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Adsorptive Removal of Aromatic Compounds Present in Wastewater by Using Dealuminated Faujasite Zeolite Bachar Koubaissy, Guy Joly, Isabelle Batonneau-Gener,* and Patrick Magnoux Laboratoire de Catalyse en Chimie Organique, Faculte des Sciences, Universite de Poitiers, UMR CNRS 6503, 40 Avenue du recteur Pineau, 86022 Poitiers Cedex, France ABSTRACT: The adsorption of aromatic compounds (nitrophenols, nitroaniline, chlorophenols, chloroanilines) present in wastewater using dealuminated faujasite zeolite has been investigated. The adsorption capacity of faujasite zeolite depends on the pH, (the neutral form of the pollutants is more easily adsorbed into zeolite than the dissociated form), and on the solubility in water of the aromatic compounds. The adsorption capacity for a family of compounds increases with decreasing water solubility. In this study, we have shown that the pollutant acidic character enhances their adsorption into the zeolite. Thus, the changeover of phenol to aniline decreases the adsorbentadsorbate interaction, as well as in the substitution of the NO2 group by a Cl group. The adsorption data was analyzed using the FowlerGuggenheim isotherm. The sorption mechanism of nitrophenol in faujasite zeolite was investigated using Raman spectroscopy and through a thermodesorption kinetic study. The relative affinity of the phenolic compounds toward the surface of the dealuminated faujasite was related to the electron donoracceptor complex formed between the basic sites on the zeolite (oxygen) and the hydrogens (acidic site) of the aromatic ring and of the phenols and anilines functions.
1. INTRODUCTION The aromatic compounds, particularly phenol, aniline, and their derivatives, which have a certain toxicity are considered today as microcarcinogenic and dangerous even when they exist as trace.1,2 These molecules (chloroanilines, nitroanilines,and chlorophenols) are largely used in industrial productions (pigments, pharmaceutical, dyes, pesticides) as reagents or synthesis intermediates and can be found at high concentrations in surface water contaminated by industrial wastes. Their concentration in water and soils is continuously increasing, due to their low degradability and large diffusion. To meet the stringent regulations of the European directive, many treatment technologies were developed to remove the toxic compounds from industrial wastewaters by using chemical oxidation, filtration, and activated carbon adsorption processes.35 Adsorption is a well-known separation process. It is widely applied to organic compound removal in wastewater treatment6 with high removal efficiency. It is an efficient and economic method for water decontamination applications and for separation for analytical purposes.79 The adsorbents may have a mineral, organic, or biological origin: activated carbons,1013 polymeric resins,1416 clays,17 agricultural wastes,18 mesoporous materials,19,20 and zeolites.2124 Zeolites adsorbents have been recently noted as a practical alternative to activated carbon because of the high surface area, their high selectivity, and their economic cost for regeneration after saturation.2527 In this work, the zeolite used is a faujasite type (HFAU) and consists of cubic-octahedrons called sodalite cages or β-cages. The assembly of β-cages linked together by hexagonal prisms leads into a larger cavity of diameter 13 Å called supercage. The window of the supercage is made up of 12 oxygen atoms forming a ring of diameter of 7.4 Å. β-cages are only accessible to water or ammonia, whereas supercages are accessible for water and organic compounds.28 r 2011 American Chemical Society
In our previous paper,27 we showed that the solubility and the pH of the aqueous solution play a crucial role in the adsorption of nitrophenols compounds on HFAU100 (Si/Al = 100), the optimum pH value was found to be 4. Since the physicochemical mechanisms in the sorption are complex, no simple theory of adsorption could adequately describe experimental results. Some models such as Langmuir, Freundlich, and FolwerGuggenheim have been used. On the other hand some researchers have found that high adsorption capacities of adsorbent were associated with the low solubilities of pollutants in water. For the same type of molecules, the lower the solubility of the molecule, the more important the adsorption. The saturation quantities of nitrophenols adsorbed over HFAU100 are reported in Table 1, and we also demonstrated the advantage of zeolites in the treatment of water due to their high adsorption capacities and especially their stability after regeneration while keeping these initial properties after 5 adsorption-regeneration cycles.27 In this work, our objectives are to continue to investigate the adsorption behavior of various aromatic compounds with different functions having different acidities and to study the effect of the electronegative character of some substituting aromatics, and determine the main parameters governing adsorption, in order to collect information about the mechanisms involved in the retention processes on dealuminated HFAU zeolite (HFAU100).
