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 fly 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 fly ash, a sugar industry solid waste with disposal problems, was utilized as a source for the synthesis of zeolitic material. The efficiency 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 fits the equilibrium data which concur with physical sorption. Kinetic studies showed better correlation coefficients for pseudo-second-order and intraparticle diffusion model, confirming that the sorption rate was controlled by film 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 fly 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; modified bagasse fly 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 refining, 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 difficult owing to the high cost of treatment. Various methods exist for their removal from aqueous solutions, i.e. coagulation, reverse osmosis by membrane filtration, 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 fly ash into zeolites,11 – 17 but apart from one earlier study,18 there are no reports on the conversion of bagasse fly ash into zeolites. In this present study, attempts have been made to develop a low-cost sorbent using bagasse fly ash (BFA) by converting it into zeolitic sorbents (ZBFA). The virgin and final 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 fixed 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

J Chem Technol Biotechnol 2011; 86: 1265–1275

www.soci.org

c 2011 Society of Chemical Industry

05 464.www.20 X-ray fluorescence (XRF) analysis was performed using an X-ray XDL-B (Fischer scope.R.31 ± 0.45 CZBFA 15.44 20. micro controller pH meter. All the batch experiments were performed using a solution of 2-CP (25 cm3 . Shimadzu. 200 µm mesh.3 43.18 ± 0. Japan) at CSMCRI.12 4. Bhavnagar.2 11.89 3. with 90 µm sized sorbents (BFA. namely pH (2–12). temperature (303–333 K) and agitation time (1–24 h) were examined. Repeatedly washing with doubly distilled water removed excess sodium hydroxide and the solid was dried at 373 ± 10 K.98 ± 0.02 0. The data obtained are given in Table 1.24 of 2-chlorophenol.539 0.02 1.0057) and the mean values taken.02 0.2 12. At the end of the process. Physico-chemical properties of BFA. filtered through Whatman filter paper No. Sorbate All of the reagents used were Merck and Rankem chemicals of A. The effect of different operational variables. The dried zeolitic material (CZBFA) was passed through a 90–120 µm mesh sieve and used for sorption of 2-CP.22 4. grade. dried in sunlight for 8 h and then at 353 K 1266 wileyonlinelibrary. Thermo Nicolate).87 19.2 w/w) to obtain a homogeneous mixture. The initial pH (pH0 ) of the 2-CP solutions was adjusted using 1 mol L−1 solution of NaOH or HCl.350 8.89 18. the resultant solid was separated by filtration.45 5. model EQ-621) was used to measure the pH of solutions. After fixed time intervals.11 ± 0.55 ± 0. Blank experiments for each study without sorbent showed no decline in the solute concentration. 42 (pore size ca 2. at different times (t) was calculated.05 45.690 0.2 2. was mixed and ground with sodium hydroxide in a predetermined ratio (NaOH/BFA = 1.5–10 g L−1 ). Japan).46 2. The slurry was agitated mechanically for 12 h at room temperature and was then crystallized under static conditions at 363 K for 6 h.44 ± 0. dosage (0.5 h.69 ± 0.45 6. India. The dried zeolitic material (FZBFA) was passed through a 90–120 µm mesh sieve.3 75. Powder X-ray diffraction (PXRD) patterns of the sorbents were carried out using a Panalyticals X Pert Pro instrument at Panjab University. CZBFA. CZBFA.408 8. India. Table 1.05 368.63 ± 0.46 2.2 2.3 70.556 0.2 16.45 ± 0.02 1. 200 µm mesh. The results of these findings are discussed in the present paper. The moisture contents of the sorbents were determined by a Karl-Fischer (1204R of VMHI) instrument.01 7. Chlorophenol concentration was measured at λmax 274 nm using a UV-Visible spectrophotometer (UV-Visible EV 300.75 3.7 44. The dried BFA and zeolitic materials (CZBFA and FZBFA) were stored in airtight desiccators until required. was suspended in a 3 mol L−1 NaOH solution (10 : 1 liquid/solid ratio) and refluxed for 72 h with intermittent stirring at 373 ± 5 K. blackish gray in colour was procured from a local sugar mill.07 ± 0. FT-IR spectra were recorded on a Thermo-Nicolet iS-10 Fourier Transform Infrared (FT-IR) spectrometer from 4000 to 400 cm−1 .46 FZBFA 18. and FZBFA). The initial 2-CP concentration (C0 ) was ascertained before the start of each experimental run. and FZBFA Values obtained Characteristics Proximate analysis Loss on drying (%) Moisture content (%) Ash content (%) Physico. unless otherwise noted. The yield of the final product (FZBFA) was about 82 ± 5%.62 ± 0. Gujarat. India employing nickel filtered CuKα radiations.2 1.6 47.3 65.84 ± 0.org B Shah.67 ± 0.15 ± 0.59 4. 