Research Article

Received: 21 December 2010 Revised: 26 February 2011 Accepted: 5 April 2011 Published online in Wiley Online Library: 12 May 2011

(wileyonlinelibrary.com) DOI 10.1002/jctb.2646

Sorptive sequestration of 2-chlorophenol by zeolitic materials derived from bagasse y ash

Bhavna Shah,a Ritesh Tailora and Ajay Shahb
Abstract
BACKGROUND: Water pollution by toxic organic compounds is of great concern and increasingly there are demands for effective sorbents to remove them. Bagasse y ash, a sugar industry solid waste with disposal problems, was utilized as a source for the synthesis of zeolitic material. The efciency of virgin and synthesized material was examined for the sorption of 2-chlorophenol. RESULTS: Zeolitic materials have been synthesized by alkaline hydrothermal and fusion methods. Zeolite P and Analcime were the major components of the zeolitic material. These materials were characterized by XRF, PXRD, FTIR and SEM and were found to have improved morphology with new crystalline phases. Batch sorption experiments for the removal of 2-chlorophenol by virgin and zeolitic materials were carried out to evaluate isotherm capacities and kinetics of sorption processes. The Langmuir isotherm better ts the equilibrium data which concur with physical sorption. Kinetic studies showed better correlation coefcients for pseudo-second-order and intraparticle diffusion model, conrming that the sorption rate was controlled by lm diffusion followed by pore diffusion. Desorption studies were performed to regenerate the activity of the spent sorbents. The practical utility of sorbents was tested by column study. CONCLUSION: Bagasse y ash, readily available at very low cost was successfully converted into zeolitic material. The synthesized zeolitic material showed enhanced capacities for the sorption of 2-chlorophenol and can be utilized as a low cost sorbent for treatment of phenolic waste-water. c 2011 Society of Chemical Industry Keywords: 2-chlorophenol; modied bagasse y ash; sorption; kinetics; desorption; column

INTRODUCTION
The occurrence of various organic chemicals in natural water sources presents a major obstacle to the use and reuse of water resources. Thus, the removal of organic contaminants from water and waste-water has become a major focus of research. Among various organic pollutants, phenol and its analogues has been the subject of great concern, as they are both toxic and carcinogenic when present at elevated levels in the environment. They cause adverse effect on receiving bodies and hence are recognized as pollutants by US Environmental Protection Agency (EPA),1 imparting unpleasant taste and odour to drinking water and exerting negative effects on different biological processes. They are common contaminants in the waste-waters from various industries such as high temperature coal conversion, petroleum rening, resins, and plastics. These compounds cause serious environmental problems since their biological degradation occurs too slowly or not at all.2 The removal of phenolic compounds from water is difcult owing to the high cost of treatment. Various methods exist for their removal from aqueous solutions, i.e. coagulation, reverse osmosis by membrane ltration, electrochemical oxidation, catalytic oxidation, ion exchange, biological methods, enzyme treatment, solvent extraction, advanced oxidation processes, disinfection by ozone, activated sludge, photo-catalysis, sorption, etc.4,5 Among these, sorption is the most versatile and widely used for their

removal.6 9 A number of workers6 9 have used different materials as adsorbents. Activated carbon has frequently been used to remove various phenolic compounds from water,10 but it is very costly and so recently the search for low-cost sorbents has grown.6,8 Extensive work has been done to access the conversion of coal y ash into zeolites,11 17 but apart from one earlier study,18 there are no reports on the conversion of bagasse y ash into zeolites. In this present study, attempts have been made to develop a low-cost sorbent using bagasse y ash (BFA) by converting it into zeolitic sorbents (ZBFA). The virgin and nal products have been examined for the removal of 2-chlorophenol (2-CP) from a simulated water system. In continuation of our study on batch mode operation, this report also deals with the design, operation, and performance of a xed bed BFA and CZBFA column for removal

Correspondence to: Bhavna Shah, Department of Chemistry, Veer Narmad South Gujarat University, Surat-395007, Gujarat, India. E-mail: bhavna606@gmail.com

a DepartmentofChemistry,VeerNarmadSouthGujaratUniversity,Surat-395007, Gujarat, India

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b Science and Humanities Department, Vidyabharti Polytechnic Trust, Umrakh, Bardoli-394 345, Surat, Gujarat, India

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B Shah, R Tailor, A Shah for 4 h in a hot air oven. The dried BFA sieved through 90120 m mesh was used for sorption studies. Conventional hydrothermal treatment of BFA The dried BFA material, 200 m mesh, was suspended in a 3 mol L1 NaOH solution (10 : 1 liquid/solid ratio) and reuxed for 72 h with intermittent stirring at 373 5 K. The resultant mixture was ltered and washed with doubly distilled water until free from sodium hydroxide and dried at 373 10 K. The dried zeolitic material (CZBFA) was passed through a 90120 m mesh sieve and used for sorption of 2-CP. The yield of the nal product (CZBFA) was about 75 5%. Fusion treatment of BFA The dried BFA, 200 m mesh, was mixed and ground with sodium hydroxide in a predetermined ratio (NaOH/BFA = 1.2 w/w) to obtain a homogeneous mixture. The mixture was fused in a stainless steel crucible at 823 10 K for 1.5 h. The resultant fused product was cooled to room temperature, ground further and added to 128 cm3 of doubly distilled water. The slurry was agitated mechanically for 12 h at room temperature and was then crystallized under static conditions at 363 K for 6 h. At the end of the process, the resultant solid was separated by ltration. Repeatedly washing with doubly distilled water removed excess sodium hydroxide and the solid was dried at 373 10 K. The dried zeolitic material (FZBFA) was passed through a 90120 m mesh sieve. The yield of the nal product (FZBFA) was about 82 5%. The dried BFA and zeolitic materials (CZBFA and FZBFA) were stored in airtight desiccators until required. Sorbate All of the reagents used were Merck and Rankem chemicals of A.R. grade. The stock solution of 2-CP (1000 mg L1 ) was prepared, stored in a brown coloured glass bottle and diluted to desired concentration with doubly distilled water. The initial 2-CP concentration (C0 ) was ascertained before the start of each experimental run. Batch operations Batch experiments were carried out to determine the equilibrium time and for the development of sorption isotherms. All the batch experiments were performed using a solution of 2-CP (25 cm3 , 100 mg L1 initial concentration (C0 )) at 303 K, unless otherwise noted, with 90 m sized sorbents (BFA, CZBFA, and FZBFA). The mixture was held in an airtight stoppered conical ask (50 cm3 ) and agitated at 150 rpm in an incubator shaker until equilibrium was attained. The effect of different operational variables, namely pH (212), dosage (0.510 g L1 ), initial 2-CP concentration (50300 mg L1 ), temperature (303333 K) and agitation time (124 h) were examined. After xed time intervals, a sample of solution was removed, ltered through Whatman lter paper No. 42 (pore size ca 2.5 m) and the concentration of solute measured. Blank experiments for each study without sorbent showed no decline in the solute concentration, indicating no sorption by either the container or lter material. The amount of solute sorbed per gram of sorbent (qt ), at different times (t) was calculated. Each experiment was repeated three times (standard deviation value < 0.0057) and the mean values taken. The initial pH (pH0 ) of the 2-CP solutions was adjusted using 1 mol L1 solution of NaOH or HCl.