2. EXPERIMENTAL SECTION 2.1. Adsorbent. The dealuminated faujasite zeolite (H1,9Al1,9 Si190,1O384; Si/Al = 100, HFAU100) was supplied by Zeolyst Received: February 25, 2010 Accepted: March 11, 2011 Revised: February 1, 2011 Published: March 28, 2011 5705
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International, the micropore and mesopore volume was, respectively, close to 0.285 cm3 3 g1 and 0.056 cm3 3 g1, these characteristics were determined by adsorptiondesorption measurements at 196 C in a gas adsorption system Tristar. The microporous volume VDR was determined by Dubinin Radushkevich equation. The mesoporous volume is assumed to be the difference between the total volume and the microporous volume. It differs from ordinary acidic zeolite (H32Al32Si160O384 ; ratio Si/Al = 5) with a micropore volume equal to 0.255 cm3 3 g1. 2.2. Sorbates. 2-Nitroaniline (ONA) and 4-nitroaniline (PNA) were purchased from Acros; all other chemical compounds (dichloroanilines (DCA), chlorophenols (CP), and dichlorophenols (DCP)) were purchased from Fluka. The solutions were prepared using distilled water. The main physiochemical properties of these compounds are reported in Table 2. 2.3. Adsorption Methods. The experimental isotherms for aromatic compounds from distilled aqueous solutions on HFAU100 zeolite were measured at 298 K at constant pH. The pH of the solution was adjusted using 1 M HCl solution. For each equilibrate isotherm, 100 mg of the adsorbent was added to 200 mL of solution to equilibrate for 24 h (total equilibrium) in a batch equipment. The initial concentrations of adsorbates in water and buffer range from 1 to 500 mg 3 L1. The adsorbed amounts are calculated by mA ðQ Þ ¼ V ðC0 CÞ
The pollutant water mixture was fed into the column using in HPLC pump (Gilson 307) allowing release at a constant flow rate of 2 mL 3 min1. The solution is collected in the output of column in a graduated cylinder and then analyzed by HPLC. It is equipped with a reverse phase column (chromospher pesticides) and ultraviolet detector (254 nm, model 340) with a mobile phase of 70% methanol and 30% water at a rate of 1 mL 3 min1. 2.4. Theoretical Model. 2.4.1. Batch Reactor. The adsorption of aromatic compounds on HFAU100 zeolite adsorbents takes place in aqueous phase using a buffer solution to stabilize the pH. However, the use of a single-component model has been successfully used to describe adsorption of aromatic compound. The FowlerGuggenheim29 model follows eq 2: θ 2θω exp KC ¼ ð2Þ 1θ RT where K is the equilibrium constant for adsorption of the adsorbate on an active site (L/mol); C is the concentration at equilibrium adsorption (mol/L); ω is the empirical interaction energy between two molecules adsorbed on nearest neighboring sites (J 3 mol1); R is the ideal gas constant (8.314 J 3 mol1 3 K1); T is the thermodynamic temperature (K); and θ is the fractional coverage of the surface. FowlerGuggenheim equation is one of the simplest equations taking into account the lateral interactions. This model is based on the hypothesis that interaction energy is constant and independent of the surface fractional coverage θ, and hence the number and distribution of adsorbed molecules. 2.4.2. Flow Reactor. The empirical equation proposed by Wolborska was found to describe the breakthrough curves in a fixed bed column.30,31 The Wolborska model is described by eq 3
ð1Þ
where mA is the mass of zeolite (g), V is the volume of solution (L), C is the concentration after adsorption (mg 3 L1), C0 is the initial concentration (mg 3 L1), and Q is the amount adsorbed (mg 3 g1 of zeolite). For adsorption in a flow apparatus, stainless steel column was used with a length of 100 mm and internal diameter of 4.6 mm. The amount of HFAU100 zeolite is 0.5 g, which gives a height of bed surging from 30 to 50 mm. The adsorbed bed volumes were about 2 cm3.
