Chemical Product and Process Modeling

Volume 4, Issue 5 2009 Article 8

S PECIAL I SSUE - WCCE8 2009

A New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

Maria Gomez Jose Luis Gomez Hans Peterson Maria Dolores Murcia Nick Christo

Edinburgh Napier University, maria.gomez@um.es Murcia University, carrasco@um.es Edinburgh Napier University, md.murcia@um.es Safe Drinking Water Foundation, hans.peterson@hotmail.com Edinburgh Napier University, n.christo@napier.ac.uk

Copyright c 2009 The Berkeley Electronic Press. All rights reserved.

A New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

Maria Gomez, Jose Luis Gomez, Maria Dolores Murcia, Hans Peterson, and Nick Christo

Abstract
The adsorption of 4-chlorophenol on an expanded commercial clay used in water purication has been studied. Experiments using 4-chlorophenol concentrations of 50, 100, 250, 500, 750, 1000, 1250 and 1500 mg L-1 were carried out in column reactors at 25o C. A new adsorption kinetics equation has been developed based on the equation for the variation in solute concentration in the liquid phase, representing the difference between the adsorption rate minus the desorption rate that at equilibrium represents the Langmuir isotherm. This was used to derive a new nite equation for the development of the adsorption curve. KEYWORDS: 4-chlorophenol, adsorption, clay, kinetic model, wastewater

We would like to thank the Maxit Group for the sample of Filtralite MC 1.5-2.5 mm. During this study M. Gomez and M. D. Murcia were beneciaries of a postdoctoral grant from Fundaci on S eneca (Comunidad Aut onoma de la Regi on de Murcia, Spain).

Gomez et al.: New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

1.

INTRODUCTION

In general, chlorophenols are used as agricultural chemicals, pharmaceuticals, biocides and dyes. However, they are also widely used for the extraction of sulphur and nitrogen from coal, as an intermediate in the synthesis of dyes and drugs, as a denaturant in alcohol or as a solvent in the refining of oils, in the herbicide 2,4-dichlorophenol, the germicides 4-chlorophenol-o-cresol and 2,4chlorophenol. It has been reported that the global production of chlorophenols is 100,000 t/a, where 35,000-40,000 t/a represent chlorophenols with 4 or 5 chorine atoms and 60,000 t/a include chlorophenols with less than 4 chlorine atoms. It is widely known that the chlorophenols are toxic compounds. Chlorophenols are listed pollutants by the US EPA in the Clean Water Act and by the European Directive 2455/2001/EC. Besides, the European Pollutant Emission Register classifies chlorophenols within the group called phenols. In this classification, Spain and the UK lead the list of European countries for the direct discharge of phenol into receiving waters. Not all the substitution sites on the phenol molecule are equal with respect to their toxic effect on organisms since the location of the chlorines affects the efficiency of microbial breakdown. Among the monochlorophenols, 4chlorophenol (parachlorophenol) is much more toxic than either 2- or 3chlorophenol. The 50% Lethal Dose (LD50) of 4-chlorophenol for rats is 261 mg kg-1 for oral doses and 1390 for percutaneous injection. There are many methods to remove phenolic compounds from wastewaters. Although much research have been done in this area, none of the proposed methods are completely satisfactory and all have advantages and disadvantages. Current methods for the removal of these compounds include biological, chemical and physical treatments. Microorganisms and free and immobilised soluble enzymes have proved to be an effective method for removing phenolic compouds. Microorganisms have the advantage that the phenolic compounds are used as carbon source, which leads to a high degree of elimination, although the high quantity of biomass which is produced may be considered a disadvantage. Some of the microorganisms that have been used to remove phenolic compounds include the following: Comamonas terrigena N3H (Zamocky et al., 2001), Neurospora crassa (Luke et al., 2001), Phanerochaete chrysosporium, Aspergillus Niger, Aspergillus terreus and Geotrichum candidum (Garca et al., 2000), Candida tropicales (Jurez et al., 2001), Pseudomonas putida (McLaughlin et al., 2006), Agrobacterium spp. and Pseudomonas spp. (Chin et al., 2000), mixed cultures (Soda et al., 1999), Pseudomonas fluorescens (Chauhan and Thakur, 2002), Pseudomonas