Table 1. Physico-chemical properties of BFA, CZBFA, and FZBFA Values obtained Characteristics Proximate analysis Loss on drying (%) Moisture content (%) Ash content (%) Physico- properties Specic density Bulk density (g cc1 ) Dry density (g cc1 ) Void ratio Porosity (fraction) pHpzc BET surface area Chemical constituents SiO2 % Al2 O3 % Fe2 O3 % CaO % MgO% Na2 O % K2 O % BFA 12.56 0.2 11.69 0.3 75.84 0.2 1.93 0.02 1.75 0.02 1.16 0.02 0.690 0.408 8.07 0.05 45.6 47.44 20.45 5.76 5.12 4.59 4.66 3.45 CZBFA 15.63 0.2 12.11 0.3 70.45 0.2 2.04 0.02 1.98 0.02 1.31 0.02 0.556 0.359 8.62 0.05 368.3 43.89 18.75 3.89 3.12 3.45 6.79 2.46 FZBFA 18.44 0.2 16.18 0.3 65.55 0.2 2.15 0.02 2.13 0.02 1.39 0.02 0.539 0.350 8.67 0.05 464.7 44.87 19.46 2.89 3.22 4.01 7.46 2.24

of 2-chlorophenol. To simulate the design of column operation knowledge of sorption isotherms and ow dynamics is essential. The results of these ndings are discussed in the present paper.

MATERIALS AND METHODS

Instrumental methods The physico-chemical characteristics of sorbents were determined using standard procedures.19 A pH meter (Equip-Tronics, micro controller pH meter, model EQ-621) was used to measure the pH of solutions. The BrunauerEmmettTeller (BET) specic surface area of the sorbents were measured by adsorption of nitrogen at 77 K using a Micromeritics automatic surface area analyzer (Gemini 2360, Shimadzu, Japan) at CSMCRI, Bhavnagar, India. The point of zero charge (pHpzc ) for BFA and synthesized zeolitic materials were determined by mass titration as proposed by Noh and Schwarz.20 X-ray uorescence (XRF) analysis was performed using an X-ray XDL-B (Fischer scope, Japan). The moisture contents of the sorbents were determined by a Karl-Fischer (1204R of VMHI) instrument. The data obtained are given in Table 1. FT-IR spectra were recorded on a Thermo-Nicolet iS-10 Fourier Transform Infrared (FT-IR) spectrometer from 4000 to 400 cm1 . Powder X-ray diffraction (PXRD) patterns of the sorbents were carried out using a Panalyticals X Pert Pro instrument at Panjab University, Panjab, India employing nickel ltered CuK radiations. Chlorophenol concentration was measured at max 274 nm using a UV-Visible spectrophotometer (UV-Visible EV 300, Thermo Nicolate). Raw material (bagasse y ash) Bagasse y ash (BFA), blackish gray in colour was procured from a local sugar mill, Shree Khedut Sahkari Khand Udhyog Mandali Ltd., Bardoli, Gujarat, India. The BFA was washed thoroughly with doubly distilled water, dried in sunlight for 8 h and then at 353 K

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Sorption of 2-chlorophenol by modied bagasse y ash Column study A glass column (10 0.5 cm), containing (BFA or CZBFA) was prepared with 1.0 g of sorbent (90120 m mesh) on glass wool support. The weighed material was slurried with hot water and fed slowly into the column to avoid air entrapment.21 The sorbate solution of known concentration was loaded onto the column, and allowed to percolate through the column under gravity (ow rate = 0.5 cm3 min1 ). The concentration of sorbate leaving the column was measured to determine the amount of 2-CP retained. At about 90% sorption capacity the column operation was stopped. The chosen method for operation of a xed bed sorber is to a large extent dependent on the shape of the breakthrough curve obtained by plotting C/C0 versus time or volume. For most sorption processes in water and waste-water treatment, breakthrough curves exhibit a characteristic S shape but with varying degrees of steepness and breakpoint positions. The breakthrough capacity of the column was determined by loading BFA and CZBFA at pH 2.0 with 2-CP concentration (0.4 mg cm3 ) using a plot of C/C0 against volume (Ve ).

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RESULTS AND DISCUSSION

Characteristics of sorbents The chemical and mineralogical compositions of the BFA, CZBFA and FZBFA as their stable oxides obtained using an XRF technique are summarized in Table 1. The amounts of SiO2 and Al2 O3 within zeolites (CZBFA and FZBFA) were a little lower than the corresponding oxides in the original BFA. This may be due to dissolution of the glass phase (aluminium-silicate) into the alkaline solution during treatment. During hydrothermal treatment, alumina and silicate ions are condensed to form an aluminasilicate gel, which is the source material for zeolite crystals on the outer surface of BFA particles. An increase in Na2 O content of CZBFA and FZBFA is caused by the captured of sodium ions neutralizing the negative charge on the aluminate in the zeolite structure when zeolite crystals are formed.11 Alkali fusion enhances the dissolution of y ash converting most of the ash into sodium silicate and aluminate and the calcium magnesium oxides and other components were reduced after synthesis. This indicates that these impurities dissolved in the alkaline solution during the hydrothermal synthesis of CZBFA and FZBFA. The physicochemical properties obtained by classical methods are presented in Table 1. BET surface area follows the order FZBFA (464.7 m2 g1 ) > CZBFA (368.3 m2 g1 ) > BFA (45.6 m2 g1 ) indicating that, following treatment of the BFA, the surface area of the zeolitic sorbents has been increased signicantly. The pHpzc values obtained by mass titration method were 8.07, 8.61 and 8.67 pH for BFA, CZBFA, and FZBFA, respectively. FT-IR analysis FT-IR spectra of BFA, CZBFA, and FZBFA (gure not shown) showed a broad band between 3700 and 3100 cm1 indicating the presence of OH groups on the surface. This stretching frequency arises from both the silanol groups (SiOH) and sorbed water (peak at around 3400 cm1 ). The band between 1250 and 850 cm1 can be ascribed to TO4 (where T = Si, Al) asymmetric stretching vibrations of internal tetrahedra. The bands between 720 and 650 cm1 and between 420 and 500 cm1 can be due to symmetric stretching and bending mode of these internal tetrahedral, respectively. The shift of the band maximum of 1096.34 cm1 in the unzeolitized BFA to 1022.33 cm1 in CZBFA