86: 1265–1275 .12 3. The resultant mixture was filtered and washed with doubly distilled water until free from sodium hydroxide and dried at 373 ± 10 K.properties Specific density Bulk density (g cc−1 ) Dry density (g cc−1 ) Void ratio Porosity (fraction) pHpzc BET surface area Chemical constituents SiO2 % Al2 O3 % Fe2 O3 % CaO % MgO% Na2 O % K2 O % BFA 12. ground further and added to 128 cm3 of doubly distilled water. Panjab.75 ± 0.16 ± 0.soci. To simulate the design of column operation knowledge of sorption isotherms and flow dynamics is essential.66 3. A Shah for 4 h in a hot air oven.02 2. The dried BFA sieved through 90–120 µm mesh was used for sorption studies.19 A pH meter (Equip-Tronics. initial 2-CP concentration (50–300 mg L−1 ). The mixture was fused in a stainless steel crucible at 823 ± 10 K for 1.02 1. The amount of solute sorbed per gram of sorbent (qt ). The BFA was washed thoroughly with doubly distilled water. R Tailor. The yield of the final product (CZBFA) was about 75 ± 5%. The Brunauer–Emmett–Teller (BET) specific surface area of the sorbents were measured by adsorption of nitrogen at 77 K using a Micromeritics automatic surface area analyzer (Gemini 2360. a sample of solution was removed.79 2.89 3. 100 mg L−1 initial concentration (C0 )) at 303 K.com/jctb c 2011 Society of Chemical Industry J Chem Technol Biotechnol 2011.359 8.02 1. Batch operations Batch experiments were carried out to determine the equilibrium time and for the development of sorption isotherms.76 5..04 ± 0. Fusion treatment of BFA The dried BFA. Shree Khedut Sahkari Khand Udhyog Mandali Ltd.02 1. stored in a brown coloured glass bottle and diluted to desired concentration with doubly distilled water. The stock solution of 2-CP (1000 mg L−1 ) was prepared.39 ± 0. Conventional hydrothermal treatment of BFA The dried BFA material. Each experiment was repeated three times (standard deviation value < 0. The point of zero charge (pHpzc ) for BFA and synthesized zeolitic materials were determined by mass titration as proposed by Noh and Schwarz.56 ± 0. MATERIALS AND METHODS Instrumental methods The physico-chemical characteristics of sorbents were determined using standard procedures.5 µm) and the concentration of solute measured.13 ± 0. Raw material (bagasse fly ash) Bagasse fly ash (BFA).02 0. The mixture was held in an airtight stoppered conical flask (50 cm3 ) and agitated at 150 rpm in an incubator shaker until equilibrium was attained. Bardoli.93 ± 0. The resultant fused product was cooled to room temperature. indicating no sorption by either the container or filter material.

breakthrough curves exhibit a characteristic ‘S’ shape but with varying degrees of steepness and breakpoint positions. 86: 1265–1275 c 2011 Society of Chemical Industry wileyonlinelibrary.97◦ and 1267 J Chem Technol Biotechnol 2011.11 Alkali fusion enhances the dissolution of fly ash converting most of the ash into sodium silicate and aluminate and the calcium magnesium oxides and other components were reduced after synthesis. For most sorption processes in water and waste-water treatment. The most intense new peaks at 2θ = 15. which is the source material for zeolite crystals on the outer surface of BFA particles. The shift of the band maximum of 1096.34 cm−1 in the unzeolitized BFA to 1022.11 cm−1 are attributed to deformation of − OH vibration of absorbed water and bending vibration of H2 O.61 and 8. Al) asymmetric stretching vibrations of internal tetrahedra. The weighed material was slurried with hot water and fed slowly into the column to avoid air entrapment.92 cm−1 confirm the formation of zeolite phases. CZBFA. This may be due to dissolution of the glass phase (aluminium-silicate) into the alkaline solution during treatment. PXRD patterns of BFA. The identification 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). 1. www.07 to 765.33 cm−1 in CZBFA Figure 1. alumina and silicate ions are condensed to form an alumina–silicate gel. and allowed to percolate through the column under gravity (flow rate = 0. For FZBFA.12 PXRD analysis Analysis of sorbents by powder X-ray diffraction provides dspacing values of their corresponding minerals and crystalline phases. shifting of the bands from 1096. and FZBFA. BET surface area follows the order FZBFA (464. containing (BFA or CZBFA) was prepared with 1.22 The powder X-ray diffraction patterns of BFA. CZBFA. CZBFA.0 with 2-CP concentration (0.23 CZBFA shows a comparatively flat and weak peak after treatment and also gives several new sharp diffraction peaks which were not seen in BFA. The bands between 720 and 650 cm−1 and between 420 and 500 cm−1 can be due to symmetric stretching and bending mode of these internal tetrahedral.21 The sorbate solution of known concentration was loaded onto the column.5 cm). The bands at about 1651 and 1441.org RESULTS AND DISCUSSION Characteristics of sorbents The chemical and mineralogical compositions of the BFA.5 cm3 min−1 ). This stretching frequency arises from both the silanol groups (Si–OH) and sorbed water (peak at around 3400 cm−1 ).3 m2 g−1 ) > BFA (45.Sorption of 2-chlorophenol by modified bagasse fly ash Column study A glass column (10 × 0. The band between 1250 and 850 cm−1 can be ascribed to TO4 (where T = Si.12. This indicates that these impurities dissolved in the alkaline solution during the hydrothermal synthesis of CZBFA and FZBFA.13 cm−1 and 795. The chosen method for operation of a fixed bed sorber is to a large extent dependent on the shape of the breakthrough curve obtained by plotting C/C0 versus time or volume. and FZBFA (figure not shown) showed a broad band between 3700 and 3100 cm−1 indicating the presence of − OH groups on the surface. and FZBFA are shown in Fig. respectively. At about 90% sorption capacity the column operation was stopped. several small peaks of mullite (JCPDS 15–0776). CZBFA.6 m2 g−1 ) indicating that. the surface area of the zeolitic sorbents has been increased significantly. 8.34 to 981. confirms the tetrahedral coordination of aluminium in the zeolite framework.4 mg cm−3 ) using a plot of C/C0 against volume (Ve ).67 pH for BFA. 