lnðC=C0 Þ ¼ ðβC0 =Q ads Þt ðβ=uÞh
where C0 is initial concentration of pollutant (mol/g); Qads is the concentration of pollutant in the adsorbent (mol 3 g1); β is the external mass-transfer kinetic coefficient (min1); h is the height of the adsorbent bed (cm); and u is the flow rate of a pollutant solution (cm 3 min1). The β coefficient, which is not constant in our case, determined from the breakthrough curve, represents the interaction between the adsorbate and the adsorbent: β = a 3 Qads/C0, where
Table 1. Quantities of Nitrophenols Adsorbed over HFAU100 Zeolite at pH = 427 Qmax (mmol 3 g1)
ONP
PNP
MNP
2,4-DNP
1.73
1.05
1.02
1.52
ð3Þ
Table 2. Physicochemical Properties of Chemicals pollutants
symbol
molecular weight
water solubility
(g 3 mol1)
(g 3 L1) 1.26
molecular volume at pKa
20 C (cm3 3 mol1)
dipole moment (D)
2-nitrophenol
ONP
139.1
7.17
93.9
3.74
4-nitrophenol
PNP
139.1
12.6
7.15
94
5.7
3-nitrophenol 2,4-dinitrophenol
MNP 2,4-DNP
139.1 184.1
13.5 5.4
8.4 4.07
94 110
5.15 4.8
2-chlorophenol
OCP
128.5
28.5
8.49
100
1.33
4-chlorophenol
PCP
128.5
27.0
9.18
2,4-dichlorophenol
2,4-DCP
163.0
4.5
7.8
118
1.93
3,4-dichlorophenol
3,4-DCP
163.0
9.26
8.63
118
2.5
2,4-dichloroaniline
2,4-DCA
162.0
0.48
2.05
116
2.8
3,4-dichloroaniline
3,4-DCA
162.0
0.84
2.96
118
4.11
3,-dichloroaniline 2-nitroaniline
3,5-DCA ONA
162.0 138.1
0.84 1.2
2.51 0.26
118 95.8
3.3 4.06
4-nitroaniline
PNA
138.1
0.8
1
95.8
6.29
5706
98.5
2.11
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Figure 1. Effect of pH on the chlorophenols adsorption (Ce = 5 mg L1), (() 2,4-DCP, (þ) 3,4-DCP, (2) PCP, and (0) OCP.
a represents the slope of the curve (interaction strength between the adsorbate and the adsorbent), Qads is the quantity of pollutant adsorbed at the equilibrium, and C0 is the initial pollutant concentration. For saturation capacity we use Qmax. In a previous work,27 this model has been used to describe the entire curve. For competitive adsorption, the breakthrough of non-desorbed compound has a form similar to a compound absorbed without competition. To describe the breakthrough curve of desorbed compounds we propose the model below: 0
βa C2, 0 B Bexp a2, 0 C2 B ¼B B Cm @ exp βh u
!1 C C C C C A
þ
" ! βC 1 2exp a 2, 0 t 1=2 βh a2, 0 exp a u
0 < t < t 1=2
!# βa C2, 0 exp 2t 1=2 t a2, 0 t 1=2 < t < ¥ !1 0 βa C1, 0 B C Bexp a1, 0 t C C B C ðCm 1ÞB C B βh A @ exp u
3. RESULTS AND DISCUSSION 3.1. Adsorption of Chlorophenols Isomers over FAU Zeolite. 3.1.1. Influence of the pH on Chlorophenols Adsorption. In
C2 C1
0 < t < t 01=2
"
2.5. Thermodesorption Analysis. A thermodesorption experiment has been performed to analyze aromatics desorption from a HFAU100 zeolite, using a microbalance (Symetric thermogravimetric analyzer Setaram B24) coupled with a mass spectrometer (Balzer Thermostar). Temperature and sample weight are continuously recorded. The experiment used a carrier gas controlled by a mass flowmeter, at a flow rate of 2 L 3 h1. The heating rate is fixed at 10 C 3 min1, from an ambient temperature up to 800 C. The initial sample weight was about 50 mg in this experiment. 2.6. Raman Spectroscopy. The surface functional groups and adsorptive form of organic compounds were identified using Raman spectroscopy. The measurements were made on PerkinElmer NIR FT-Raman spectrometer GX 2000 (laser Nd:YAG, λ = 1064 nm). The Raman spectra were recorded at room temperature in the range between 400 and 4000 cm1.