Figure 1. PXRD patterns of BFA, CZBFA, and FZBFA.

conrms the tetrahedral coordination of aluminium in the zeolite framework. For FZBFA, shifting of the bands from 1096.34 to 981.13 cm1 and 795.07 to 765.92 cm1 conrm the formation of zeolite phases, which can be assigned to asymmetric and symmetric stretching of internal tetrahedra (TO4 ) of amorphous aluminosilicates formed by the reaction of dissolved Si4+ and Al3+ .12,16 Decrease in frequency of the asymmetric stretching vibration of tetrahedra indicates that the amount of aluminium is increased in tetrahedral sites of the aluminosilicate framework. The bands at about 1651 and 1441.11 cm1 are attributed to deformation of OH vibration of absorbed water and bending vibration of H2 O.12 PXRD analysis Analysis of sorbents by powder X-ray diffraction provides dspacing values of their corresponding minerals and crystalline phases. The identication of crystalline characteristics and mineralogy of sorbents was made by comparing the diffraction data against a database maintained by the International Centre for Diffraction Data and the data provided by Joint Committee on Powder Diffraction Standards (JCPDS).22 The powder X-ray diffraction patterns of BFA, CZBFA, and FZBFA are shown in Fig. 1. A large wide peak at low diffraction angle in the BFA diffraction pattern indicates the presence of a glass phase.17 The diffractogram of BFA shows -quartz peaks (JCPDS 5490), several small peaks of mullite (JCPDS 150776), a small peak of stilbite and other amorphous materials.23 CZBFA shows a comparatively at and weak peak after treatment and also gives several new sharp diffraction peaks which were not seen in BFA. The most intense new peaks at 2 = 15.97 and

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www.soci.org 2 = 26.13 , can be attributed to the formation of zeolites, with positive identication of zeolite P (Phillipsite, JCPDS 390219), analcime (JCPDS 760901), and chabazite (JCPDS 120194). The observed d-spacing values of phillipsite (P) = 6.95, 4.22, 3.74, 3.66, 3.32, 2.89, 2.68, 1.97, 1.89, 1.80, 1.71, 1.68 and analcime (A) = 5.54, 4.82, 3.41, 2.27, 2.22, 1.74 in CZBFA indicate their presence as major constituents.13 The PXRD pattern of FZBFA shows the peak at low diffraction angle is even more suppressed compared to BFA and CZBFA. The crystalline phases identied in the FZBFA were zeolite P (JCPDS 390219), analcime (JCPDS 760901), zeolite A (JCPDS 1490), zeolite X (JCPDS 281036), and calcined ZSM 12 (JCPDS 15274). Zeolite P and analcime were dominant in the zeolites formed by fusion. From the disappearance of quartz and mullite peaks, it is reasonable to deduce that both quartz and mullite in the BFA have reacted with NaOH during fusion to form sodium aluminosilicates. The results for the FZBFA are probably related to the fact that more aluminosilicates have been dissolved in the solutions due to the formation of sodium silicates during fusion and amorphous aluminosilicates during crystallization. SEM analysis Scanning electron microscopic (SEM) analysis has been useful in understanding the surface morphology of solid materials. SEM micrographs of BFA, CZBFA, and FZBFA are shown in Fig. 2 at 500 magnication. The SEM image of BFA shows a brous structure with large irregular silicate masses and a lamellar structure with large but shallow pore size and strands in each fold. BFA also possesses irregular shapes and surfaces. The SEM micrograph shows the presence of spherical particles in CZBFA and FZBFA due to the alkaline treatment, which reduces the glass phase as shown in X-ray diffraction patterns.17 After treatment, the particles of CBZFA and FZBFA seem to be more uffy and porous. This may be due to changes in the surface of the particles, which show crystalline forms with compact structures. The SEM micrograph of CZBFA shows honeycomb apertures and holes indicating the sorbent to be more porous than BFA. Furthermore, the surface shows hollow particles with interior voids, creating more folded strands with deeper pores. The SEM micrograph of FZBFA exhibits trapezohedral analcime crystals approximately 10 m in size with morphology similar to that reported by Lin et al.13 Overall, the transformation of y ash to different zeolite phases can be demonstrated by SEM, albeit with some crystals (with the exception of analcime) not very distinct. In the case of FZBFA the agglomeration of particles to form clusters can be expected due to its softer texture. Batch sorption studies Effect of pH The sorption of 2-CP (Fig. 3) was found to decrease gradually with increasing pH of solution (up to 8 pH) for BFA, CZBFA, and FZBFA and after pH 8 a sharp decrease was observed up to pH 12. The pH dependent behaviour of 2-CP can be explained by considering the surface charge of the sorbents (pHpzc ) and the ionization of 2-CP (pKa = 8.56). At pH < pHpzc , a positive charge is developed at the oxide surface of the sorbents and also at low pH the presence of H+ suppresses the ionization of 2-CP. At pH > pHpzc the sorbent possess a negative charge on the surface and 2-CP is ionized to form phenolate ions which are repelled by the negatively charged surface, hence, the decrease in sorption at pH > 8.5 pH. Similar results were reported by Kao

B Shah, R Tailor, A Shah

Figure 2. SEM micrographs of BFA, CZBFA, and FZBFA at 500X magnication.

et al.24 and Gupta et al.25 The maximum soprtion of 2-CP at pH 2 could be due to dispersive interactions which are promoted in solutions with pH values below the pHpzc of the sorbent, at which repulsive interactions between the charged surface groups and uncharged molecules are minimized. So, it can be assumed that 2CP molecules are sorbed on the sorbents mainly through dispersive forces as suggested by Coughlin and Ezra.26 In addition, another sorption mechanism may be expected based on the formation of donoracceptor complexes between the surface basic groups (electron donors, e.g. OH, oxides) and the aromatic rings of 2-CP. Therefore, it may be concluded that the combined effects of all these factors, namely, pHpzc of sorbents, pKa of 2-CP, and tendency to form donoracceptor complexes play an important role during sorption of 2-CP on the surface of BFA, CZBFA, and FZBFA. The 2-CP uptake at 2 pH after 360 min is 28.02, 44.99, 48.22 mg g1 by BFA, CZBFA, and FZBFA, respectively, with the sorption efciency following the order FZBFA > CZBFA > BFA.