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+ .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 physicochemical properties obtained by classical methods are presented in Table 1. The pHpzc values obtained by mass titration method were 8.7 m2 g−1 ) > CZBFA (368. A large wide peak at low diffraction angle in the BFA diffraction pattern indicates the presence of a glass phase. CZBFA and FZBFA as their stable oxides obtained using an XRF technique are summarized in Table 1. and FZBFA.com/jctb . a small peak of stilbite and other amorphous materials. The amounts of SiO2 and Al2 O3 within zeolites (CZBFA and FZBFA) were a little lower than the corresponding oxides in the original BFA. The concentration of sorbate leaving the column was measured to determine the amount of 2-CP retained. The breakthrough capacity of the column was determined by loading BFA and CZBFA at pH 2. FT-IR analysis FT-IR spectra of BFA. respectively.soci.07. following treatment of the BFA. During hydrothermal treatment.0 g of sorbent (90–120 µm mesh) on glass wool support. 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.17 The diffractogram of BFA shows α-quartz peaks (JCPDS 5–490).

1. with the sorption efficiency following the order FZBFA > CZBFA > BFA. with positive identification of zeolite P (Phillipsite. zeolite X (JCPDS 28–1036). So.41. creating more folded strands with deeper pores.74.22 mg g−1 by BFA. JCPDS 39–0219). and FZBFA at 500X magnification. at which repulsive interactions between the charged surface groups and uncharged molecules are minimized. 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. and calcined ZSM 12 (JCPDS 15–274).68. 1. The SEM micrograph shows the presence of spherical particles in CZBFA and FZBFA due to the alkaline treatment.97.32.27.22. In the case of FZBFA the agglomeration of particles to form clusters can be expected due to its softer texture. 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. From the disappearance of quartz and mullite peaks. Batch sorption studies Effect of pH The sorption of 2-CP (Fig. The observed d-spacing values of phillipsite (P) = 6. analcime (JCPDS 76–0901).24 and Gupta et al. BFA also possesses irregular shapes and surfaces. SEM analysis Scanning electron microscopic (SEM) analysis has been useful in understanding the surface morphology of solid materials. 3. can be attributed to the formation of zeolites. R Tailor. oxides) and the aromatic rings of 2-CP. pKa of 2-CP. At pH < pHpzc . 3.17 After treatment.68 and analcime (A) = 5. Zeolite P and analcime were dominant in the zeolites formed by fusion. analcime (JCPDS 76–0901).95.13◦ .89. SEM micrographs of BFA.71.com/jctb c 2011 Society of Chemical Industry J Chem Technol Biotechnol 2011. zeolite A (JCPDS 14–90). The SEM image of BFA shows a fibrous structure with large irregular silicate masses and a lamellar structure with large but shallow pore size and strands in each fold. CZBFA. The SEM micrograph of CZBFA shows honeycomb apertures and holes indicating the sorbent to be more porous than BFA. 3. 2. A Shah Figure 2. 1. it may be concluded that the combined effects of all these factors. The crystalline phases identified in the FZBFA were zeolite P (JCPDS 39–0219).org 2θ = 26. 1.89. which show crystalline forms with compact structures. namely. et al.soci. 3) was found to decrease gradually with increasing pH of solution (up to 8 pH) for BFA.80. Therefore. respectively.13 Overall. CZBFA. Furthermore. 48. This may be due to changes in the surface of the particles. 2 at 500× magnification.g. 2.02. another sorption mechanism may be expected based on the formation of donor–acceptor complexes between the surface basic groups (electron donors. 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. 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. and FZBFA. e. and FZBFA and after pH 8 a sharp decrease was observed up to pH 12. it is reasonable to deduce that both quartz and mullite in the BFA have reacted with NaOH during fusion to form sodium aluminosilicates. it can be assumed that 2CP molecules are sorbed on the sorbents mainly through dispersive forces as suggested by Coughlin and Ezra.56). the surface shows hollow particles with interior voids.5 pH.66. pHpzc of sorbents.99. and chabazite (JCPDS 12–0194). Similar results were reported by Kao B Shah. and FZBFA are shown in Fig.82.www. SEM micrographs of BFA. the decrease in sorption at pH > 8. The 2-CP uptake at 2 pH after 360 min is 28. 1. 4. which reduces the glass phase as shown in X-ray diffraction patterns. CZBFA.13 The PXRD pattern of FZBFA shows the peak at low diffraction angle is even more suppressed compared to BFA and CZBFA. 86: 1265–1275 . the particles of CBZFA and FZBFA seem to be more fluffy and porous. 44. and FZBFA. 3. 2. and tendency to form donor–acceptor complexes play an important role during sorption of 2-CP on the surface of BFA. The SEM micrograph of FZBFA exhibits trapezohedral analcime crystals approximately 10 µm in size with morphology similar to that reported by Lin et al.74 in CZBFA indicate their presence as major constituents. albeit with some crystals (with the exception of analcime) not very distinct. OH. 1268 wileyonlinelibrary. 1. 4. hence.26 In addition. CZBFA. 2. the transformation of fly ash to different zeolite phases can be demonstrated by SEM. CZBFA.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.54.22.