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testosterona, Pseudomonas aeruginosa and Agrobacterium radiobacter (Lu et al., 1996) and Pseudomonas pictorum (Chitra et al., 1995). On the other hand, the use of enzymes has no resulting biomass since the phenolic compounds are transformed into insoluble polymers that precipitate from the bulk solution. Although, in this case, there is the disadvantage that enzyme activity may be lost through inhibition and/or deactivation phenomena, and coprecipitation with polymers may occur if the enzyme is used in its soluble form. The use of peroxidase (E.C.1.11.1.7) to remove phenolic compounds from aqueous solutions was first proposed by Klibanov and colleagues (Klibanov et al., 1980; Klibanov and Morris, 1981) and, since then, the method has been extensively researched to maximise technical and economic factors. The main improvement was the immobilization of the peroxidases which leads us to treat large volumes of wastewaters. Reactors containing immobilized enzymes are desirable because of the high cost of enzymes (Tatsumi et al., 1996). The main advantage of the immobilization enzymes is to have a support that does not increase the final cost of the process. The chemical oxidation of toxic and hazardous organic pollutants is often carried out using single oxidants such as chlorine, ozone, UV radiation, hydrogen peroxide, etc. However, decomposition by conventional treatments may be difficult if pollutants are present in low concentrations or if they are especially resistant to the oxidants used. Among the methods considered, photochemical degradation of the contaminants in water is of particular interest and potential. The use of UV radiation and strong chemical oxidizing agents constitutes one type of many combined advanced oxidation processes (AOPs) (Pera-Titus et al., 2004), that can be particularly effective in the removal of toxic chlorophenols from water and wastewater (Ghaly et al., 2001; Ledakowicz et al., 2001; Silva et al., 2004; Sun et al., 2006). The main disadvantage of these treatments is the formation of photoproducts that can be as toxic or more toxic that the previous pollutants. Among the physical methods, the most widely used is adsorption onto the surface of activated carbon in wastewater treatment. Although activated carbons are among the most effective adsorbent, their high cost has stimulated interest in examining the feasibility of using cheaper raw materials. Many others materials have been used as adsorbents. Kuleyin (2007) used a surfactant-modified zeolite to study the adsorption characteristics of phenol and 4-chlorophenol. Carmona et al. (2006) studied the adsorption of phenol on Amberlite IRA-420, and Kamble et al. (2008) used other types of zeolite to adsorb phenol and o-chlorophenol. Recently, modified clay has been of considerable interest because of its low cost and better adsorption capability. There are many studies of the adsorption on phenolic compounds in modified clay including rectorite (Huang et al., 2008), tetramethyl ammonium- and tetramethyl phonium-exchanged montmorillonite (Lawrence et al., 1998), inorganic-organic pillared montmorillonite (Wu et al.,

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Gomez et al.: New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

2001), Ca-montmorillonite (Yu et al., 2004), bentonite (Mortland et al., 1986), sepiolite (Yildiz and Gr, 2007) and porous clay heterostructure (Arellano et al., 2005). The adsorption of phenols on clays has been explained using a number of mathematical models. The adsorption of these phenolic compounds on clay materials usually follows the Langmuir or Freundlich equations. The kinetics of the adsorption in these kind of adsorbent materials has also been described using the well-known first order Lagergren rate equation (Huang et al., 2008; Vimonses et al., 2008) which, with the nomenclature adopted in this work, can be written as:
dC L = k1 (CSeq CS ) dt

(1)

where CSeq and CS are the concentrations of solute adsorbed on the solid phase at equilibrium and time t, respectively, CL is the concentration of solute in the liquid phase at time t and k1 is the pseudo-first order adsorption rate constant. Using the same nomenclature, the second order equation derived by Ho and Mckey (1999) and later used by Kuleyin (2007) and Vimonses et al. (2008) is the following:
dC L 2 = k 2 (CSeq CS ) dt

(2)

where k2 is the pseudo-second order adsorption rate constant. The intraparticle diffusion model presented by Kobya (2004) and later used by Kuleyin (2007) is expressed as: log R = log k id + log t (3)

where R is the percentage of adsorbed chlorophenols, t is the contact time, is the gradient of linear plots, and kid may be taken as a rate factor. A further kinetic model is the Elovich model (Bekta et al., 2004) given by the following equation: q t = ln ( ) + ln t (4)

where qt is the concentration of solute adsorbed at time t and and are the rate constants for Elovich model. In this work, an expanded commercial clay was used to adsorb different concentrations of 4-chlorophenol. The equilibrium experimental data have been