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www.soci.org comparable with those obtained by Gupta et al.3 on red mud and higher than the value (2-CP = 0.21 mg g1 ) reported by Shiundu et al. on rice husk.32 The Freundlich isotherm plot of ln qe versus ln Ce gives a straight line with lower correlation coefcients than Langmuir (Table 2). The multilayer sorption capacity, Kf , of sorbent was in the range 11.50 to 40.98 L g1 . The value obtained for FZBFA is comparable with a reported value for activated carbons (51 L g1 ).10 The value of heterogeneity factor n > 1 indicates intense sorption but the correlation coefcients are lower than for the Langmuir isotherm. This observation could also be attributed to molecular interaction between the sorbate species and subsequent aggregation in the surface monolayer. Such mechanistic paths could explain the conformity of our data with both Langmuir and Feundlich isotherms for all the systems studied. The D-R isotherm model presumes a pore lling mechanism in micropores of the sorbent, rather than layer-by-layer formation of a lm on the walls of the pores. The slope of the plot gives the value of and the intercept yields the value of sorption capacity, Xm (23.8646.63 mg g1 ) (Table 2). The sorption mechanism whether ion-exchange or physical in nature, can be deduced from the value of sorption energy, E, calculated using the value of slope of the plot . If the magnitude of E is between 8 and 16 kJ mol1 , the sorption process follows by ion-exchange, while for values of E < 8 kJ mol1 , the sorption process is of a physical nature.33 The values of sorption energy E were found to be < 8 kJ mol1 (Table 2) thus suggesting physisorption. The value of correlation coefcient of BFA is close to unity, which indicates that BFA data also better t the D-R isotherm due to its variable micro- and meso-porous nature as observed in the N2 sorption isotherm (gure not shown). The sorption capacity Xm was found to be less than that for the Langmuir isotherm (Table 2). In the Temkin isotherm model plots of qe versus ln Ce enable determination of the isotherm constants KT and B1 . The values of KT and B1 obtained are shown in Table 2. For BFA, the Temkin equation represents the poorest t of experimental data. The R2 value obtained for FZBFA is very close to its value for the Langmuir isotherm. This indicates that the heat of sorption of all the molecules in the layer decreases linearly with coverage due to sorbentsorbate interactions. So, the sorption of 2-CP on FZBFA can be characterized by a uniform distribution of the binding energies, up to some maximum binding energy. The sorption data of 2-CP on BFA follows the order Langmuir D-R > Freundlich > Temkin while sorption data of 2-CP on CZBFA and FZBFA follows the order Langmuir > Temkin > Freundlich > D-R. Effect of temperature The temperature dependence of a sorption process is a complex phenomenon. Thermodynamic parameters, such as the heat of sorption and the energy of activation play an important role in predicting the sorption behaviour as both are strongly dependent on temperature. The sorption of 2-CP on BFA, CZBFA, and FZBFA increased with increase in temperature indicating that the process is endothermic. Similar results were reported by Tutem et al. for the sorption of chlorophenols on bituminous shale.34 The rise in temperature also causes more dissociation of the 2-CP molecule. However, it is plausible to explain the effect of temperature mainly on the basis of hydrogen bonding.35 In an aqueous solution of 2-CP there is extensive hydrogen bonding between 2-CP molecules and water, resulting in appreciable solubility. These hydrogen bonds become broken at higher temperature and this would cause 2-CP

Figure 3. Effect of pH on the sorption of 2-CP by BFA, CZBFA, and FZBFA.

Effect of initial 2-CP concentration and dosage The uptake of 2-CP increases with increase in initial concentration (C0 ) for all systems (gure not shown). This is due to the availability of a large number of vacant sorbent sites and a high concentration gradient between the solution and the solid phase. C0 provides the necessary driving force to overcome the resistances to the mass transfer between the aqueous and solid phases.27 The increase in C0 also enhances the interaction between 2-CP and sorbents. Initially, the rate of removal of 2-CP was rapid and then slowed down as the dose concentration increased. The initial rise in sorption with sorbent or sorbate concentration is probably due to a stronger driving force, larger available surface area, and more sorption sites. The rate of sorption is higher initially as the sites on the sorbents are vacant and easily accessible by the sorbates. As the sorbent dose increases, the removal of sorbates also increases until the sorbant becomes saturated by the sorbate (2-CP) and removal tends to a constant value. Sorption isotherms Four sorption isotherm models were used to t the equilibrium sorption data in order to design the sorption system; the linearized equations of all isotherms have been obtained from published work: Langmuir,28 Freundlich,29 Temkin,30 and Dubinin Redushkwich (D-R).31 The models for characterization of equilibrium distribution relate the quantity qe (mg g1 ) to concentration at a xed temperature; i.e. the amount qe of solute sorbed per unit weight of sorbent at Ce the concentration (mg L1 ) of the solute remaining in the solution at equilibrium. The parameters obtained from the isotherms studied are presented in Table 2. The Langmuir isotherm graphs of Ce /qe plotted against Ce , gave a straight line with correlation coefcient values closer to unity (Table 2) than the other isotherms, indicating that sorption data better ts the Langmuir isotherm model. The value of dimensionless parameter, RL , was less than unity (Table 2), which indicates that sorption is favourable at the applied conditions. The comparatively smaller value of RL for sorption on FZBFA than CZBFA and BFA indicates sorption to be more feasible. According to the Langmuir assumption the monolayer capacity of the sorbents follow the order FZBFA (85.68 mg g1 ) > CZBFA (78.80 mg g1 ) > BFA (52.52 mg g1 ). These values are