soci.80 mg g−1 ) > BFA (52. 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.27 The increase in C0 also enhances the interaction between 2-CP and sorbents. Sorption isotherms Four sorption isotherm models were used to fit the equilibrium sorption data in order to design the sorption system. the sorption of 2-CP on FZBFA can be characterized by a uniform distribution of the binding energies. and FZBFA increased with increase in temperature indicating that the process is endothermic. The sorption of 2-CP on BFA. the removal of sorbates also increases until the sorbant becomes saturated by the sorbate (2-CP) and removal tends to a constant value. the amount qe of solute sorbed per unit weight of sorbent at Ce the concentration (mg L−1 ) of the solute remaining in the solution at equilibrium. The Langmuir isotherm graphs of Ce /qe plotted against Ce . The value obtained for FZBFA is comparable with a reported value for activated carbons (51 L g−1 ). resulting in appreciable solubility.10 The value of heterogeneity factor n > 1 indicates intense sorption but the correlation coefficients are lower than for the Langmuir isotherm. The value of correlation coefficient of BFA is close to unity. These values are 1269 J Chem Technol Biotechnol 2011. it is plausible to explain the effect of temperature mainly on the basis of hydrogen bonding. indicating that sorption data better fits the Langmuir isotherm model. Initially. The sorption mechanism whether ion-exchange or physical in nature. According to the Langmuir assumption the monolayer capacity of the sorbents follow the order FZBFA (85. For BFA. The values of KT and B1 obtained are shown in Table 2. The multilayer sorption capacity.29 Temkin. C0 provides the necessary driving force to overcome the resistances to the mass transfer between the aqueous and solid phases. on rice husk. As the sorbent dose increases. gave a straight line with correlation coefficient values closer to unity (Table 2) than the other isotherms.30 and Dubinin Redushkwich (D-R). The sorption capacity Xm was found to be less than that for the Langmuir isotherm (Table 2). This indicates that the heat of sorption of all the molecules in the layer decreases linearly with coverage due to sorbent–sorbate interactions. for the sorption of chlorophenols on bituminous shale. If the magnitude of E is between 8 and 16 kJ mol−1 . E. larger available surface area.63 mg g−1 ) (Table 2). The rate of sorption is higher initially as the sites on the sorbents are vacant and easily accessible by the sorbates.98 L g−1 .86–46. which indicates that sorption is favourable at the applied conditions.com/jctb . and FZBFA. Xm (23. of sorbent was in the range 11. The initial rise in sorption with sorbent or sorbate concentration is probably due to a stronger driving force. Similar results were reported by Tutem et al.32 The Freundlich isotherm plot of ln qe versus ln Ce gives a straight line with lower correlation coefficients than Langmuir (Table 2). Such mechanistic paths could explain the conformity of our data with both Langmuir and Feundlich isotherms for all the systems studied. The slope of the plot gives the value of β and the intercept yields the value of sorption capacity. CZBFA. CZBFA.28 Freundlich. These hydrogen bonds become broken at higher temperature and this would cause 2-CP Figure 3. can be deduced from the value of sorption energy. However. This observation could also be attributed to molecular interaction between the sorbate species and subsequent aggregation in the surface monolayer.e. the linearized equations of all isotherms have been obtained from published work: Langmuir. 86: 1265–1275 c 2011 Society of Chemical Industry wileyonlinelibrary. the sorption process follows by ion-exchange. and more sorption sites. the Temkin equation represents the poorest fit of experimental data. 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. which indicates that BFA data also better fit the D-R isotherm due to its variable micro.org comparable with those obtained by Gupta et al. RL .52 mg g−1 ). Kf . was less than unity (Table 2). rather than layer-by-layer formation of a film on the walls of the pores.35 In an aqueous solution of 2-CP there is extensive hydrogen bonding between 2-CP molecules and water. 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.3 on red mud and higher than the value (2-CP = 0. So.68 mg g−1 ) > CZBFA (78.21 mg g−1 ) reported by Shiundu et al.34 The rise in temperature also causes more dissociation of the 2-CP molecule. while for values of E < 8 kJ mol−1 .33 The values of sorption energy E were found to be < 8 kJ mol−1 (Table 2) thus suggesting physisorption. In the Temkin isotherm model plots of qe versus ln Ce enable determination of the isotherm constants KT and B1 . The R2 value obtained for FZBFA is very close to its value for the Langmuir isotherm. the sorption process is of a physical nature. calculated using the value of slope of the plot β.50 to 40.and meso-porous nature as observed in the N2 sorption isotherm (figure not shown). The D-R isotherm model presumes a pore filling mechanism in micropores of the sorbent.31 The models for characterization of equilibrium distribution relate the quantity qe (mg g−1 ) to concentration at a fixed temperature. up to some maximum binding energy. Effect of initial 2-CP concentration and dosage The uptake of 2-CP increases with increase in initial concentration (C0 ) for all systems (figure not shown). i. The parameters obtained from the isotherms studied are presented in Table 2. The value of dimensionless parameter. Effect of pH on the sorption of 2-CP by BFA. The comparatively smaller value of RL for sorption on FZBFA than CZBFA and BFA indicates sorption to be more feasible.Sorption of 2-chlorophenol by modified bagasse fly ash www. Thermodynamic parameters. Effect of temperature The temperature dependence of a sorption process is a complex phenomenon. the rate of removal of 2-CP was rapid and then slowed down as the dose concentration increased.