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Chemical Product and Process Modeling, Vol. 4 [2009], Iss. 5, Art. 8

fitted to a Langmuir equation and from the classical mechanism that gives this isotherm type a new adsorption kinetics model is proposed and compared with first and second order ones. 2. MATERIALS AND METHODS The expanded clay is a commercial product (Filtralite MC 1.5-2.5 mm) manufactured by the Maxit Group in Norway. Filtralite is made of illite clay that consists of layers of aluminosilicate, repeating tetrahedron-octahedron-tetrahedron layers with potassium in the interlayer spaces that resist swelling and has a cation exchange capacity of between 20-30 meq/100 g. The average chemical composition of the expanded clay is shown in the Table 1. Table 1. Chemical composition, average values SiO2 (%) 62 Al2O3 (%) 18 FeO3 (%) 7 K2O (%) 4 MgO (%) 3 CaO (%) 3 Na2O (%) 2 Ctot (%) 0.02

The adsorption experiments were carried out in a jacketed glass column. Water from the thermostatic bath maintained the reactor column at 25C. 20 g of expanded clay were placed inside the column together with 40 mL of a 4chlorophenol solution with initial 4-chlorophenol concentration, CL0, in the range of 50 to 1500 mg L-1. The 4-chlorophenol solutions were pumped using a single peristaltic pump from the bottom to the top of the reactor. The flow rate was kept constant at 20 mL min-1 in all the assays. Samples (0.5 mL) from the column were taken at regular time intervals and 4-chlorophenol concentrations, CL, were measured by a colorimetric standard method (Greenberg et al., 1992) using solutions of potassium ferricyanide (83.4 mM in 0.25 M sodium hydrogencarbonate solution) and 4-aminoantipiryne (AAP; 20.8 mM in 0.25 M sodium hydrogencarbonate solution). Aliquots of the sample (0.8 mL) were placed in a spectrophotometer cuvette (1 mL) together with 0.1 mL of ferricyanide solution and 0.1 mL of AAP solution. After a few minutes to allow the colour to develop fully, absorbance was measured at 505 nm against a blank. Absorbance values were transformed to 4-chlorophenol concentrations by using a calibration curve (CL = 126.95 A505, r=0.999). 3. THEORY: THE NEW ADSORPTION KINETIC MODEL Several authors have described the kinetics of the adsorption process by first or second order kinetic models. However, these are empiric equations that are not

http://www.bepress.com/cppm/vol4/iss5/8 DOI: 10.2202/1934-2659.1400

Gomez et al.: New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

deduced from the Langmuir equation. It is very well established that the Langmuir isotherm is a consequence of the following equation for the overall adsorption rate: dC L = k ad C L (1 ) k des (5) dt Where, the first term in the second part of the equation is the adsorption rate and the second one the desorption rate. is the active centre fraction of adsorbent that in time t becomes occupied by the adsorbed molecules of solute, and is given by the following equation:
= CS CSmax

(6)

Where, CSmax is the maximum concentration that is possible to adsorb when the total active centres are occupied by the adsorbed species. Taking into account equation (6), equation (5) can be rewritten as:

dC L CS C = k ad C L k des S 1 dt CSmax Csmax

(7)

Multiplying and dividing the last fraction of the second term of equation (7) by kadCL, taking into account the definition of the adsorption equilibrium constant, K = kads/kdes, and making transformations, equation (7) can be expressed as:
1 + KC L dC L = k adC L 1 CS KC C dt Smax L

(8)

Considering the following approximation: 1 + KCLeq 1 + KC L 1 = KCSmax C L KCSmax C Leq CSeq (9)

And taking into account that, if V and m are the volume of liquid phase and the mass of solid phase, respectively, the mass balance equations for the solute, at time t and in the equilibrium, are given by:

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Chemical Product and Process Modeling, Vol. 4 [2009], Iss. 5, Art. 8

V(C L0 C L ) = mCS
V(C L0 C Leq ) = mC Seq and by grouping the constant terms:

(10) (11)

k=

k ad (CL0 CLeq )

(12)

the equation (8) can be expressed as:

dC L = k C L (C L C Leq ) dt

(13)

with the initial condition: t = 0; CL = CL0, the equation (13) can be integrated as:
C L C Leq ln C L = k C Leq t ln C C C Leq L0 L0

