, Figure 7(b) also showed that the adsorption capacity of 2, 4-DCP is higher than that of 2, 6-DCP, which may be because 2, 4-DCP is slightly soluble in water, but 2, 6-DCP is completely soluble in water. Our previous studies have shown that the solubility of 2, 4-DCP in alkaline conditions is quite higher than acidic conditions. Therefore, with the increase in solution pH, Fe3O4@(StDVB) porous microspheres also showed stronger adsorption performance for 2,4-DCP.

650

Ping Yu et al./Adsorption Science & Technology Vol. 31 No. 7 2013

3.3. Adsorption Isotherm Adsorption isotherm can well describe the adsorption process and adsorption capacity of the adsorbent at a constant temperature. Several equations have been adopted to describe the experimental data of adsorption isotherms, which indicate when the adsorption process reaches an equilibrium state (Li et al. 2010). The equilibrium data of adsorption of 2, 4-DCP and 2, 6-DCP were fitted to the Langmuir and Freundlich isotherm equation. The applicability of the isotherm models to the adsorption behaviours was studied by analyzing the correlation coefficient (R2). The Langmuir equation can be expressed as linear and non-linear forms by equations (2) and (3), respectively. Ce C 1 = + e Qe Qm KL Qm Qe = KL Qm Ce 1 + KL Ce (2)

(3)

where Qm (mg g1) is the maximum adsorption capacity; Ce is the equilibrium concentration of adsorbate (mg l1); Qe is the equilibrium adsorption capacity (mg g1) and KL represents the affinity constant. For predicting the favourability of an adsorption system, the Langmuir equation can also be expressed in terms of a dimensionless separation factor RL [equation (4)], which is defined as follows (Zhang et al. 2009): RL = 1 1 + Cm KL (4)

where Cm is the maximal initial concentration of the adsorption solution. The RL indicates the favourability and the capacity of adsorption system. When 0 < RL < 1, a good adsorption performance is indicated. The Freundlich isotherm equation can be expressed as linear and non-linear forms by equations (5) and (6), respectively. 1 lnQe = lnKF + lnCe n Qe = KF Ce1/n (5)

(6)

where KF (mg g1) and n are the adsorption constants that indicate the adsorption capacity. A value of 1/n ranging from 0.1 to 1 represents a favourable adsorption condition. Table 2 lists the adsorption isotherm constants at room temperatures. Furthermore, a comparison of the Langmuir and Freundlich isotherm models for 2, 4-DCP and 2, 6-DCP adsorption onto Fe3O4@(StDVB) microspheres was illustrated in Figure 8. From Table.2, it is obvious that the correlation coefficient that fitted to the Langmuir isotherm is higher than that of the Freundlich isotherm model. From Figure 8 it can be seen that with the increase in the solution concentration, the equilibrium adsorption capacity (Qe) for 2, 4-DCP and 2, 6-DCP increased

Magnetic Porous Microspheres for DCP Adsorption

651

TABLE 2. Adsorption Isotherm Constants for 2, 4-DCP and 2, 6-DCP onto Microspheres at 298 K Adsorption isotherm models Langmuir equation Contents R2 Qm,c (mg g1) KL (l mg1) RL R2 KF (mg g1) N 2, 4-DCP 0.997 132.834 0.153 0.017 0.702 25.244 2.732 2, 6-DCP 0.996 128.519 0.14 0.017 0.626 27.219 3.025

Freundlich equation

Note: Sorbent dose = 0.01 g; solution volume = 10.0 ml; agitation speed = 600 rpm; solution pH = 2 for 2, 4-DCP and 2 for 2, 6-DCP and contact time = 12 hours.

(a)
180 160 140

(b)

180 160 140

Qe (mg g1)

120 100 80 60 40 20 0 0 50
Experimental data at 298 K Langmuir fit Freundlich fit

Qe (mg g1)

120 100 80 60 40 20 0
Experimental data at 298 K Langmuir fit Freundlich fit

100

150

200

50

100

150

200

Ce (mg g1)

Ce (mg g1)

Figure 8. Comparison of Langmuir and Freundlich isotherm models for (a) 2,4-DCP adsorption onto microspheres and (b) 2,6-DCP adsorption onto microspheres.