88 46.63 KT (L mg−1 ) 1. and FZBA Isotherms Langmuir BFA CZBFA FZBFA Freundlich BFA CZBFA FZBFA D-R BFA CZBFA FZBFA Temkin BFA CZBFA FZBFA Sorbents qm (mg g−1 ) 52.018 0.9389 0.98 Xm (mg g−1 ) 23.68 Kf (L g−1 ) 11. Thermodynamic parameters for sorption of 2-CP on BFA. although no significant variation in residual 2-CP concentration was detected after 250 min (Fig.71 4.org B Shah. 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 first 150 min.71 6.67 9. Initially uptake of 2-CP increases with increasing agitation time and then the uptake slows near to equilibrium.31 18. R Tailor.9625 0. The H0 values were in the range 9.35 During sorption. 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. 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. and 333 K).73 11.86 43. exhibit a higher tendency for sorption on the surface rather than remaining in the solution.50 Parameter values B (L mg−1 ) 0.19 × 10−5 4.34 involving weak attraction forces. CZBFA.61 mg g−1 ) indicating that FZBFA has more potential to sorb 2-CP than CZBFA where Kd is the distribution coefficient.08 × 10−7 6. After this time.63 14.9958 R2 0. 313 K. S0 is the entropy change (J K−1 mol−1 ). R is the gas constant (8.47 12.317 n 3.51 40.177 0.9991 0. it would be expected that an increase in temperature of the sorbate–sorbent system would result in decreased sorption capacity. 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.36 Further argument would be that the rise in temperature creates changes in sorbent pore structure or increase the equilibrium constant.9876 0. Isotherm parameters for 2-CP sorption by BFA.35 The positive value of S0 indicates an increase in randomness at the solid–solution interface during sorption and the sorption process is thermodynamically favourable.82 × 10−8 B1 8.314 J mol−1 K−1 ) and T is absolute temperature (K).9199 0. the sorption capacity will rise with temperature because diffusion is an endothermic process.21 5.9982 to be less soluble and therefore.52 78.34 As sorption is an exothermic process.9253 R2 0.36 106.83 10.63 11.9832 0.11 RL 0.60 10.707 R2 0.50 24.07 6. 323 K.9675 0.80 85. 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. Between these two stages the rate of sorption is nearly constant. CZBFA.9811 1.76 kJ mol−1 and the positive value confirms the endothermic nature of the overall sorption process. Among the three sorbents studied FZBFA exhibits higher sorption capacity than CZBFA and BFA due to its larger surface area and larger pore volume.076 0. Furthermore. The equilibrium sorptive removal follows the order FZBFA (48.9827 0.010 R2 0.107 2. 1270 wileyonlinelibrary.12 mg g−1 ) > BFA (28. A Shah Table 2.70 11. A value of H0 less than ∼20 kJ mol−1 indicates sorption is physical rather than chemical.14 6. Thermodynamic parameters were evaluated from Van’t Hoff plots. H0 is the enthalpy change (kJ mol−1 ).49 mg g−1 ) > CZBFA (45. However.93 92.43 B (mol2 J−2 ) 5.3.17 20.soci.www.41 13. occupation of the remaining vacant surface sites is difficult due to repulsive forces between the solute molecules in the solid and bulk phase and the rate slows.23 37. if the sorption process is influenced by cylindrical (or spherical) diffusion and convective diffusion (intra-particle transport-pore diffusion).60 47.31–20.9878 E (kJ mol−1 ) 0. 86: 1265–1275 . 4). R ln Kd = − G0 = T S0 − H0 T (1) Table 3. and FZBFA − G0 (kJ mol−1 ) Sorbents BFA CZBFA FZBFA 303 313 323 333 H0 (kJ mol−1 ) 9.041 0. and FZBFA) and the uptake curves are smooth and continuous leading to saturation after 360 min.76 S0 mol−1 ) (J K−1 5.02 6.com/jctb c 2011 Society of Chemical Industry J Chem Technol Biotechnol 2011.24 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.58 12. The efficiency of sorbents for the removal of 2-CP has the order FZBFA > CZBFA > BFA. Effect of agitation time The solutions were agitated with a known amount of sorbents (BFA. CZBFA. which will result in increase of 2-CP sorption.

