Defluoridation of water using phosphoric acid modified activated carbon obtained from sugarcane-thrash

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ABSTRACT Carbon obtained from sugarcane thrash was chemically activated using different concentrations of phosphoric acid and tested for their capability for the adsorption of fluoride ions from drinking water. Physicochemical characterization of the raw and the activated carbons were performed using XRD, microanalysis and surface area analyzer. The results revealed that the adsorption capacity of carbon increased considerably on treatment with phosphoric acid. A comparison of the surface area of the carbons did not reveal significant change due to activation. Adsorption isotherm and kinetic studies were used to explain the fluoride adsorption characteristics of the adsorbents. Keywords: Activated carbon, adsorption, fluoride, isotherm, kinetics INTRODUCTION Fluorine in the range of 0.5 - 1.5 mg/l is a micronutrient that contributes to calcification of dental enamel and bone formation in human beings. It exists in water as fluoride ion (F - species). Higher concentration of fluoride in drinking water can lead to fluorosis. The WHO recommended maximum contaminant level (MCL) for fluoride in drinking water is 1.5 mg/l [1]. Fluoridation of drinking water is a world-wide problem, occurring primarily due to natural weathering of the fluoride minerals present in the earths crust [2] and the discharge of fluoride containing wastewater coming from various industries. Increased incidents of fluorosis among the people are being reported from all over the world [3]. The existing fluoride removal techniques include precipitation-coagulation, membrane filtration and ion exchange or adsorption based processes. Among these, adsorption is considered to be the most efficient and applicable technology for removal of fluoride from drinking water as the fluoride concentration in ground water is very low (5 40 mg/l). A wide variety of adsorbents (e.g. activated and impregnated alumina [4], natural and synthetic clays [5, 6], carbonaceous materials [7], bio-polymeric adsorbents [8], industrial wastes like red mud and fly ash [9]) have been tested for defluoridation of water. The carbonaceous materials obtained from agricultural wastes have attracted considerable attention to the researchers, from economic and environmental point of view. Adsorbents like, wood charcoal, carbons obtained from rice straw [10], coconut shell [11], have been explored for their fluoride removal capability. The present study reports adsorption of fluoride in water on activated carbon made from sugarcane thrash. The carbon obtained from sugarcane thrash was chemically activated, characterized using different techniques and tested for their fluoride adsorption capacity from drinking water. Adsorption isotherm and kinetic studies were used to explain the fluoride adsorption characteristics of the adsorbent. EXPERIMENTAL

Reagents

Ortho-Phosphoric acid (H3PO4, 85 % pure, Merck) was used for chemical activation of the carbon. Fluoride solutions for adsorption study were prepared from AR Grade Sodium Fluoride (Merck). Distilled water was used for preparing the standard solutions.
Adsorbent activation A fixed weight (10 g) of the pristine carbon obtained from sugarcane thrash was added to 100 ml of 0.25 N ortho-phosphoric acid, stirred well and kept overnight. The solid carbon was then separated by filtration followed by washing with distilled water till the washed liquid was neutral to litmus. This treated carbon was then dried overnight at 110 C in an air oven to obtain the C-25AC. Two other adsorbent samples, C-50AC and C-75AC were prepared by following a similar procedure using 0.50 N and 0.75 N ortho-phosphoric acid, respectively. The pristine carbon obtained from sugarcane thrash is denoted as C-NAC. Characterization techniques The chemically activated carbon adsorbents were characterized for their chemical composition, crystallinity and BET surface area using different characterization techniques. Concentrations of N, H and S present in the adsorbent samples were analyzed using C, H, N, S, analyzer (CARLO-ERBA, Italy). The mineralogical phases and crystallinity of the raw- and activated- carbons were studied by X-ray diffraction (XPERT-PRO from PANalytical Instruments, Netherlands) using Cu-K radiation. BET surface area was determined by N2 adsorption-desorption technique using Autosorb-1 from Quantachrome Instruments, USA. Batch adsorption experiments Batch adsorption experiments were carried out under isothermal conditions at 25 C in a thermostatic shaker (Julabo SW-21C). 50 cm3 of fluoride solution of known concentration (5-25 mg/l) was contacted with 0.2 g of the adsorbent in polypropylene (PP) bottles for 24 h in thermostatic shaker. Residual fluoride concentration was analyzed at specific time intervals using fluoride ion selective electrode (ISE, Metrohm 781 pH/Ion Meter) in presence of total ionic strength adjustment buffer (TISAB). The adsorption capacity of the clay was estimated using the formula:

q e (mg / g ) =

(C 0 C e ) V .(1) w 1000

where, C0 : initial fluoride concentration (mg/l); Ce : equilibrium fluoride concentration (mg/l); V : volume of solution (ml); w : weight of adsorbent (g); qe : amount of fluoride adsorbed per unit gram of the adsorbent at equilibrium (mg/g). RESULTS AND DISCUSSIONS Characterization of the adsorbent Concentrations of N, H and S present in the adsorbent samples and their specific surface area are presented in Table 1. Table 1. Physico-chemical characteristics of the pristine and activated carbons. Adsorbent N (%) H(%) S(%) Specific surface area (m2/g)

C-NAC 0.65 C-25AC 0.43 C-50AC 0.60 C-75AC 0.54 n.d. - not detected.

