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Removal of Cr(VI) from waste water using hyacinth roots: kinetic, equilibrium and thermodynamic studies

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Abstract Heavy metals such as chromium, copper, lead, cadmium, mercury, zinc etc., in wastewater are hazardous even in extremely minute quantities to the environment. Because of their toxicity, their pollution effect on our ecosystem presents a possible human health risk. Cr(VI) is one of the highly toxic metal entire into the environment from mining, leather tanning, cement industries, electroplating, production of steel and other metal alloys, photographic material and corrosive paints etc. It act as carcinogens, mutagens and teratogens in biological systems. So it is essential to remove from the environment. The efficiency of hyacinth roots as an adsorbent for removing of Cr(VI) ions from aqueous solution has been investigated. Batch adsorption experiments have been carried out to optimize the dependent parameter like pH, initial Cr(VI) ion concentration, adsorbent dosage and equilibrium contact time on the adsorption process. Maximum metal sorption was found to occur at initial pH 2. Kinetic data were best described by pseudo-second order model. The equilibrium adsorption data were better fitted to Freundlich isotherm model. The sorption energy calculated by using DubininRadushkevich isotherm model which indicated that the adsorption processes were chemical in nature. In addition, the thermodynamics parameters like standard free energy ( G 0 ), standard enthalpy ( H 0 ), standard entropy ( S 0 ) of the adsorption process were determined and results found that adsorption process is spontaneous and endothermic in nature. Keywords: Adsorption, hyacinth roots, kinetic data, thermodynamic parameter. 1. Introduction The presence of heavy metals in the environment is a major concern because of their toxicity and threat to human life and to the environment. Lead, cadmium, mercury, arsenic, copper, chromium etc. are examples of heavy metals that have been classified as priority pollutants. These pollutants tend to accumulate in bottom sediments from which they may be released by various processes of remobilization, thereby reaching human beings where they produce chronic and acute aliments. Cr(VI) as an example of such heavy metal which is toxic to animals, humans and it is also known to be carcinogenic[1]. The concentration of Cr(VI) in industrial waste water varies in the ranges from 0.5 to 270 mg/L [2]. The tolerance limit for Cr(VI) for discharge into inland surface water is 0.1mg/L and in potable water is 0.05 mg/L [3], [4]. In order to comply with this limit, it is essential that industries treat their effluents to reduce the Cr(VI) concentration in water and waste water to acceptable levels before its transport and cycling into the natural environment. Several methods are utilized to

remove Cr(VI) from industrial waste water. These include reduction followed by chemical precipitation, ion exchange, reduction, adsorption, electrochemical precipitation, cementation, evaporation, reverse osmosis, foam separation, freeze separation, bio-sorption [5]-[12]. Adsorption is by far most versatile and effective method for such removal, especially, if combined with appropriate regeneration steps. In this study hyacinth roots were used to remove Cr(VI) from aqueous solution. Factors affecting the adsorption characteristics such as initial pH, contact time, adsorbent dosage and initial Cr(VI) ion concentration were studied. Rate kinetics and isotherm models were also investigated to know the adsorption behavior of the adsorbent considered for study. 2. Experimental 2.1 Adsorbent used The water hyacinth roots used in this study were obtained from a pond of local area of Howrah district near Kolkata, West Bengal, India. The collected roots were extensively washed with distilled water to remove soil and dust. It was dried to the sunlight for 7 days. The sliced material was dried 1050C for 6 hr to remove the adherent moisture, sieved to obtain particle size of 250-350 m and then kept in desicators. 2.2 Reagent and equipments All the chemicals and regents used in the study were obtained from E. Merck Limited, Mumbai, India and had a pure analytical quality. Characterization of adsorbents were carried out by scanning electron microscope (SEM) Scanning electron microscope (S-3400N, Hitachi, Japan) studies was conducted to observe the surface texture and porosity of the adsorbents. UV-Spectrophotometer (U4100 spectrophotometer, Hitachi, Japan) was used to determine the Cr(VI) content in standard and treated solutions after adsorption experiments. The pH of the solution was measured with a EUTECH make digital microprocessor based pH meter previously calibrated with standard buffer solutions. Fig. 1 shows the scanning electron micrographs of hyacinth roots. This figure showed that it had an irregular and porous surface. 2.3 Preparation of standard Cr(VI) solution The stock solution containing 1000 mg/L of Cr(VI) was prepared by dissolving 3.73 g of A. R. grade K2CrO4, 2H2O in 1000 ml of de-ionized, double distilled water. 1 ml of the above stock solution =1 mg of Cr(VI). Required initial concentration of Cr(VI) standards were prepared by appropriate dilution of the above stock Cr(VI) standard solution. 2.4 Batch adsorption studies The quantitative amount of adsorbents were taken in a 250 ml stopper conical flask containing 100 ml of desired concentration of the test solution at the desired pH value, contact time and adsorbent dosage level. The pH of the solution was measured with a 5500 EUTECH pH Meter using FET solid electrode calibrated with standard buffer solutions. The contents in the flask were shaken for the desired contact time in an electrically thermostated reciprocating shaker @ 120-130 strokes/minute at 300C. The contents of the flask were filtered through filter paper and the filtrate