β C1 , 0 0 1 ðCm 1Þ 2exp a t βh a1, 0 1=2 exp a u !# βa C1, 0 C2 exp 2t 1=2 t a1, 0 C1 0 t 1). This desorption corresponds to 18% of the maximum amount adsorbed and indicates that 2,4-DNP is more favorably adsorbed than 2,4-DCP over HFAU100 zeolite. Adsorption capacity of 2,4-DNP is higher (Table 5) despite the slightly lower solubility of 2,4-DCP. So this result seems to be related to the electron donation properties of Cl substituent compared to electron withdrawing groups such as -NO2. Indeed, the effect of electron donation of Cl group by mesomeric effect increases the electronic density of the aromatic ring structure. At the same time, the hydroxyl group acidic character decreases (pKa decreases from DCP to DNP), and also the acidity of the hydrogen of aromatic ring (results confirmed by RMN Table 6), and thus leads to a decrease of the adsorption capacity. So, the adsorption occurs especially between acidic hydrogen of the molecule and the zeolite basic oxygen. This result is correlated with other studies34 which showed that the increase in electronegativity of aromatic structure reduces significantly the adsorption capacity of the compounds.
Figure 5. Adsorption isotherms obtained on HFAU100 zeolite for ONA(2) and PNA (9) (a) at lower concentrations for pH = 4 and (b) at higher concentrations for pH = 4.
To extend this hypothesis, a study was carried out with aniline derivatives. 3.2. Adsorption of Nitroanaline and Chloroaniline over HFAU100. The various aniline derivatives (nitroanilines, ONA and PNA, and chloroanilines, 2,4-DCA, 3,5-DCA and 3,4-DCA) were investigated under the same operating conditions; we have been able to compare the behavior of these compounds during adsorption on HFAU100 zeolite. 3.2.1. Adsorption of Nitroaniline Compounds over FAU100 Zeolite. Adsorption isotherms of ONA and PNA are reported in Figure 5. It was observed (Table 3) that the interactions (ω) between adsorbed molecules are similar as are the quantities adsorbed at saturation (Qmax = 210220 mg 3 g1). However the equilibrium constant for adsorption of the adsorbate on the active sites (K) is higher for ONA than for PNA. It can be noticed that the solubility of both molecules in water is relatively low and similar (Table 2). 3.2.2. Adsorption of Different Chloroaniline Compounds over HFAU100 Zeolite. The evolution of zeolite adsorption capacity as a function of Cl atoms position on the aromatic ring of aniline was also studied at pH = 4, in order to compare these results with those obtained previously. The various parameters are reported in Table 3. The HFAU100 adsorption capacities for 2,4-DCA are more important than for the capacities corresponding to 3,4-DCA and 3,5-DCA. This may be due to its lower solubility in water (450 mg 3 L1 compared with 840 mg 3 L1 for both 3,4-DCA and 3,5DCA). Different authors34,35 have studied the influence of acidity 5709
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Figure 6. Capacity of the different compounds adsorbed at equilibrium on HFAU100 zeolite at pH = 4.
on adsorption for different types of adsorbent and have concluded that the molecules with an acid character have more affinities with basic adsorbents. The various chloro- and nitro-derivatives of aniline were studied under the same conditions of pH, so we could compare their behavior over HFAU100. In Table 3, the adsorption capacities are reported in mmol 3 g1 for these compounds. It is shown that nitro-anilines have maximal adsorption capacities greater than those of chloro-anilines, despite lower solubility of the 2,4-DCA compared with the nitroanilines compounds (Table 2). This result can be explained by the less basic character of nitroanilines compounds, and at the same time by their molar volumes, which are lower than for dichloroanilines (Table 2). Furthermore, 3,5-DCA adsorbs slightly better than the 3,4DCA, despite their identical water solubilities; however, 3,4DCA is slightly more basic than the first one (pKa2 = 2.96 for the 3,4-DCA and 2.51 for 3,5-DCA). Both capacities (Qmax) are not strongly different but the differencies of the K constant are not negligible (Table 3). Pan et al.35 in a study of phenol derivative adsorption (especially nitro and chloro- phenols) over polymer concluded also that the molecule pKa plays an important role in the adsorption process. 3.3. Comparison of Adsorption Evolution during the Changeover of the Phenol to the Aniline. In the first part of our previous study,27the major role of the solubility of various pollutants in water on the adsorption capacities on zeolite have been demonstrated. To compare the results obtained in the case of nitrophenols with those obtained for nitroanilines, we summarize in Figure 6 the different results of experiments in static adsorption of phenol and aniline derivatives on the HFAU100 zeolite in terms of molecules per supercage. The number of molecules per supercage has been obtained using eq 4: Number of molecules per cage ¼
Qmax NA N cages per g of HFAU100
ð4Þ
where Qmax is the quantity adsorbed at saturation equilibrium on HFAU100 (mmol 3 g1); NA is Avogadro’s number; N cages per g
Figure 7. Breakthrough curves for the equimolar mixture adsorption of the (0) ONA/ ()) ONP in water on HFAU100 zeolite at pH = 4.