2.77 2.53 2.91 2.46

n.d n.d n.d n.d

16.6 14.9 17.9 8.7

Table 1 show that there is no change in hydrogen content of pristine carbon on activation with phosphoric acid. The nitrogen content in the carbons is very low and sulfur was present below the detection limit. A comparison of the surface area of the pristine carbon and activated carbons reveal no significant change due to activation using low concentrations of phosphoric acid. However the surface area reduces considerably on activation with 0.75 N phosphoric acid. X-ray diffraction pattern of the raw- and activated-carbon adsorbents are presented in Fig. 1a-d. The broad hump in the XRD patterns indicates amorphous nature of the pristine and activated carbons. The XRD pattern shows reflections corresponding to graphitic carbon phases.

Intensity (a.u.)

(d) (c) (b)

10 20 30 40 50 60

(a)

2 Theta (Degree)

Figure 1.

X-ray diffraction pattern of the pristine carbon (a) and carbons activated using different concentrations of phosphoric acid, 0.25 N (b), 0.50 N (c) and 0.75 N (d).

Adsorption isotherm Fluoride adsorption isotherm of the pristine and activated carbons studied at 25 C with an initial fluoride concentration ranging between 4 to 25 mg/l is presented in Figure 2. There is a distinct enhancement in adsorption capacity due to activation but the concentration of phosphoric acid above 0.50 N did not affect significantly on the adsorption capacity. The defluoridation capacity varied between 1.0 to 1.3 mg/g on changing the concentration of phosphoric acid solution between 0.25 to 0.75 N at an initial fluoride concentration of 25 mg/l. Among all the adsorbents studied, C-50AC and C-75AC showed maximum fluoride adsorption capacity of 1.95 mg/g. The adsorption data were fitted to Langmuir and Freundlich isotherm models. The form of the Langmuir isotherm model used is given below:

1 1 1 = + ..(2) qe bV m C e Vm Here, b and Vm are Langmuir isotherm constants representing adsorption bond energy and monolayer adsorption capacity (mg/g) respectively; Ce and qe are the equilibrium concentration and equilibrium adsorption capacity.

Freundlich isotherm constant may be represented as 1 ln q e = ln K F + ln C e ..(3) n where, n and KF are Freundlich isotherm constants representing adsorption intensity and adsorption capacity respectively.
2.5 2 1.5 1 0.5 0 0 5 10 15

Eq. Ads. Cap. (mg/g)

C-NAC C-25AC C-50AC C-75AC

20 NAC)

Poly. (C-

25

Eq. Conc. (mg/l)

Figure 2. Fluoride adsorption isotherm of the pristine and activated carbons at 25 C (Vol. of solution 50 ml; contact time 24 h; adsorbent dose 0.2 g). The values of isotherm constants calculated from the slopes and intercepts of the plots of Langmuir and Freundlich isotherm equations are presented in Table 2. Although the values of correlation coefficients for both the isotherm models represent good fittings of the adsorption data, the Langmuir model explains the fluoride adsorption behavior of the pristine and activated carbons more precisely than the Freundlich model. The adsorption bond energy (b from Langmuir model) clearly shows that the adsorption intensity decreases with increase in phosphoric acid concentration beyond 0.5 N, during chemical activation of the adsorbent. Table 2. Langmuir and Freundlich isotherm constants for pristine and activated carbons Adsorbents C-NAC C-25AC C-50AC C-75AC Langmuir constants b Vm R 0.03 2.99 0.76 0.53 1.61 0.94 0.53 1.94 0.97 0.18 2.06 0.85 Freundlich constants n KF R 1.33 0.12 0.81 3.37 0.67 0.99 3.15 0.78 0.99 1.65 0.34 0.89

Adsorption Kinetics

The fluoride adsorption kinetics of the pristine and activated carbons was studied up to 24 h. The rate of adsorption for all the activated carbons (except the untreated adsorbent, C-NAC) was slow. The equilibrium was attained within 24 h. The Lagergren first-order kinetic model was used to study the fluoride adsorption kinetics of the pristine and activated carbons. Lagergren first-order kinetic model is given below:
ln( q e q t ) = ln( q e ) K 1 .t

..(4)