(14)

Finally, defining for 4-chlorophenol, which is the solute used to test the model, the adsorption progress, X4CP, with the following relation:
X 4CP = C L0 C L C L0

(15)

Equation (14) can be written as: X 4CP a 1 e bt = 1 ae bt

(16)

with the parameters a and b derived from: a =1 CLeq C L0 b = k ad C Leq C k ad Leq (CL0 CLeq ) C L0 (17)

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Gomez et al.: New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

4. EXPERIMENTAL RESULTS
4.1 Isotherm type and equilibrium constant

Several experiments with different 4-chlorophenol concentration (50, 100, 250, 500, 750, 1000, 1250 and 1500 mg L-1) were carried out. The experimental equilibrium data fitted well to the Langmuir isotherm: CSeq = KCSmax C Leq 1 + KCLeq (18)

with a correlation coefficient of 0.9984. Figure 1 shows the isotherm for the clay. The values of CLeq and CSeq in all the cases are the mean of the last three samples taken from the column. From the fit, the values obtained for the product KCSmax and for the equilibrium constant, K, were 11.28 L kg-1 and 2.04x10-3 L mg-1, respectively, and, from these values, the maximun adsorption capacity of the clay for 4-chlorophenol can be established as 5529.4 mg kg-1.
2500

2000

Cs (mg / kg)

1500 Cs (mg/kg) 1000 Cs_model

500

0 0 100 200 300 400

CL (mg / L)

Figure 1. Clay isotherm for 4-chlorophenol at 25 C.

4.2 Adsorption kinetics: checking the model and comparison with first and second order adsorption models

The experimental data for the adsorption progress curves of 4-chlorophenol with time have been fitted to equation (16) using the Curve Expert program and the parameters a and b generated. High regression coefficients were obtained in all the cases, as seen in Table 2. In Figure 2, the variation of calculated values of a
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Chemical Product and Process Modeling, Vol. 4 [2009], Iss. 5, Art. 8

and b, together with an experimental value of a obtained directly from the equation for a in (17) and the experimental data of CLeq and CL0, are plotted according to equations (17). Table 2. Parameters for the proposed model CL0 (mg L-1) 50.0 100.0 250.0 500.0 750.0 1000.0 1250.0 1500.0
1.0 0.8

a 0.941 0.858 0.832 0.798 0.815 0.768 0.723 0.736

b a (Eq. 17) 0.005 0.923 0.017 0.877 0.011 0.859 0.012 0.825 0.009 0.816 0.017 0.796 0.023 0.774 0.021 0.771

R 0.9864 0.9853 0.9806 0.9688 0.9955 0.9800 0.9671 0.9829

Parameters

y = -1.3071x + 1.031 0.6 0.4 0.2 0.0 0.00 y = 0.0841x R = 0.5764

2

R = 0.9631

a b a experimental

0.05

0.10

0.15

0.20

0.25

CLe q/CLo

Figure 2. Variation of parameters a and b with CLeq/CL0. It can be seen that the variation of the parameters with CLeq/CL0 is very close to those predicted by the model. In addition, from the slope of the parameter b it is possible to obtain an approximate value of the adsorption rate constant, kad = 0.0841 min-1, and, from this value and the previously estimated for the equilibrium constant, K, a value of 41.23 mg L-1 min for the desorption rate constant can be calculated. In Figure 3C all the experimental values of adsorption progress for 4chlorophenol and those calculated by the model are presented over time for all the experimental conditions assayed, demonstrating a good level of accuracy. In Figure 3A and 3B, the progress curves for first and second order kinetic models,

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Gomez et al.: New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

calculated by fitting the experimental data to Equation (23) and (28) of Appendix, are, also, presented.
1.0 0.8 0.6 0.4 0.2

A
X50exp X100exp X250exp X500exp X750exp X1000exp

Adsorption progress, X

0.0 0.8 0.6 0.4 0.2 0.0 0.8 0.6 0.4 0.2 0.0 0 100 200 300 400

X1250exp X1500exp Model

Time (min)