is the number of cages per 1 g of HFAU100 (=2.3 1020 per gram). This number is obtained by considering that there is a direct relationship between the proportion porous volume and the supercage number per gram of zeolite, noting that for a dealuminated zeolite HY having a porous volume equal to 0.341 cm3 per gram, the supercage number per gram is 3.77 1020. With the exception of ONP, the substituted aniline derivatives are always better adsorbed than similar phenol derivatives, but the latter ones have the highest solubility. To analyze the influence of the actual changeover of NH2 to OH, it is necessary that the other parameters influencing adsorption are the same (position and nature of the groups on the cycle, nondissociated form is majority, and especially have the same solubility). From all the results obtained, it is possible to compare the ONP and ONA sorption properties on HFAU100. ONP and ONA solubilities are very close, 1.26 g 3 L1 and 1.20 g 3 L1, respectively. We can notice that ONP is slightly more adsorbed on zeolite (4.7 molecules per cage) compared to ONA (4.5 molecules per cage). To confirm the predominance of ONP for a better adsorption, a competitive adsorption in dynamic conditions was undertaken. Foremost, a competitive adsorption between ONP and ONA was studied from an equimolar mixture (1.8 mmol 3 L1 for each compound) at pH = 4. 5710
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Table 7. Parameters Values from the Breakthrough Curves of the ONP/ONA Equimolar Mixture in Contact with HFAU100 Zeolite (pH = 4) compounds 1
Qads max (mg.g )
ONP
ONA
160
109
R(ONP/ONA)
1.98
KH(ONP)/KH(ONA)
1.06
Table 8. Protons Chemical Shift for ONP and ONA
Figure 8. Count of the mass spectrometer signal calibrated on the ( 3 3 3 ) ONP, (---) PNP, (—) OCP main peak as a function of temperature (C) in the desorption of these compounds from HFAU100 zeolite.
Table 9. Raman Bands Vibration for ONP Alone and for ONP Occluded in HFAU100 Zeolite The breakthrough curve of ONP and ONA in the competition adsorption is presented in the Figure 7. The figure shows a preferential adsorption of ONP. In batch conditions the adsorption capacity of ONP was only slightly higher than that of the ONA but in competitive adsorption, the affinity toward ONP becomes more important and a significant desorption of the ONA is observed on the breakthrough curve which exhibits a maximum at C/C0 = 1.4. The adsorption capacities are reported in Table 7 and show that the presence of the ONP modifies completely the ONA adsorption which decreases from 220 mg 3 g1 when it is alone (Table 3) to 80.4 mg 3 g1 in the presence of ONP. The adsorption is favored for the ONP with an adsorption capacity two times higher than that of ONA. We may notice that the ratio of Henry constants is 1.06. The influence of the functional group on the behavior of pollutant in the adsorption over HFAU100 zeolite is clearly demonstrated: the acidic hydrogen of the phenolic compounds is more attracted by the zeolite oxygen than those of aniline compounds. Hydrogen of aromatic ring present on ONP is more acid than that of ONA (this result is confirmed by RMN, Table 8). We can therefore observe that phenol function promotes adsorption compared with the aniline function. Furthermore it is possible to confirm this result from all adsorption tests carried out. Indeed, if no other compounds have structures and solubilities identical, it is possible to compare the influence of changeover (from OH to NH2) in adsorption using compounds with similar adsorption capacities but different solubilities. Thus the 3,4-DCP and 3,4-DCA have similar adsorption capacities (about 3.5 molecules per cage), while 3,4-DCA has a very much lower solubility (0.84 g 3 L1) than 3,4-DCP (9.26 g 3 L1). Differences in capacity must be important; this is not the case even if 2,4-DCA is slightly more adsorbed. So this deduction confirms the predominance of the phenol function (at same solubility) on the aniline function during the adsorption over HFAU100 zeolite. 3.4. Approach of the Interaction AdsorbentAdsorbate. To understand the adsorption mechanism, we have proposed to study the interaction energies between the different compounds