sharply at first, and then increased slightly, and finally reached to maximum point. The experimental data were fitted to the Langmuir and Freundlich isotherm equations. Figure 8 shows that the Langmuir isotherm model fitted the equilibrium data much better than the Freundlich model. In addition, Figure 8 also revealed that equilibrium concentration of 2, 4-DCP is a little higher than that of 2, 6-DCP. 3.4. Adsorption Kinetics The kinetic behaviour of the adsorbents was examined by performing a series of experiments with different contact time; the adsorption kinetic data were analyzed by pseudo-first-order and pseudo-second-order equations (Anirudhan and Suchithra 2010). The pseudo-first-order equation can be expressed as linear and non-linear forms by equations (7) and (8), respectively. ln(Qe Qt ) = lnQe k1 t Qt = Qe Qe e k1t (7) (8)

652

Ping Yu et al./Adsorption Science & Technology Vol. 31 No. 7 2013

The pseudo-second-order equation can be expressed as linear and non-linear forms by equations (9) and (10), respectively t 1 t = + Qt K2 Qe2 Qe Qt =
2 k2 Qe t 1 + k2 Qe t

(9)

(10)

where Qe and Qt (mg g1) are the amounts of 2, 4-DCP and 2, 6-DCP adsorbed onto Fe3O4@(StDVB) polymer microspheres at the equilibrium and at time t (minutes), respectively. K1 (minutes1) is the equilibrium rate constant, the parameter k1 can be obtained by plotting ln (Qe Qt) versus t. K2 (g mg1 minute1) is the second-order-model rate constant and can be calculated from the plot of t/Qt versus t (Li et al. 2010). The experiment data were calculated using pseudo-first-order and pseudo-second-order equations and the results are shown in Figure 9. Compared with pseudo-first-order, pseudosecond-order equation showed better results for experimental kinetic data with higher values of

(a)

140 120

(b)

140 120

Qt (mg g1)

Qt (mg g1)

100 80 60 40 0 100 200 300 400 500 600 700

Experimental data at 298 K Pseudo-first-order rate model Pseudo-second-order rate model

100 80 60 40 0 100 200 300 400 500 600 700

Experimental data at 298 K Pseudo-first-order rate model Pseudo-second-order rate model

t (min)

t (min)

Figure 9. Comparison of pseudo-first-order and pseudo-second-order kinetic models for (a) 2,4-DCP adsorption onto microspheres and (b) 2,6-DCP adsorption onto microspheres.

correlation coefficient (R2 > 0.99), which indicated that the adsorption of 2, 4-DCP and 2, 6-DCP onto Fe3O4@(StDVB) polymer microspheres followed second-order kinetics. Figure 9 also shows that the time required to achieve adsorption equilibrium was approximately 100 and 70 minutes for 2, 4-DCP and 2, 6-DCP, respectively, which concludes that 2, 6-DCP could reach the balance status faster than 2, 4-DCP. Table 3 summarizes the comparison of the adsorption of 2,4-DCP onto different adsorbents reported in the literature (Li et al. 2009a; Sathishkumar et al. 2009; Pan et al. 2011). Obviously, although the equilibrium time was slightly longer than that of the other adsorbents, the adsorption capacity of Fe3O4@(StDVB) microspheres was prominent. The magnetic porous polymer microspheres not only had excellent adsorption performance, but can also be separated by efficiently applying an external magnetic field. The microspheres have broad application in wastewater treatment.

Magnetic Porous Microspheres for DCP Adsorption

653

TABLE 3. Comparison of the Adsorption Properties for 2, 4-DCP on Different Adsorbents Adsorbent -Cyclodextrin/attapulgite composites Maize cob carbon composites Non-covalent imprinted microspheres Fe3O4@(StDVB) magnetic porous microspheres Qmax(mg g1) 23 7 80 125 T (minutes) 400 40 50 150 Reference [26] [31] [32] This work

3.5. Adsorption Thermodynamics Thermodynamic parameters such as change in Gibbs free energy (G), enthalpy (H) and entropy (S) were calculated using equations (11) and (12) (Li et al. 2009b) Q S H ln e = R RT Ce
G = H TS

(11)