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Table 2. Isotherm parameters for 2-CP sorption by BFA, CZBFA, and FZBA Isotherms Langmuir BFA CZBFA FZBFA Freundlich BFA CZBFA FZBFA D-R BFA CZBFA FZBFA Temkin BFA CZBFA FZBFA Sorbents qm (mg g1 ) 52.52 78.80 85.68 Kf (L g1 ) 11.50 24.51 40.98 Xm (mg g1 ) 23.86 43.88 46.63 KT (L mg1 ) 1.07 6.23 37.50 Parameter values B (L mg1 ) 0.041 0.177 0.317 n 3.71 4.02 6.43 B (mol2 J2 ) 5.19 105 4.08 107 6.82 108 B1 8.70 11.60 10.11 RL 0.076 0.018 0.010 R2 0.9675 0.9625 0.9878 E (kJ mol1 ) 0.9811 1.107 2.707 R2 0.9389 0.9827 0.9958 R2 0.9832 0.9199 0.9253 R2 0.9876 0.9991 0.9982

to be less soluble and therefore, exhibit a higher tendency for sorption on the surface rather than remaining in the solution.3,34 As sorption is an exothermic process, it would be expected that an increase in temperature of the sorbatesorbent system would result in decreased sorption capacity. However, if the sorption process is inuenced by cylindrical (or spherical) diffusion and convective diffusion (intra-particle transport-pore diffusion), the sorption capacity will rise with temperature because diffusion is an endothermic process.36 Further argument would be that the rise in temperature creates changes in sorbent pore structure or increase the equilibrium constant, which will result in increase of 2-CP sorption. Among the three sorbents studied FZBFA exhibits higher sorption capacity than CZBFA and BFA due to its larger surface area and larger pore volume. The efciency of sorbents for the removal of 2-CP has the order FZBFA > CZBFA > BFA. Evolution of thermodynamic parameters Thermodynamic parameters were evaluated to study the feasibility of the sorption process and application of the sorbents at different temperatures (303 K, 313 K, 323 K, and 333 K). Thermodynamic parameters were evaluated from Vant Hoff plots. The change of enthalpy ( H0 ) and change of entropy ( S0 ) evaluated from the slope and intercept of Equation (1) and the values obtained are given in Table 3. R ln Kd = G0 = T S0 H0 T (1)

Table 3. Thermodynamic parameters for sorption of 2-CP on BFA, CZBFA, and FZBFA G0 (kJ mol1 ) Sorbents BFA CZBFA FZBFA 303 313 323 333 H0 (kJ mol1 ) 9.31 18.17 20.76 S0 mol1 )

(J K1

5.21 5.71 6.14 6.67 9.83 10.73 11.58 12.63 11.47 12.41 13.63 14.60

47.93 92.36 106.24

the positive value can be explained on the basis of the breaking of hydrogen bonds with increase in temperature resulting in increased sorption of 2-CP.35 The positive value of S0 indicates an increase in randomness at the solidsolution interface during sorption and the sorption process is thermodynamically favourable.35 During sorption, it can be presumed that the 2-CP molecules on the sorbent surface were more chaotically arranged compared with its arrangement in the aqueous solution. Effect of agitation time The solutions were agitated with a known amount of sorbents (BFA, CZBFA, and FZBFA) and the uptake curves are smooth and continuous leading to saturation after 360 min, although no signicant variation in residual 2-CP concentration was detected after 250 min (Fig. 4). Initially uptake of 2-CP increases with increasing agitation time and then the uptake slows near to equilibrium. Initially a large number of vacant sorbent sites are available and there is a high concentration gradient between solution and solid interphase thus uptake was fast for the rst 150 min. After this time, occupation of the remaining vacant surface sites is difcult due to repulsive forces between the solute molecules in the solid and bulk phase and the rate slows. Between these two stages the rate of sorption is nearly constant. The equilibrium sorptive removal follows the order FZBFA (48.49 mg g1 ) > CZBFA (45.12 mg g1 ) > BFA (28.61 mg g1 ) indicating that FZBFA has more potential to sorb 2-CP than CZBFA

where Kd is the distribution coefcient, H0 is the enthalpy change (kJ mol1 ), S0 is the entropy change (J K1 mol1 ), R is the gas constant (8.314 J mol1 K1 ) and T is absolute temperature (K). The negative values of G0 indicate that the sorption process is feasible and spontaneous in nature without any induction period and more favourable at higher temperatures. The H0 values were in the range 9.3120.76 kJ mol1 and the positive value conrms the endothermic nature of the overall sorption process. A value of H0 less than 20 kJ mol1 indicates sorption is physical rather than chemical,34 involving weak attraction forces. Furthermore,

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www.soci.org experimentally from the slope and intercept of a plot of t/qt versus t. Kinetic parameters with correlation coefcients are listed in Table 4. The range of correlation coefcients is much closer to unity than for the pseudo-rst-order model. Therefore, sorption can be more appropriately described by the pseudo-secondorder kinetic model. Similar behaviour has been observed in the sorption of phenol on bagasse y ash and activated carbon27 and activated carbon prepared from coconut coir pith.39 It can be seen that the initial sorption rate (h value) is higher for sorption of 2-CP by FZBFA than by BFA and CZBFA. Thus the applicability of the pseudo-second-order model suggests a somewhat complex mechanism of sorption instead of a single step process. Banghams equation Kinetic data were further used to study the slow step occurring in the later stage of sorption using Banghams equation.37 The straight line nature of the plots indicates that sorbate pore diffusion plays an important role in the sorption process for all sorbents. The values of constants (<1) and k0 are given in Table 4. The double logarithmic plots (gure not shown) according to the Banghams equation were not perfectly linear as the diffusion of 2-CP into the sorbent pores is not the only the rate controlling step.34 It can be expected that both lm and pore diffusion are important to different extents in the removal process. With increased contact time, the effect of diffusion on the overall sorption could be ignored. Similar results were reported by Mall et al. for the removal of phenol on activated carbon and bagasse y ash, the observed in the present studies are lower than those reported ( = 0.356, 0.309, 0.347).36 External diffusion model To distinguish between lm and intra-particle diffusion, data were tted to the external diffusion model. The correlation coefcient and external diffusion coefcient (ked ) calculated from the plots of ln (Ct /C0 ) versus t are presented in Table 4. The plots exhibit good correlation coefcients with the correlation coefcient of 2-CP on FZBFA much closer to unity (Table 4). Further, R2 values > 0.9 for all the systems studied indicate that sorption is probably a surface phenomenon, occurring on the exterior of the sorbent particles. Thus, external diffusion plays an important role in the process. Intra-particle diffusion study The overall sorption process may be controlled either by one or more steps, e.g. lm or external diffusion, pore diffusion, surface diffusion, and sorption on the pore surface, or a combination of more than one step. The role of pore diffusion as the single rate controlling step was tested with the aid of the Morris and Weber procedure40 using plots of qt vs. t1/2 . The results (Fig. 5) for sorption on BFA, CZBFA, and FZBFA, indicate macropore/mesopore diffusion and micropore diffusion.41 The intercepts provide a measure of the boundary layer thickness, i.e. the larger the value of intercept the greater the boundary layer effect. Curved plots for the initial period are usually attributed to boundary layer diffusion effects or external mass transfer effects.36,40,41 The slope of the linear portion of the gure can be used to derive values of the rate parameter, kid , for intra-particle diffusion (Table 4). These values are in the range 0.6970.886 mg g1 min1/2 , while in the second portion it is in the range 0.0910.152 mg g1 min1/2 . Though