9 for all the systems studied indicate that sorption is probably a surface phenomenon. data were fitted to the external diffusion model. and the slight dependence of Kf on C0 may be indicative of a complex sorption process.34 It can be expected that both film and pore diffusion are important to different extents in the removal process. possibly because the qe values depend on the initial 2CP concentration (C0 ) and are well below the monolayer capacities found by equilibrium modeling. The correlation coefficient and external diffusion coefficient (ked ) calculated from the plots of ln (Ct /C0 ) versus t are presented in Table 4. 86: 1265–1275 c 2011 Society of Chemical Industry wileyonlinelibrary. or a combination of more than one step. Though Figure 4. Intra-particle diffusion study The overall sorption process may be controlled either by one or more steps.886 mg g−1 min−1/2 . for intra-particle diffusion (Table 4). t1/2 . Curved plots for the initial period are usually attributed to boundary layer diffusion effects or external mass transfer effects. The plots exhibit good correlation coefficients with the correlation coefficient of 2-CP on FZBFA much closer to unity (Table 4). pore diffusion. i. 0. Kinetic parameters with correlation coefficients are listed in Table 4. the equilibrium sorption capacity obtained using the intercept of the model does not yield reasonable values. log (qe − qt ) was plotted against t (figure not shown) and the linearity of the Lagergren (pseudo-first-order) plots with good correlation coefficients (Table 4) confirms its applicability for this process. Sorption kinetics were determined by applying pseudo-first-order and pseudosecond-order kinetic models. These values are in the range 0.41 The intercepts provide a measure of the boundary layer thickness.091–0.36 External diffusion model To distinguish between film and intra-particle diffusion. the linear Lagergren’s equation plots do not strictly pass through the origin. Therefore. and CZBFA is more efficient than BFA. kid . Bangham’s equation Kinetic data were further used to study the slow step occurring in the later stage of sorption using Bangham’s equation. and FZBFA. film or external diffusion. Further. The double logarithmic plots (figure not shown) according to the Bangham’s equation were not perfectly linear as the diffusion of 2-CP into the sorbent pores is not the only the rate controlling step. Pseudo-first-order kinetics model The pseudo-first-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. sorption can be more appropriately described by the pseudo-secondorder kinetic model.36. The pseudo-first-order kinetics. external diffusion plays an important role in the process.soci.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 equilibrium sorption capacity (qe ) and the pseudo-second-order constant ks can be determined 1271 J Chem Technol Biotechnol 2011. Effect of agitation time on the sorption of 2-CP by BFA.com/jctb . and sorption on the pore surface.309. Diffusion of sorbate was ascertained using Bangham’s equation. 0. surface diffusion. The linear forms of all the models were used from earlier work. The results (Fig.697–0.347). Similar results were reported by Mall et al. R2 values > 0.39 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. The initial sorption rate (h).e.356. CZBFA. With increased contact time.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 α (<1) and k0 are given in Table 4.g. Thus the applicability of the pseudo-second-order model suggests a somewhat complex mechanism of sorption instead of a single step process.152 mg g−1 min−1/2 . This may be due to the high surface area and high pore volume of FZBFA and CZBFA. CZBFA. indicate macropore/mesopore diffusion and micropore diffusion. for the removal of phenol on activated carbon and bagasse fly ash.Sorption of 2-chlorophenol by modified bagasse fly ash www. Similar behaviour has been observed in the sorption of phenol on bagasse fly ash and activated carbon27 and activated carbon prepared from coconut coir pith. the α observed in the present studies are lower than those reported (α = 0. e.40. Sorption can be considered as a reversible reaction with equilibrium established between two phases. the effect of diffusion on the overall sorption could be ignored. and FZBFA.37 The applicability of a particular rate expression for the 2-CP–sorbents systems was evaluated from the goodness of data fit and regression coefficient value. 5) for sorption on BFA. Thus. Similar results were reported by Tutem et al. SORPTION KINETICS The sorption kinetics are important as they control process efficiency. and BFA. intra-particle diffusion and external diffusion. Further. occurring on the exterior of the sorbent particles. 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.org experimentally from the slope and intercept of a plot of t/qt versus t.41 The slope of the linear portion of the figure can be used to derive values of the rate parameter. while in the second portion it is in the range 0. compared with BFA. The range of correlation coefficients is much closer to unity than for the pseudo-first-order model. the larger the value of intercept the greater the boundary layer effect. However. suggesting that sorption is not a true first-order reaction.