(12)

where R is the gas constant (8.314J mol1 K1) and T is the absolute temperature (K). G is Gibbs free energy, S and H represent entropy and enthalpy, respectively. The S and H values are obtained from the slope and intercept of the line plotted by ln(Qe/Ce) versus 1/t, respectively. A G value < 0 represents that the adsorption process is spontaneous, whereas H > 0 represents that the process is endothermic. Table 4 lists the obtained thermodynamic parameters. A negative G shows that the microsphere adsorption of 2, 4-DCP and 2, 6-DCP was spontaneous. As 2, 4-DCP and 2, 6-DCP were adsorbed onto the surface of microspheres, the number of water molecules in the solution decreased, but the degrees of freedom of the water molecule increased (Mellah et al. 2006). The positive values of entropy change (S) suggested increased randomness at the solidsolution interface during the adsorption 2, 4-DCP and 2, 6-DCP onto the surface of the microspheres (Pan et al. 2010). The positive value of enthalpy change (H) showed that the adsorption process was endothermic. As the temperature was increased, the adsorption of 2, 4-DCP and 2, 6-DCP onto Fe3O4@(StDVB) microspheres gradually enhanced.
TABLE 4. Thermodynamic Parameters for the Adsorption of 2, 4-DCP and 2, 6-DCP onto Microspheres Thermodynamic parameters phenol 2, 4-DCP Temperature(K) 298 308 318 298 308 318 G (kJ mol1) 19.55 20.21 20.93 18.066 18.673 19.28 H (kJ mol1) 23.28 S (J mol1 k1) 65.68

2, 6-DCP

19.95

60.69

Note: Sorbent dose = 0.01 g; solution volume = 10.0 ml; initial concentration = 50 mg/l; solution pH = 2 for 2, 4-DCP and 2 for 2, 6-DCP; contact time = 12 hours; temperature = 298 K, 308 K, 318 K.

654

Ping Yu et al./Adsorption Science & Technology Vol. 31 No. 7 2013

3.6. Regenerability Regenerability is a key factor for an effective absorbent. The adsorption and desorption experiments were repeated four times (sequentially) in order to verify the regenerability performance of the magnetic porous microspheres. Both acetic acid and sodium hydroxide were used as desorption agents, but acetic acid showed better desorption effect than sodium hydroxide. The adsorption and desorption capacities of Fe3O4@(StDVB) polymer microspheres are shown in Figure 10. As can been seen from the figure, the adsorption capacity of the microsphere decreased after four cycles. In the previous two cycles, the adsorption of phenol could almost be completely cleared. The rate of adsorption loss was calculated using equation (13) as follows:

(a)
50 40
Adsorption Desorption

Qe (mg g1)

30 20 10 0 0 1 2 3 4

Recycle numbers (b)

50 40
Adsorption Desorption

Qe (mg g1)

30 20 10 0 0 1 2 3 4

Recycle numbers Figure 10. Adsorption and desorption experiments at 298 K to evaluate the regeneration capacity of the adsorbent. Acetic acid: methanol (vol: vol) = 1: 49 as the eluent; sorbent dose = 0.01 g; solution volume = 5 ml and contact time = 12 hours.

Magnetic Porous Microspheres for DCP Adsorption

655

R=

(CF CL ) CF

(13)

where CF is the adsorption capacity of the first time, and CL is the adsorption capacity of the last time. The adsorption capacity of microspheres for 2, 4-DCP was about 15.6% loss and 20.06% loss for 2, 6-DCP, which confirm that the microspheres had favourable adsorption capacity even using them repeatedly.

4. CONCLUSIONS In this study, Fe3O4@StDVB magnetic porous microspheres were successfully synthesized based on suspension polymerization, and then the novel adsorbent Fe3O4@(StDVB) efficiently adsorbed 2, 4-DCP and 2, 6-DCP from solution systems. The resulting Fe3O4@(StDVB) microspheres had a spherical structure, porous and saturation magnetization, and all these attributes are suggestive of improved adsorption performance. A series of adsorption experiments showed that the adsorption capacity of the Fe3O4@(StDVB) microspheres for phenols was largely influenced by the pH value, the initial concentration of the solution and temperature. Between pH 2 and 9, the adsorption capacity of 2, 4-DCP is higher than that of 2, 6-DCP. The kinetic data fitted well with pseudo-second-order kinetic model than pseudo-first-order kinetic model, and 2, 6-DCP achieved balance status faster than 2, 4-DCP. The adsorption isotherms were also described by Langmuir and Freundlich isotherm models, respectively. It was found that the Langmuir isotherm model fitted the equilibrium data much better than the Freundlich model, and the equilibrium adsorption capacity of 2, 4-DCP is higher than 2, 6-DCP. The Gibbs free energy function showed that the adsorption process was spontaneous and endothermic. Furthermore, desorption experiment indicated that Fe3O4@(StDVB) microspheres were excellent reusable adsorbents. Therefore, there is a broad application prospect for these microspheres in the phonetic wastewater treatment.