Figure 4. Effect of agitation time on the sorption of 2-CP by BFA, CZBFA, and FZBFA.

and BFA, and CZBFA is more efcient than BFA. This may be due to the high surface area and high pore volume of FZBFA and CZBFA, compared with BFA.

SORPTION KINETICS
The sorption kinetics are important as they control process efciency. Sorption can be considered as a reversible reaction with equilibrium established between two phases. Sorption kinetics were determined by applying pseudo-rst-order and pseudosecond-order kinetic models. Diffusion of sorbate was ascertained using Banghams equation, intra-particle diffusion and external diffusion. The linear forms of all the models were used from earlier work.37 The applicability of a particular rate expression for the 2-CPsorbents systems was evaluated from the goodness of data t and regression coefcient value. Pseudo-rst-order kinetics model The pseudo-rst-order kinetic model assumes that the rate of change of sorbate uptake with time is directly proportional to the difference in the saturation concentration and the amount of solute uptake with time. The pseudo-rst-order kinetics, log (qe qt ) was plotted against t (gure not shown) and the linearity of the Lagergren (pseudo-rst-order) plots with good correlation coefcients (Table 4) conrms its applicability for this process. However, the equilibrium sorption capacity obtained using the intercept of the model does not yield reasonable values, suggesting that sorption is not a true rst-order reaction. Further, the linear Lagergrens equation plots do not strictly pass through the origin, possibly because the qe values depend on the initial 2CP concentration (C0 ) and are well below the monolayer capacities found by equilibrium modeling, and the slight dependence of Kf on C0 may be indicative of a complex sorption process. Similar results were reported by Tutem et al.34 Pseudo-second-order kinetics model The pseudo-second-order equation developed by Ho and Mckay38 is based on the amount of sorbate on the sorbent. The initial sorption rate (h), the equilibrium sorption capacity (qe ) and the pseudo-second-order constant ks can be determined

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Table 4. Kinetic parameters for the removal of phenols by BFA, CZBFA, and FZBFA Pseudo-rst-order qe (mg g1 ) BFA CZBFA FZBFA Pseudo-second-order qe (mg g1 ) BFA CZBFA FZBFA Bangham BFA CZBFA FZBFA External diffusion ked (cm min1 ) BFA CZBFA FZBFA Intra-particle diffusion kid, 1 (mg g1 min1/2 ) BFA CZBFA FZBFA 0.85 0.89 0.69 I1 (mg g1 ) 15.75 31.62 37.37 R2 0.9898 0.9924 0.9949 kid, 2 (mg g1 min1/2 ) 0.127 0.091 0.152 I2 (mg g1 ) 26.14 43.36 45.53 R2 0.9657 0.9785 0.9664 8.88 104 3.37 104 3.85 104 R2 0.9554 0.9819 0.9930 0.205 0.234 0.260 k0 (g) 1.65 3.73 4.49 R2 0.9811 0.9485 0.9239 29.82 46.38 49.33 ks (g mg1 min1 ) 2.03 103 2.06 103 2.45 103 h (mg g1 min1 ) 1.80 4.44 5.96 R2 0.9989 0.9992 0.9995 13.18 13.82 11.15 kf (min1 ) 1.18 103 8.41 103 8.13 103 R2 0.9926 0.9902 0.9897

the coefcient values (Table 4) for the intra-particle diffusion model are lower than those obtained for the pseudo-secondorder model, the values are close to each other, which signies that intra-particle diffusion is not the only rate controlling step.36 In the present study the plots do not pass through the origin and have intercepts, I, in the range 15.7545.53 mg g1 . It may be concluded that surface sorption and intra-particle diffusion operate concurrently during the sorbatesorbent interactions. The lower values of kid, 2 than kid, 1 suggest that 2-CP diffuses into the pores of the sorbents. As the diffusion resistance increases with time the diffusion rate decreases, thus, sorption is a multi-step process involving transport of 2-CPs to the surface of the sorbents followed by diffusion into the interior of the pores. Designing of xed bed sorption column For a system involving a feasible sorption process, a straightforward approach may be adopted for the design of a xed bed sorber.42 A column study for the sorption of 2-CP by FZBFA was not feasible as the column blocked within 30 min. Thus column studies were carried out with BFA and CZBFA. The breakthrough point was selected arbitrarily at some low value Cb (break point concentration) for the efuent concentration and Cx (exhaustion point concentration) closely approaching C0 (inuent concentration of

Figure 5. Intra-particle diffusion curves of 2-CP sorption on BFA, CZBFA, and FZBFA.

2-CP), at which the sorbent is considered to be essentially exhausted. Mass units for C and Ve are used to illustrate the concept of mass balance in the sorption system.

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Sorption of 2-chlorophenol by modied bagasse y ash Two design parameters are important: (i) the total mass, i.e. quantity of efuent, Vb , passed per unit cross-section to the break point and (ii) the nature of the curve between the value Vb and Vx . Here Vb is the volume of efuent corresponding to Cb and Vx is the volume of efuent corresponding to Cx . The parameters, primary sorption zone (PSZ = ), total time taken for the establishment of PSZ (tx ), mass ow rate (Fm ), time required for the downward movement of PSZ (t ), time required for initial formation of PSZ (tf ), and fractional capacity (f ) were evaluated using reported equations.42,43 The percentage saturation of the column at break point is obtained from: % saturation = D + (f 1) 100 D (2)