37 R2 0. Thus column studies were carried out with BFA and CZBFA.9992 0. in the range 15. which signifies that intra-particle diffusion is not the only rate controlling step. 86: 1265–1275 .org B Shah.9554 0.44 5. 2 (mg g−1 min−1/2 ) 0.091 0.42 A column study for the sorption of 2-CP by FZBFA was not feasible as the column blocked within 30 min.75 31. 1272 wileyonlinelibrary.9926 0.85 × 10−4 R2 0.36 45. 2 than kid.80 4.03 × 10−3 2.152 I2 (mg g−1 ) 26.38 49. a straightforward approach may be adopted for the design of a fixed bed sorber.260 k0 (g) 1. I.53 mg g−1 .37 × 10−4 3.127 0. 1 suggest that 2-CP diffuses into the pores of the sorbents.9989 0.9657 0.18 13.com/jctb c 2011 Society of Chemical Industry J Chem Technol Biotechnol 2011.www.82 46. The breakthrough point was selected arbitrarily at some low value Cb (break point concentration) for the effluent concentration and Cx (exhaustion point concentration) closely approaching C0 (influent concentration of Figure 5.06 × 10−3 2. 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.15 kf (min−1 ) 1. 1 (mg g−1 min−1/2 ) BFA CZBFA FZBFA 0.9949 kid. CZBFA. As the diffusion resistance increases with time the diffusion rate decreases.36 In the present study the plots do not pass through the origin and have intercepts.9924 0.33 ks (g mg−1 min−1 ) 2.49 R2 0.9902 0. Intra-particle diffusion curves of 2-CP sorption on BFA.18 × 10−3 8. Mass units for C and Ve are used to illustrate the concept of mass balance in the sorption system.9811 0.9785 0. The lower values of kid.14 43.13 × 10−3 R2 0.62 37.53 R2 0.41 × 10−3 8.205 0.75–45.9995 13. It may be concluded that surface sorption and intra-particle diffusion operate concurrently during the sorbate–sorbent interactions. Designing of fixed bed sorption column For a system involving a feasible sorption process.88 × 10−4 3.89 0.65 3.96 R2 0.9239 29. R Tailor.45 × 10−3 h (mg g−1 min−1 ) 1. 2-CP).82 11. and FZBFA.9898 0.9897 the coefficient values (Table 4) for the intra-particle diffusion model are lower than those obtained for the pseudo-secondorder model.234 0.9819 0.73 4. A Shah Table 4.85 0.9485 0.69 I1 (mg g−1 ) 15. thus. Kinetic parameters for the removal of phenols by BFA. the values are close to each other. at which the sorbent is considered to be essentially exhausted.soci. and FZBFA Pseudo-first-order qe (mg g−1 ) BFA CZBFA FZBFA Pseudo-second-order qe (mg g−1 ) BFA CZBFA FZBFA Bangham α BFA CZBFA FZBFA External diffusion ked (cm min−1 ) BFA CZBFA FZBFA Intra-particle diffusion kid.9930 0.9664 8. CZBFA.

The results reveal that for 2-CP the total time (tx ) required for the primary zone to establish itself.19 Exhaustion capacity (mg g−1 ) 81. δ and percentage saturation at breakpoint (Table 5). f .019 1. 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 higher the percentage saturation in contrast with results obtained by Gupta et al.600 0. tf .019 D (cm) 12 12 % saturation 75.80 Breakthrough capacity (mg g−1 ) 61. From these observations a direct relationship between the length of the sorption zone (δ) and percentage saturation at break point can be developed.57 98.600 and 0.org 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.66 Sorbents BFA CZBFA these sorbents can be effectively used in columns to remove 2-CP from waste-waters.571 Fm (mg cm−2 min−1 ) 1. The smaller the length of the sorption zone. respectively. apart from protecting the environment from a disposal problem.5 h for both sorbents. The higher capacity of column operations was explained by a continuously large concentration gradient at the interface zone as it passes through the column.22 Vx − Vb (mg cm−2 ) 305.0 for BFA while it is 77. Furthermore.78 1273 J Chem Technol Biotechnol 2011. quantity of effluent. Table 6. Desorption studies Disposal or regeneration of spent sorbent is an important economic factor in assessing the feasibility of a sorption system. the loaded sorbents were washed gently with distilled water to remove any unsorbed 2-CP. Desorption was Table 5.61 tf (min) 120 120 Vb (mg cm−2 ) 305. i. Table 6 shows that the degree of column utilization is 74. 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 effluent corresponding to Cb and Vx is the volume of effluent corresponding to Cx . The time taken for initial formation of the primary sorption zone (tf ) is 1.73 285. Cx .09 Column utilization (%) 74.35 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.43 The percentage saturation of the column at break point is obtained from: % saturation = D + δ(f − 1) × 100 D (2) www.00 77. respectively. Breakthrough curves and desorption plots of 2-CP on BFA and CZBFA.35 f 0.3 for chlorophenols and Bhatnagar Amit for bromophenols.02 81. 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.4 tx (min) 600 660 Cx (mg cm−3 ) 0. time required for initial formation of PSZ (tf ). 