ν (cm1)
ONP
ONP occluded
ν CH
1180
1191
ν CO
1248
1255
ν CdC
1454
1455
ν NO asy ν CdC
1530 1588
1538 1590
ν CH
3072
3086
and the HFAU100 zeolite; for that thermodesorption and Raman studies were carried out. 3.4.1. Thermodesorption. Thermodesorption is usually used in adsorption to collect information about the interaction energy between organic compounds and adsorbent. The corresponding desorption average temperature is proportional to the adsorbent/organic compound interaction energy. On other hand, the study carried out in our laboratory27 showed if different peaks appear on the thermodesorption curve, each peak corresponds to an adsorption on a particular site type. Figure 8 shows that PNP is desorbed at a temperature higher than ONP. However, it was observed before that ONP is much more adsorbed on zeolite HFAU100 than PNP (Figure 6). This indicates that the interaction energies between adsorbent and organic compounds are very low and are the hydrogen bonding type. The energy required to establish this kind of interaction varies between 0.5 and 30 kJ 3 mol1. Here, the boiling temperatures correspond to the molecular interactions and are more important than the adsorbateadsorbent interactions. PNP has the highest boiling point (279 C) compared to ONP (210 C) and OCP (175 C). There is a good correlation between the desorption temperatures of these compounds and their boiling points. This result confirms the polarity secondary role. The weak adsorbateadsorbent interactions were already apparent during the fitting of the different adsorption isotherms by the FowlerGuggenheim model: the shape S is typical of this weak interaction. 3.4.2. Raman Spectroscopy. The sorption mechanism of nitrophenol on HFAU100 zeolite has been investigated using Raman spectroscopy. The different Raman bands in the case of 5711
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Industrial & Engineering Chemistry Research the ONP and ONP occluded state in HFAU100 zeolite are presented in Table 9. After the adsorption; the bands corresponding to (aromatic CH) at 3070 and 1180 cm1, and the bands corresponding to (NO) at 1530 cm1 were strengthened, but the other ones at 1586 and 1454 cm1 (CdC) did not change. This indicates that ONP was adsorbed principally by hydrogen bonding between zeolite oxygen and the hydrogens of the aromatic cycle and the ones of functional group. The other bands did not seem to be affected by adsorption.
4. CONCLUSION Adsorption of organic aromatic compounds from water was studied. The adsorption capacity increased with decreased pH of the solution (up to pH = 4), also the molecules possessing a neutral forms are preferentially adsorbed. A linear relationship was observed between the adsorption capacities and the solubility for the same family compounds. Then, the role of the substituent acidic character was studied, and it was demonstrated that the changeover of NO2 to Cl, or OH to NH2 was a factor in decreasing of the adsorption capacity into the zeolite. The acidic character increase of functional hydrogen and of the aromatic ring hydrogen promotes the adsorption on the zeolite basic oxygens. The dynamic adsorption studies toward aniline derivatives confirm the results obtained in static conditions, and the breakthrough curves on adsorbent were experimentally determined and predicted by Wolborska modified model. Competitive adsorption between various compounds shows the important role of the substituent where ONP remarkably decreased ONA adsorption and 2,4-DNP desorbed 2,4-DCP. The proposed sorption mechanism involving a physical interaction takes place in adsorption over HFAU100 zeolite as hydrogen bond interactions. ’ AUTHOR INFORMATION Corresponding Author
*Tel.: 33 5 49 45 34 04. E-mail:
[email protected].