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The breakthrough curve of 2-CP sorption on BFA and CZBFA is expressed in terms of C/C0 against total quantity of 2-CP solution, Ve , which passes through the column (Fig. 6). The values of Vb , Vx , Cx , and Cb obtained from this graph were used to calculate tx , tf , t , f , and percentage saturation at breakpoint (Table 5). The results reveal that for 2-CP the total time (tx ) required for the primary zone to establish itself, move down the length of the column and out of the bed is 600 and 660 min on BFA and CZBFA, respectively. The time taken for initial formation of the primary sorption zone (tf ) is 1.5 h for both sorbents. The fractional capacity f of the column in the sorption zone at breakpoint to continue to remove solute from solution is 0.600 and 0.571 on BFA and CZBFA, respectively. The percentage saturation at breakpoint is 75.0 for BFA while it is 77.78 on CZBFA. From these observations a direct relationship between the length of the sorption zone () and percentage saturation at break point can be developed. The smaller the length of the sorption zone, the higher the percentage saturation in contrast with results obtained by Gupta et al.43 The value of Vx Vb is 305.733 and 285.351 mg cm2 for BFA and CZBFA, respectively, indicating the additional quantity of sorbate loaded per unit cross-sectional area that will result in complete exhaustion of the sorbent capacity in a given bed. The breakthrough capacities are higher than the batch sorption capacities. The higher capacity of column operations was explained by a continuously large concentration gradient at the interface zone as it passes through the column, while in the batch isotherm test the concentration gradient decreased with time. Similar results were reported by Gupta et al.3 for chlorophenols and Bhatnagar Amit for bromophenols.35 It is further seen from Table 6 that the exhaustion capacity of the column is higher than the batch capacity for the same reason as established for the breakthrough capacity. Furthermore, Table 6 shows that the degree of column utilization is 74.80 and 77.66% for BFA and CZBFA, respectively. Thus, these results show that

Figure 6. Breakthrough curves and desorption plots of 2-CP on BFA and CZBFA.

Table 6. Sorption capacity of BFA and CZBFA for 2-CP Batch capacity (mg g1 ) 52.52 78.80 Breakthrough capacity (mg g1 ) 61.02 81.19 Exhaustion capacity (mg g1 ) 81.57 98.09 Column utilization (%) 74.80 77.66

Sorbents BFA CZBFA

these sorbents can be effectively used in columns to remove 2-CP from waste-waters. The operational parameters obtained give an idea of the time required for breakthrough to occur and how much additional solution loaded per unit cross-sectional area of the sorber would result in complete exhaustion of the sorbent column. If the technique is applied on large scale, these data can be useful for the design of xed bed sorbers for the treatment of known 2-CP concentrations. Desorption studies Disposal or regeneration of spent sorbent is an important economic factor in assessing the feasibility of a sorption system. Desorption studies help to elucidate the mechanism of sorption to recover the pollutant from the spent sorbent, apart from protecting the environment from a disposal problem. After batch sorption, the loaded sorbents were washed gently with distilled water to remove any unsorbed 2-CP. The loaded sorbents were resuspended in 50 cm3 of desorbent and equilibrated for 24 h. Desorption was

Table 5. Parameters of xed bed column design obtained from breakthrough curve Sorbent BFA CZBFA Sorbent BFA CZBFA C0 (mg cm3 ) 0.4 0.4 tx (min) 600 660 Cx (mg cm3 ) 0.392 0.391 Cb (mg cm3 ) 0.022 0.019 t (min) 300 280 Vx (mg cm2 ) 611.47 672.61 tf (min) 120 120 Vb (mg cm2 ) 305.73 387.26 7.50 6.22 Vx Vb (mg cm2 ) 305.73 285.35 f 0.600 0.571 Fm (mg cm2 min1 ) 1.019 1.019 D (cm) 12 12 % saturation 75.00 77.78

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www.soci.org carried out by suspending the loaded sorbents (0.5 g) in either 0.5 mol L1 NaOH (50 cm3 ), or 0.5 mol L1 HCl (50 cm3 ) or anionic surfactant SDS (2000 ppm). Desorption data show that HCl and SDS have a lower tendency to desorb 2-CP, with 21.95, 16.28 and 13.20% desorbed by 0.5 mol L1 HCl and 23.85, 19.55 and 16.89% by SDS from BFA, CZBFA, and FZBFA, respectively. The maximum desorption of 2-CP was obtained using 0.5 mol L1 NaOH with 82.33, 80.12 and 79.33% from BFA, CZBFA, and FZBFA, respectively. In the desorption process 2-CP reacts with NaOH to form sodium phenolates, which are readily desorbed due to their high solubility in aqueous media. Similar results were reported by Anirudhan et al.39 for desorption of phenol, p-chlorophenol, and p-nitrophenol from activated carbons. Regeneration of columns saturated with 2-CP was carried out by passing 0.5 mol L1 NaOH at a xed ow rate of 1 cm3 min1 at room temperature. To evaluate the efciency of solute recovery, the percentage 2-CP recovered was calculated from the breakthrough and recovery curves. After exhaustion the column was washed with 25 cm3 doubly distilled water to remove unsorbed phenols which were collected and analyzed for 2-CP. A negligible amount was found. Then 0.5 mol L1 NaOH was passed through the column and collected in 10 cm3 fractions and the amount of desorbed 2-CP determined (Fig. 6). The desorption plots reveal that the rst 10 cm3 aliquot elutes more than 50% of the 2-CP and the rest is desorbed in nine increments of 10 cm3 giving an overall percentage recovery of about 98% for BFA and CZBFA columns. From these desorption studies it can be concluded that about 120 cm3 of 0.5 mol L1 NaOH is sufcient for almost complete desorption of 2-CP from the sorbent column used.