86: 1265–1275 c 2011 Society of Chemical Industry wileyonlinelibrary.391 Cb (mg cm−3 ) 0. Thus. The parameters.022 0. Vx . mass flow rate (Fm ).80 77.80 and 77. move down the length of the column and out of the bed is 600 and 660 min on BFA and CZBFA. After batch sorption. while in the batch isotherm test the concentration gradient decreased with time. and Cb obtained from this graph were used to calculate tx . total time taken for the establishment of PSZ (tx ). tδ .52 78.43 The value of Vx –Vb is 305. Similar results were reported by Gupta et al.50 6.733 and 285. these data can be useful for the design of fixed bed sorbers for the treatment of known 2-CP concentrations. The breakthrough capacities are higher than the batch sorption capacities. If the technique is applied on large scale. respectively. Ve . time required for the downward movement of PSZ (tδ ).351 mg cm−2 for BFA and CZBFA.78 on CZBFA. Sorption capacity of BFA and CZBFA for 2-CP Batch capacity (mg g−1 ) 52. and fractional capacity (f ) were evaluated using reported equations.soci. The percentage saturation at breakpoint is 75.26 δ 7. primary sorption zone (PSZ = δ).392 0.com/jctb . The loaded sorbents were resuspended in 50 cm3 of desorbent and equilibrated for 24 h. Vb . which passes through the column (Fig.73 387.571 on BFA and CZBFA. Desorption studies help to elucidate the mechanism of sorption to recover the pollutant from the spent sorbent. respectively. Parameters of fixed bed column design obtained from breakthrough curve Sorbent BFA CZBFA Sorbent BFA CZBFA C0 (mg cm−3 ) 0.42. The values of Vb .4 0.47 672.019 tδ (min) 300 280 Vx (mg cm−2 ) 611.66% for BFA and CZBFA.e. these results show that Figure 6. 6). The fractional capacity f of the column in the sorption zone at breakpoint to continue to remove solute from solution is 0.Sorption of 2-chlorophenol by modified bagasse fly ash Two design parameters are important: (i) the total mass.

26 Coughlin RW and Ezra FS. The fine particle size of FZBFA prevented the column study with this sorbent. Environ Prog Sustainable Energy DOI 10. In column studies the breakthrough capacity of BFA and CZBFA was higher than the batch capacity. Rosic A and Lazic P. J Chem Technol Biotechnol 71:180–186 (1998). Utilization of NaCl for phillipsite synthesis from fly ash by hydrothermal treatment with microwave heating. Podkos’cielny P. PXRD. Coal ash conversion into effective adsorbents for removal of heavy metals and dyes from wastewater. Cincinnati. respectively. 16. 5 Gogate PR and Pandit AB. The maximum desorption of 2-CP was obtained using 0. UGC. R Tailor. 18 Shah BA. 1274 wileyonlinelibrary. Yadav IS and Mohan D. Process Biochem 40:997–1026 (2005). 5th edn. ACKNOWLEDGEMENT The authors are grateful to SAP meritorious fellowship.org carried out by suspending the loaded sorbents (0. 80. New York. Environ Sci Technol 29:1109–1117 (1995). Factors affecting sorption of organic compounds in natural sorbent/water systems and sorption coefficients for selected pollutants. After exhaustion the column was washed with 25 cm3 doubly distilled water to remove unsorbed phenols which were collected and analyzed for 2-CP. 24 Gupta VK. Int J Miner Proc 64:1–17 (2002). 13 Lin Cheng-Fang and His Hsing-Cheng. Desorption data show that HCl and SDS have a lower tendency to desorb 2-CP.89% by SDS from BFA. 10 Da browski A. Yamamoto T and Yoshida H. From these desorption studies it can be concluded that about 120 cm3 of 0. Oxford. respectively. Adsorption of phenolic compounds by activated carbon – a critical review. Similar results were reported by Anirudhan et al. The desorption plots reveal that the first 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. Ali I and Saini VK. Equilibrium and kinetic studies of the adsorption of basic dye from aqueous solutions by zeolite synthesized from bagasse fly ash. OH (1987). J Colloid Interface Sci 130:157–164 (1989). 19. 12 Wang Y.5 mol L−1 HCl and 23.com/jctb c 2011 Society of Chemical Industry J Chem Technol Biotechnol 2011. Then 0. Batch studies indicated sorption followed a Langmuir monolayer sorption isotherm. REFERENCES 1 US Environmental Protection Agency. 23 Treacy MMJ and Higgins JB. Amsterdam. J Hazard Mater 76:237–249 (2000). p-chlorophenol. Fuel 84:1482–1486 (2005).5 mol L−1 NaOH with 82. 7 Delle Site A. The uptake of 2-CP can be explained by external and intra-particle diffusion processes. Water Quality and Treatment. Yamamoto N and Shibata J.33. A Text Book of Quantitative Analysis. McGraw-Hill Inc.28 and 13. Li L and Zhu ZH.1002/ep.10505 (2011). which are readily desorbed due to their high solubility in aqueous media.soci. Katoh M. Cai H and Xavier Q. 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