’ ACKNOWLEDGMENT B. Koubaissy wishes to acknowledge the “Region PoitouCharentes” for his scholarship. ’ REFERENCES (1) Chao, W.; Guanghua, L.; Zhuyun, T.; Xiaoling, G. Quantitative Structure-Activity Relationships for Joint Toxicity of Substituted Phenols and Anilines to Scenedesmus obliquus. J. Environ. Sci. 2008, 20, 115. (2) Damborskyl, J.; Wayne Schultz, T. Comparison of the QSAR Models for Toxicity and Biodegradability of Anilines and Phenols. Chemosphere 1997, 34, 429. (3) Milone, C.; Fazio, M.; Pistone, A.; Galvagno, S. Catalytic Wet Air Oxidation of p-Coumaric Acid on CeO2, Platinum and Gold Supported on CeO2 Catalysts. Appl. Catal., B 2006, 68, 28. (4) Jarusutthirak, C.; Amyb, G.; Croue, J. P. Fouling Characteristics of Wastewater Effluent Organic Matter (EfOM) Isolates on NF and UF Membranes. Desalination 2002, 145, 247. (5) Laszlo, K.; Podkoscielny, P.; Da-browski, A. Heterogeneity of Activated Carbons with Different Surface Chemistry in Adsorption of Phenol from Aqueous Solutions. Appl. Surf. Sci. 2006, 252, 5752. (6) Busca, G.; Berardinelli, S.; Resini, C.; Arrighi, L. Technologies for the Removal of Phenol from Fluid Streams: A Short Review of Recent Developments. J. Hazard. Mater. 2008, 160, 265.
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(7) Han, Y.; Quan, X.; Shuo Chen, S.; Zhao, H.; Cui, C.; Zhao, Y. Electrochemically Enhanced Adsorption of Aniline on Activated Carbon Fibers. Sep. Purif. Technol. 2006, 50, 365. (8) Chen, K. H.; Tsai, W. T.; Shie, J. L.; Chen, Y. H.; Chang, C. F.; Chang, C. Y. Adsorption of Naphthalene on Zeolite from Aqueous Solution. J. Colloid Interface Sci. 2004, 277, 29. (9) Ahmaruzzaman, M. Adsorption of Phenolic Compounds on Low-Cost Adsorbent. Adv. Colloid Interface Sci. 2008, 143, 48. (10) Mollah, A. H.; Robinson, C. W. Pentachlorophenol Adsorption and Desorption Characteristics of Granular Activated Carbon—II. Kinetics. Water. Res. 1996, 12, 2907. (11) Fernandez, E.; Hugi-Cleary, D.; Lopez-Ramon, M. V.; Stoeckli, F. Adsorption of Phenol from Dilute and Concentrated Aqueous Solutions by Activated Carbons. Langmuir 2003, 19, 9719. (12) Chingombe, P.; Saha, B.; Wakeman, R. J. Effect of Surface Modification of an Activated Carbon on the Sorption of 2,4-Dichlorophenoxy Acetic Acid and Benazolin from Water. J. Colloid Interface Sci. 2006, 302, 408. (13) Potgieter, J. H.; Bada, S. O.; Potgieter-Vermaak, S. S. Adsorptive Removal of Various Phenols from Water by South African Coal Fly Ash. Water SA 2009, 35, 89. (14) Zhang, W.; Chen, J.; Pan, B.; Zhang, Q. Modelling Cooperative Adsorption of Aromatic Compounds in Aqueous Solutions to Nonpolar Adsorbent. Sep. Purif. Technol. 2006, 49, 130. (15) Robberson, K. A.; Waghe, A. B.; Sabatini, D. A.; Butler, E. C. Adsorption of the Quinolone Antibiotic Nalidixic Acid onto AnionExchange and Neutral Polymers. Chemosphere 2006, 63, 934. (16) Lin, S.; Juang, R. Adsorption of Phenol and its Derivatives from Water Using Synthetic Resins and Low-Cost Natural Adsorbents: A Review. J. Environ. Management 2009, 90, 1336. € Ozcan, € € (17) G€ok, O.; A.; Ozcan, A. Adsorption Kinetics of Naphthalene onto Organosepiolite from Aqueous Solutions. Desalination 2008, 220, 96. (18) Delval, F.; Crini, G.; Vebrel, J. Removal of Organic Pollutants from Aqueous Solutions by Adsorbents Prepared from an Agroalimentary By-Product. Bioresour. Technol. 