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2 Mukherjee S, Kumar S, Misra AK and Fan M, Removal of phenols from water environment by activated carbon, bagasse ash and wood charcoal. Chem Eng J 129:133142 (2007). 3 Gupta VK, Ali I and Saini VK, Removal of chlorophenols from wastewater using red mud: an aluminum industry waste. Environ Sci Technol 38:40124018 (2004). 4 Bhatnagar A and Minocha AK, Conventional and nonconventional adsorbents for the removal of pollutants from water a review. Indian J Chem Technol 13:203217 (2006). 5 Gogate PR and Pandit AB, A review of imperative technologies for wastewater treatment II: hybrid methods. Adv Environ Res 8:553597 (2004). 6 Crini G, Non-conventional low-cost adsorbents for dye removal: a review. Bioresource Technol 97:10611085 (2006). 7 Delle Site A, Factors affecting sorption of organic compounds in natural sorbent/water systems and sorption coefcients for selected pollutants. a review. J Phys Chem Ref Data 30:187439 (2001). 8 Lin SH and Juang RS, Adsorption of phenol and its derivatives from water using synthetic resins and low-cost natural adsorbents: a review. J Environ Manage 90:13361349 (2009). 9 Zumriye A, Application of biosorption for the removal of organic pollutants: a review. Process Biochem 40:9971026 (2005). 10 Da browski A, Podkoscielny P, Hubicki Z and Barczak M, Adsorption of phenolic compounds by activated carbon a critical review. Chemosphere 58:10491070 (2005). 11 Murayama N, Yamamoto N and Shibata J, Mechanism of zeolite synthesis from coal y ash by alkali hydrothermal reaction. Int J Miner Proc 64:117 (2002). 12 Wang Y, Guo Y, Yang Z, Cai H and Xavier Q, Synthesis of zeolites using y ash and their application in removing heavy metals from water. Sci China Ser D 46:967976 (2003). 13 Lin Cheng-Fang and His Hsing-Cheng, Resource recovery of waste y ash: synthesis of zeolite-like materials. Environ Sci Technol 29:11091117 (1995). 14 Fukui K, Katoh M, Yamamoto T and Yoshida H, Utilization of NaCl for phillipsite synthesis from y ash by hydrothermal treatment with microwave heating. Adv Powder Technol 20:3540 (2009). 15 Wang S, Soudi M, Li L and Zhu ZH, Coal ash conversion into effective adsorbents for removal of heavy metals and dyes from wastewater. J Hazard Mater 133:243251 (2006). 16 Vucinic D, Miljanovic I, Rosic A and Lazic P, Effect of Na2 O/SiO2 mole ratio on the crystal type of zeolite synthesized from coal y ash. J Serb Chem Soc 68:471478 (2003). 17 Inada M, Tsujimoto H, Eguchi Y, Enomoto N and Hojo J, Microwaveassisted zeolite synthesis from coal y ash in hydrothermal process. Fuel 84:14821486 (2005). 18 Shah BA, Patel HD and Shah AV, Equilibrium and kinetic studies of the adsorption of basic dye from aqueous solutions by zeolite synthesized from bagasse y ash. Environ Prog Sustainable Energy DOI 10.1002/ep.10505 (2011). 19 Vogel AI, A Text Book of Quantitative Analysis, 5th edn. ELBS publication, London (1989). 20 Noh JS and Schwarz JA, Estimation of the point of zero charge of simple oxides by mass titration. J Colloid Interface Sci 130:157164 (1989). 21 Pontius FW, Water Quality and Treatment, 4th edn. McGraw-Hill Inc., New York (1990). 22 Joint committee on powder diffraction standards, Index (Inorganic to the powder diffraction le, Publication PDIS-211; Newton Square, PA (1971). 23 Treacy MMJ and Higgins JB, Collection of simulated XRD powder patterns for zeolites, fourth revised edition published on behalf of the Structure Commission of the International Zeolite Association. Elsevier, Amsterdam, London, New York, Oxford, Paris, Shannon, Tokyo (2001). 24 Gupta VK, Sharma S, Yadav IS and Mohan D, Utilization of bagasse y ash generated in the sugar industry for the removal and recovery of phenol and p-nitrophenol from wastewater. J Chem Technol Biotechnol 71:180186 (1998). 25 Kao PN, Tzeng JH and Huang TL, Removal of chlorophenols from aqueous solution by y ash. J Hazard Mater 76:237249 (2000). 26 Coughlin RW and Ezra FS, Role of surface acidity in the adsorption of organic pollutants on the surface of carbon. Environ Sci Technol 2:291297 (1968). 27 Srivastava VC, Swamy MM, Mall ID, Prasad B and Mishra IM, Adsorptive removal of phenol by bagasse y ash and activated carbon:

CONCLUSIONS
Bagasse y ash from the local sugar mill was successfully transformed into zeolites by hydrothermal and fusion methods followed by hydrothermal treatment and identied by FTIR, PXRD, SEM and XRF techniques. Synthesized zeolitic materials CZBFA and FZBFA show higher sorption capacity for 2-CP than the original BFA, and the results are comparable with reported data for commercial sorbents. Batch and column studies were carried out for the removal of 2-CP. Batch studies indicated sorption followed a Langmuir monolayer sorption isotherm, was endothermic in nature, and followed a pseudo-second-order kinetic model. The uptake of 2-CP can be explained by external and intra-particle diffusion processes. In column studies the breakthrough capacity of BFA and CZBFA was higher than the batch capacity. The ne particle size of FZBFA prevented the column study with this sorbent. The sorbed 2-CP was quantitatively desorbed using 0.5 mol L1 NaOH as eluent. The column parameters calculated in this study can be useful in predicting the treatment of 2-CP-containing waste-water of known concentration by xed bed column mode.

ACKNOWLEDGEMENT
The authors are grateful to SAP meritorious fellowship, UGC, New Delhi, India.

REFERENCES
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36 Srivastava VC, Swamy MM, Mall ID, Prasad B and Mishra IM, Adsorptive removal of phenol by bagasse y ash and activated carbon: equilibrium, kinetic and thermodynamics. Colloids Surf A 272:89104 (2006). 37 Shah BA, Shah AV, Singh RR and Patel NB, Sorptive removal of nickel onto weathered basaltic andesite products: kinetics and isotherms. J Environ Sci Health Part A 44:880895 (2009). 38 Ho YS and McKay G, Pseudo-second-order model for sorption processes. Process Biochem 34:451465 (1999). 39 Anirudhan TS, Sreekumari SS and Brigle CD, Removal of phenols from water and petroleum industry renery efuents by activated carbon obtained from coconut coir pith. Adsorption 15:439451 (2009). 40 Morris JC and Weber WJ, Kinetics of adsorption of carbon from solutions. J Sanitary Eng Division Am Soc Civil Eng 89:3160 (1963). 41 Fierro V, Torne-Fernandez, V, Montane D and Celzard A, Adsorption of phenol onto activated carbons having different textural and surface properties. Micropor Mesopor Mater 111:276284 (2008). 42 Sarkar M, Acharya P and Bhattacharya B, Removal characteristics of some priority organic pollutants from water in a xed bed y ash column. J Chem Technol Biotechnol 80:13491355 (2005). 43 Gupta VK, Srivastava SK and Tyagi R, Design parameters for the treatment of phenolic wastes by carbon columns (obtained from fertilizer waste material). Water Res 34:15431550 (2000).

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