ACKNOWLEDGEMENTS This work was financially supported by grants from the National Natural Science Foundation of China (Grant Nos. 21077046, 21107037, 21176107, 21174057 and 21004031) and Natural Science Foundation of Jiangsu Province (Grant Nos. BK2011461, SBK2011459 and BK2011514).

REFERENCES
An, F.Q., Du, R.K., Wang, X.H. and Wan, M. (2012) J. Hazard. Mater. 201, 74. Andini, S., Cioffi, R., Colangelo, F., Montagnaro, F. and Santoro, L. (2008) J. Hazard. Mater. 157, 599. Anirudhan, T.S. and Suchithra, P.S. (2010) Chem. Eng. J. 156, 146. Deshpande, P.A. and Madras, G. (2010) Chem. Eng. J. 161, 136. Haviv, A.H., Grenche, J.M. and Lellouche, J.P. (2010) J. Am. Chem. Soc. 132, 12519. Kieth, L.H. and Telliard, W.A. (1979) Environ. Sci. Technol. 13, 416. Kumar, N.S., Suguna, M. and Subbaiah, M.V. (2010) Ind. Eng. Chem. Res. 49, 9238.

656

Ping Yu et al./Adsorption Science & Technology Vol. 31 No. 7 2013

Kumar, N.S., Suguna, M., Subbaiah, M.V., Reddy, A.S. and Kumar, N.P. (2010) Ind. Eng. Chem. Res. 49, 9238. Laurenti, M., Guardia, P. and Contreras-Cceres, R. (2011) Langmuir 27, 10484. Li, C., Zhong, H., Zhou, L. and Zhao, G. (2010) Can. J. Chem. Eng. 6, 417. Li, K.Q. and Wang, X.H. (2009a) Bioresour. Technol. 100, 2810. Li, L., Cheng, J. and Wen, X.F. (2006) Chin. J. Chem. Eng. 14, 471. Li, Y., Li, X., Li, Y.Q., Qi, J.Y., Bian, J. and Yuan, Y.X. (2009b) Environ. Pollut. 157, 1879. Matynia, T., Cawdzik, B. and Chmielewska, E. (2003) Faculty of Chemistry, MCS University, pl, 1971. Mellah, A., Chegrouche, S. and Barkat, M. (2006) J. Colloid Interface Sci., 296, 434. Ng, Y.S., Jayakumar, N.S. and Hashim, M.A. (2010) J. Hazard. Mater. 184, 255. Pan, J.M., Yao, H. and Li, X.X. (2011) J. Hazard. Mater., 190, 276. Pan, J.M., Zou, X.H., Wang, X. and Guan, W. (2011) Chem. Eng. J. 166, 40. Pan, J.M., Zou, X.H., Wang, X., Guan, W. and Yan, Y.S. (2010) Chem. Eng. J. 162, 910. Qu, S., Huang, F. and Yu, S.N. (2008) J. Hazard. Mater., 160, 643. Sathishkumar, M., Binupriya, A.R., Kavitha, D. and Selvakumar, R. (2009) Chem. Eng. J., 147, 265. Stehlickova, L., Svab, M., Wimmerova, L. and Kozler, J. (2009) Int. Biodeter. Biodegr. 63, 923. Tai, Y.L., Wang, L. and Gao, J.M. (2011) J. Colloid Interface Sci. 360, 731. Torres, J.J., Montejano, H.A. and Chesta, C.A. (2012) Macromol. Mater. Eng. 297, 342. Wang, X., Wang, L.Y., He, X.W., Zhang, Y.K. and Chen, L.X. (2009) Talanta 78,327. Zazo, J.A., Casas, J.A., Mohedano, A.F. and Rodriguez, J.J. (2009) Water Res., 43, 4063. Zeng, X., Yu, T., Wang, P., Yuan, R., Wen, Q., Fan, Y., Wang, C. and Shi, R. (2010) J. Hazard. Mater. 177, 773. Zhang, W., Qin, L., He, X.W., Li, W.Y. and Zhang, Y.K. (2009) J. Chromatogr. A, 1216, 4560. Zhu, H.Y., Jiang, R., Xiao, L. and Li, W. (2010) J. Hazard. Mater. 179, 251.