Figure 3. Variation with time of experimental and calculated adsorption progress for all 4-chlorophenol initial concentrations and the different kinetic models. (A) first order model, (B) second order, (C) the proposed model. The parameter values and correlation coefficients, R, for the first and second order kinetic models, are shown in Tables 3 and 4, respectively. Table 3. Parameters for the first order kinetic model CL0 (mg L-1) 50.0 100.0 250.0 500.0 750.0 1000.0 1250.0 1500.0 a1 0.881 0.804 0.773 0.754 0.772 0.731 0.684 0.700 b1 0.057 0.084 0.051 0.044 0.036 0.054 0.067 0.061 R 0.9847 0.9558 0.9498 0.9355 0.9815 0.9527 0.9365 0.9585

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Chemical Product and Process Modeling, Vol. 4 [2009], Iss. 5, Art. 8

Table 4. Parameters for the second order kinetic model CL0 (mg L-1) 50.0 100.0 250.0 500.0 750.0 1000.0 1250.0 1500.0 a2 0.082 0.111 0.060 0.053 0.042 0.065 0.073 0.069 b2 0.084 0.126 0.070 0.064 0.049 0.081 0.097 0.089 R 0.9861 0.9892 0.9855 0.9751 0.9964 0.9871 0.9821 0.9922

Finally, in Figure 4 the calculated values of the adsorption progress from the proposed model and the ones calculated with first and second order models are plotted together with the experimental ones.
1.0 y = 0.9992x

X4CP order1

0.8 0.6 0.4 0.2 0.0

R = 0.9352

y = 1.0006x

X4CP order2

0.8 0.6 0.4 0.2 0.0

R = 0.9759

y = 1.0039x

X4CP model

0.8 0.6 0.4 0.2 0.0 0.0

R = 0.9681

0.5

1.0

Xexp

Figure 4. Calculated adsorption progress from first and second order models and from the proposed model over the experimental one.

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Gomez et al.: New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

From Figure 4 we can see that the three models show a good degree of agreement with the experimental data. The highest deviations were for the first order kinetic model and the best results for the second order model. For the proposed model, the level of accuracy with experimental data is very similar to the one obtained with the second order model, being no significant differences between these two models. The principal advantage of the proposed model over the others is that it can obtain an estimation of the intrinsic adsorption and desorption rate constants, kad and kdes, that is not possible using the others models, as they are basically, empirical models and, as such, their rate constants are not intrinsic values but apparent. 5. CONCLUSIONS This work shows that the expanded clay used is an effective adsorbent for the removal of 4-chlorophenol at 25C. The equilibrium adsorption data were fitted by the Langmuir isotherm obtaining a correlation coefficient of 0.9984. From the equation for the variation in 4-chlorophenol concentration in the liquid phase, representing the difference between the adsorption rate minus desorption rate that at equilibrium gives the Langmuir isotherm, a new adsorption kinetics equation has been developed. This is used to derive a new finite equation for the adsorption progress curve. The progress curves of 4-chlorophenol adsorption for all experimental conditions were fitted to this equation using the Curve Expert program giving a good fit between the experimental data and those predicted by the kinetic model. In addition, the experimental data were fitted to first and second order kinetic models. The highest deviations were obtained for the first order kinetic model and the best results were obtained with the second order model, where the level of accuracy with experimental data is very similar to that obtained with the proposed model. However, with the proposed model we can obtain an estimation of the intrinsic adsorption and desorption rate constants that is not possible using the others models, as they are basically empirical models. 6. NOMENCLATURE a a1 a2 b b1 model parameter defined in Eqs. (17), dimensionless first order kinetic parameter defined in Eqs. (24), dimensionless second order kinetic parameter defined in Eqs. (29), min-1 model parameter defined in Eqs. (17), min-1 first order kinetic parameter defined in Eqs. (24), min-1
11

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b2 CL CS CLeq CSeq CL0 CSmax K k kad kdes k1 k2 m t V X4CP X4CPeq

second order kinetic parameter defined in Eqs. (29), min-1 4-chlorophenol concentration in the liquid phase, mg L-1 4-chlorophenol concentration in the solid phase, mg kg-1 4-chlorophenol equilibrium concentration in the liquid phase, mg L-1 4-chlorophenol equilibrium concentration in the solid phase, mg kg-1 initial 4-chlorophenol concentration in the liquid phase, mg L-1 4-chlorophenol maximum concentration in the solid phase, mg kg-1 adsorption equilibrium constant, L mg-1 parameter defined in Eq. (12), L mg-1 min-1 adsorption rate constant, min-1 desorption rate constant, mg L-1 min-1 pseudo-first order adsorption rate constant, min-1 pseudo-second order adsorption rate constant, L mg-1 min-1 mass of adsorbent, kg time, min volume of liquid phase, L 4-chlorophenol adsorption progress at time t, dimensionless 4-chlorophenol adsorption progress at equilibrium, dimensionless active centre fraction of adsorbent occupied by 4-chlorophenol at time t, dimensionless