2006, 97, 2173. (19) Qin, Q.; Ma, J.; Liu, K. Adsorption of Nitrobenzene from Aqueous Solution by MCM-41. J. Colloid Interface Sci. 2007, 315, 80. (20) Cooper, C.; Burch, R. Mesoporous Materials for Mater Treatment Processes. Water Res. 1999, 33, 3689. (21) Reungoat, J.; Pic, J. S.; Manero, M. H.; Debellefontaine, H. Adsorption of Nitrobenzene from Water onto High Silica Zeolites and Regeneration by Ozone. Sep. Sci. Technol. 2007, 42, 1447. (22) Khalid, M.; Joly, G.; Renaud, A.; Magnoux, P. Removal of Phenol from Water by Adsorption Using Zeolites. Ind. Eng. Chem. Res. 2004, 43, 5275. (23) Carvalho, R. H.; Lemos, F.; Cabral, J. M. S.; Ribeiro, F. R. Influence of the Presence of NaY Zeolite on the Activity of Horseradish Peroxidase in the Oxidation of Phenol. J. Mol. Catal. B 2007, 44, 39. (24) Carvalho, R. H.; Lemos, F.; Lemos, M. A. N. D. A.; Cabral, J. M. S.; Ribeiro, F. R. Electro-oxidation of Phenol on Zeolite/Graphite Composite Electrodes: Part 1. Electrochemical Behaviour over NaY Zeolite. J. Mol. Catal. A 2006, 248, 48. (25) Laborde-Boutet, C.; Joly, G.; Nicolaos, A.; Thomas, M.; Magnoux, P. Selectivity of Thiophene/Toluene Competitive Adsorptions onto NaY and NaX Zeolites. Ind. Eng. Chem. Res. 2006, 45, 6758. (26) Tago, T.; Nakasaka, Y.; Kayoda, A.; Masuda, T. Preparation of Hydrophilic Silicalite-1 Nanocrystal-Layered Membrane for Separation of Water from WaterAcetone Solution by Pervaporation. Sep. Purif. Technol. 2007, 58, 7. (27) Koubaissy, B.; Joly, G.; Magnoux, P. Adsorption and Competitive Adsorption on Zeolites of Nitrophenol Compounds Present in Wastewater. Ind. Eng. Chem. Res. 2008, 47, 9558. (28) Baerlocher, C.; Meier, W. M.; Olson, O. H. Atlas of Zeolite Framework Types, 5th rev. ed.; Elsevier: Amsterdam, The Netherlands, 2001. (29) Fowler, R. H.; Guggenheim, E. A. Statistical Thermodynamics, Theory of the Properties of Matter in Equilibrium; Cambridge University Press: New York, 1965. 5712
dx.doi.org/10.1021/ie100420q |Ind. Eng. Chem. Res. 2011, 50, 5705–5713
Industrial & Engineering Chemistry Research
ARTICLE
(30) Wolborska, A. Adsorption on Activated Carbon of p-Nitrophenol from Aqueous Solution. Water Res. 1989, 23, 85. (31) Wolborska, A. External Film Control of the Fixed Bed Adsorption. Chem. Eng. J. 1999, 73, 85. (32) Yousef, R. I.; El-Eswed, B. The Effect of pH on the Adsorption of Phenol and Chlorophenols onto Natural Zeolite. Colloids Surf. A 2009, 334, 92. (33) Wu, J.; Yu, H. Biosorption of Phenol and Chlorophenols from Aqueous Solutions by Fungal Mycelia. Process Biochem. 2006, 41, 44. (34) Wagner, J.; Schulz, S. Adsorption of Phenol, Chlorophenols, and Dihydroxybenzens onto Unfunctionalized Polymeric Resins at Temperatures from 294.15 to 318.15 K. Chem. Eng. J. 2001, 46, 322. (35) Pan, B. C.; Zhang, X.; Zhang, W. M.; Zhang, Q. X. Adsorption of Phenolic Compounds from Aqueous Solution onto a Macroporous Polymer and Its Aminated Derivative: Isotherm Analysis. J. Hazard. Mater. 2005, 121, 233.
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