Here, K1 represents the first-order rate constant; qt represents the adsorption capacity at time t and q e is the equilibrium adsorption capacity obtained after 24 h of adsorption. The model was found to give a good fit to the kinetic data. The values of K1 and the corresponding equilibrium adsorption capacities (qe(cal)) calculated using the kinetic model are presented in Table 3 along with their experimental adsorption capacities at different initial fluoride concentrations. The rate constants for all the activated carbons are between 0.12 x10-2 to 0.45 x 10-2. Table 3. First-order kinetic parameters for the pristine and activated carbons. Adsorbent C-NAC C-25AC C-50AC C-75AC Initial F- Conc. (mg/l) 4.38 10 20.4 5.12 10 22.7 5.14 10 22.6 4.45 10 22.7 qe(exp) mg/g 0.18 0.32 0.90 0.82 1.09 2.43 0.89 1.32 2.80 0.58 0.83 2.25 K1 x 102 min-1 1.39 0.59 0.36 0.26 0.20 0.12 0.25 0.30 0.12 0.43 0.45 0.21 qe(cal) mg/g 0.11 0.15 0.71 0.80 0.95 2.20 0.83 1.25 2.67 0.55 1.44 2.11 R2 0.87 0.61 0.87 0.99 0.87 0.83 0.97 0.98 0.95 0.98 0.91 0.95

3
C-NAC

Eq. ads. cap. (mg/g)

2.5 2 1.5 1 0.5 0 0

C-25AC C-50AC C-75AC

10

15

20

25

Initial Conc. (mg/l)

Figure 3. Equilibrium adsorption capacity of pristine and activated carbons as a function of initial fluoride concentration (Vol. of solution 50 ml; contact time 24 h; adsorbent dose 0.2 g). Plots of equilibrium adsorption capacity of pristine and treated carbons presented in Fig. 3 shows that the equilibrium capacity increases with increase in initial concentration. This increase is higher in the case of activated carbons. The increase in the equilibrium capacity is the highest for carbon activated with 0.5 N H3PO4. Activation with H3PO4 of higher concentration has a negative effect on the equilibrium adsorption capacity of the carbon indicating that there is an optimum concentration of the acid that gives the highest performance for the activated carbon. CONCLUSION Carbon obtained from sugarcane thrash can be used for defluoridation of drinking water after chemical activation with phosphoric acid. XRD study of the pristine and active materials showed the phase of carbon present was graphite. A comparison of the surface area of the carbons did not reveal significant change due to activation. This indicates that the increase in adsorption capacity is mainly because of the generation of new adsorption sites due to the acid treatment. Among the four carbon adsorbents, the activated carbon adsorbent obtained by treatment with 0.5 N H3PO4 showed maximum fluoride adsorption capacity. Adsorption data were explained using Langmuir and Freundlich isotherm models. The rate of fluoride adsorption was very slow and the adsorption kinetic followed a pseudo first-order kinetic model.

ACKNOWLEDGEMENT Sujata Mandal wishes to thank Council of Scientific and Industrial Research (CSIR), New Delhi, for financial support. REFERENCES [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] WHO (1984) Guidelines for drinking water quality, World Health Organization, Geneva, Vol. 2, P. 249. CEPA, Canadian Environmental Protection Act. (1994) Priority substance list supporting document for inorganic fluorides prepared by eco-health branch and environment, Canada, Ottawa (Ontario). Mella S., Mohira X. and Atalah E. (1994) Prevalence of endemic dental fluorosis and its relation with fluoride content of public drinking water. Revista Medica Chile 122, 1263-1270. Maliyekkal, S.M., Shukla, S., Philip, L., Nambi, I. M., 2008. Enhanced fluoride removal from drinking water by magnesia-amended activated alumina granules, Chemical Eng. J. 140, 183-192. Meenakshi, S., Sundaram, C.S., Sukumar, R.,2008. Enhanced fluoride sorption by mechanochemically activated kaolinites, J. Hazard. Mater. 153, 164-172. Mandal, S., Mayadevi, S., 2008. Adsorption of fluoride ions by Zn-Al layered double hydroxides, Appl. Clay Sci. 40, 54-62. Mohan, D., Singh, K.P., Singh, V.K., 2008. Wastewater treatment using low cost activated carbons derived from agricultural byproductsa case study, J. Hazard. Mater. 152, 1045-1053. Ma, W., Ya, F-Q., Han, M., Wang, R., 2007. Characteristics of equilibrium, kinetics studies for adsorption of fluoride on magnetic-chitosan particle, J. Hazard. Mater. 143, 296-302. Cengeloglu, Y., Kir, E., Ersoz, M., 2002. Removal of fluoride from aqueous solution by using red mud, Sep. Purif. Technol. 28, 81-86. Daifullah, A.A.M., Yakout, S.M., Elreefy, S.A., 2007. Adsorption of fluoride in aqueous solutions using KMnO4-modified activated carbon derived from steam pyrolysis of rice straw. J. Hazard. Mater. 147, 633643.

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