7. APPENDIX: ADSORPTION PROGRESS CURVES FOR FIRST AND SECOND ORDER KINETIC MODELS
First order kinetic:

With the nomenclature used in this work, the adsorption rate for a first order model is given by the following equation:
dC L = k 1 (C Seq C S ) dt

(19)

Taken into account the Eqs. (10) and (11) for the mass balance of solute, the difference CSe CS can be expressed as:

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Gomez et al.: New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

(C

Seq

CS ) =

V (C L C Leq ) m

(20)

Substituting Eq. (20) into Eq. (19) we obtain:

dC L k 1 V (C L C Leq ) = dt m

(21)

and, integrating Eq. (21) with the initial condition: t = 0, CL = CL0, the variation of CL along time is obtained:

C L = C Leq + (C L0 C Leq )e

k1V t m

(22)

Finally, taken into account the definition of adsorption progress, Eq. (22) can be expresed as:
X 4CP = a 1 1 e -b1t

)
and b1 =
k 1V m

(23) (24)

where:

a1 = X4CPeq

From the model parameters, a1 and b1, the equilibrium conversion, X4CPe, and the pseudo-first order rate constant, k1, can be obtained.
Second order kinetic:

In a similar way, the adsorption rate for a second order model is given by the following equation:
dC L = k 2 C Seq C S dt

)2

(25)

Now, taking into account Eq. (20), we obtain: dC L k 2 V 2 (C L C Leq )2 = 2 dt m (26)

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Chemical Product and Process Modeling, Vol. 4 [2009], Iss. 5, Art. 8

and, integrating Eq. (26) with the initial condition: t = 0, CL = CL0, the variation of CL along time is obtained:
C L = C Leq + (C L0 C Leq ) k V2 1 + 2 2 (C L0 C Leq ) t m

(27)

And, finally, taking into account again the definition of the adsorption progress, Eq. (27) can be expressed as:
X 4CP = a 2t 1+ b2t

(28) k 2V2 C L0 X 4CPeq m2

being: a 2 =

k2V2 C L0 X 2 4CPeq 2 m

and b 2 =

(29)

For this model, the equilibrium conversion, X4CPeq, is the quotient of the model parameters, a2/b2. 8. REFERENCES Arellano, S., Gallardo, T., Osorio, G., Lpez, M.S., Gmez, B. 2005. Adsorption of phenol and dichlorophenols from aqueous solutions by porous clay heterostructure (PCH). J. Mex. Chem. Soc., v.49, p.287-291. Bekta, N. Aim, B.A., Kara, S. 2004. Kinetic and equilibrium studies in removing lead ions from aqueous solutions by natural sepiolite. J. Hazard. Mater., v.112, p.115-122. Carmona, M., De Lucas, A., Valverde, J.L., Velasco, B., Rodrguez, J.F. 2006. Combined adsorption and iron exchange equilibrium of phenol on Amberlite IRA-420. Chem. Eng. J., v.117, p.155-160. Garca, I., Jimnez, P.R., Bonilla, J.L., Martn, A., Martn, M.A., Ramos, E. 2000. Removal of phenol compounds from olive mill wastewater using Phanerochaete chrysosporium, Aspergillus Nger, Aspergillus terreus and Geotrichum candidum. Process Biochem., v.96, p.214-220. Chauhan, N., Thakur, I.S. 2002. Treatment of pulp and paper mill effluent by Pseudomonas fluorescens in fixed film. Pollut. Res., v.21, n.4, p.429-434. Chin, W.C., Mei, L.C., Jen, L.C., Shang, C.N., Zong, H.C. 2000. Biodegradation of 2,4,6-trichlorophenol in the presence of primary substrate by immobilized pure culture bacteria. Chemosphere, v.41, p.1873-1879.

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Gomez et al.: New Kinetic Model for 4-Chlorophenol Adsorption on Expanded Clay

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http://www.bepress.com/cppm/vol4/iss5/8 DOI: 10.2202/1934-2659.1400

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