was analyzed for remaining metal ion concentration by UV visible spectrophotometer (Model No. U-4100 spectrophotometer, Hitachi, Japan) [13]. Results and discussion Fig. 2 shows the percentage removal of Cr(VI) as a function of pH. It is clearly evident that the adsorption characteristics of the adsorbent are highly pH dependent. The percentage removal reached a maximum value at an initial pH of the solution at 2. The equilibrium was reached at the contact time of 4 hr. as shown in Fig. 3. Fig. 4 shows the variation of adsorbent dosage on the percentage removal of Cr(VI). It is clear from the graph that the optimum adsorbent dosage 10 g/L for hyacinth roots. The effect of initial metal ion concentration on the removal of Cr(VI) is shown in Fig. 5. This graph indicated that the decrease in metal ion removal as the initial metal ion concentration increases. 3.1 Adsorption kinetics study 3.1.1 Pseudo first order Lagergren model The pseudo first order kinetic model was proposed by Lagergren [14]. The integral form of the model generally expressed as follows, K t log ( q e q ) = log q e ad 2.303 (1) 3.1.2 Pseudo second order model The linearized form of pseudo second order kinetic equation [15] may be expressed as, t 1 1 = + t (2) 2 q K 2 qe qe Lagergren and Pseudo second order models were presented in Fig. 6 and 7 respectively. The values of rate constants and correlation coefficients for each model were shown in Table 1. Pseudo second order model was best fitted with experimental adsorption data. 3.2 Isotherm model 3.2.1 Langmuir isotherm model The data obtained from adsorption studies were fitted to the Langmuir adsorption isotherm as [16] Ce C 1 = + e qe q max b q max (3) Linear plots of Ce/qe vs. Ce have been used to determine the value of qmax (mg/g) and b (L/mg) for the adsoption. The Langmuir constant along with correlation coefficients (r2) are listed in Table 2. 3.2.2 Freundlich isotherm model The adsorption data obtained were also fitted to the Freundlich adsorption isotherm as [17]
log q e = log K f + 1 log C e n

(4)

The values for Langmuir, Freundlich constants and correlation coefficients (r2) obtained from Figures 8 and shown in Table 2. Experimental data on adsorption were best fitted to freundlich adsorption isotherm. 3.2.3 Dubinin-Radushkevich (DR) isotherm The linear from Dubinin- Radushkevich isotherm model (18) was described as,

ln Cabs ln X m =

(5)

is the Polanyi potential (19) which is equal to:

= RT ln(1 +

1 ) Ce

(6)

From the plot of Cabc vs. 2 gave a straight line from which the values of and X m for hyacinth roots was calculated. Using the value of , the mean sorption energy, E, was evaluated as

E =

1 2

(7)

If E < 8 KJ/mol, the adsorption process is physical in nature and in the ranges from 8 to 16 KJ/mol, it is chemical in nature (20). The estimated value of E for Cr(VI) sorption was 11.5942 KJ/mol for hyacinth roots, which suggests the adsorption process is carried out chemical in nature. 3.3 Thermodynamic parameters for adsorption Adsorption experiments to study the effect of temperature were carried out at 30, 40 and 550C at optimum pH value of 2 and adsorbent dosage level 10 g/L. The equilibrium contact time for adsorption was maintained at 4 hr. 0 The thermodynamic equilibrium constant ( K c ) was calculated by determining the apparent equilibrium constant, K c at different initial concentration of Cr(VI) and extrapolating to zero. C K c' = a (8) Ce The Gibbs free energy, G0, enthalpy, H0, and entropy, S0 were computed using following equation 0 G 0 = RT ln k c (9) H 0 S 0 (10) ln k c = + RT R The value of standard free energy, G0, was calculated using Equation 9. The value of slope and intercept of the plot ln kc0 vs. 1/T, gave standard enthalpy, H0, and standard entropy, S0, respectively (Table 4). Conclusions The optimum pH for removal was found to be 2. Increase in the concentration of adsorbent, initial Cr(VI) concentration and contact time were found to be increase the percentage removal of Cr(VI). The kinetics of the Cr(VI) adsorption was found to follow pseudo second order rate
'

mechanism. Adsorption isotherm of Cr(VI) was better described by Freundlich adsorption isotherm model. The negative values of Gibbs free energy for the adsorption process reveal that the process is spontaneous. The standard enthalpy change for the adsorption indicated that the process is endothermic. Reference [1] Ranji, C. and Anirudhan, T.S. 1998. Batch Cr(VI) removal by polyacrylamide-grafted sawdust: Kinetics and Thermodynamics. Water Res., 32(12), 3772-378. [2] Patterson J. W. (1985). Industrial Wastewater Treatment Technology, 2 nd Edn. ButterworthHeinemann, London). [3] EPA (Environmental Protection Agency), Environmental Pollution Control Alternativesc Cincinnati, USA. [4] Indian standard. 1991.Drinking water- specification, first revision. IS 10500. [5] Zhou, X. Korenaga, T. Takahashi, T. Moriwake, T. and Shinoda, S. 1993. A process monitoring/ controlling system for the treatment of wastewater containing chromium (VI). Water Res., 27, 1049-1054. [6] Tiravanti, G. Petruzzelli, D. and Passiono, R. 1997. Pretreatment of tannery wastewaters by an ion exchange process for Cr(III) removal and recovery. Water Sci. Technol., 36, 197-207. [7] Seaman, J. C. Bertsch, P. M. and Schwallie, L. 1999. In situ Cr(VI) reduction within coarse textured, oxide-coated soil and aquifer systems using Fe(II) solutions. Env. Sci. Technol., 33, 938-944. [8] Dabhi, S. Azzi, M. and de la Guardia, M. 1999. Removal of Hexavalent chromium from wastewaters by bone charcoal. Fresen. J. Anal. Chem., 363, 404-407. [9] Kongsricharoern, N. and Polprasert, C. 1996. Chromium removal by a bipolar electrochemical precipitation process. Water Sci. Technol., 34, 109-116. [10] Lin, C. F. Rou, W. and Lo, K. S. 1992. Treatment strategy for Cr(VI) bearing wastes. Water Sci. Technol., 26, 2301-2304. [11] Aksu, Z. Kutsal, T. 1990. A comparative study for biosorption characteristics of heavy metal ions with C. vulgaris. Env. Technol., 11, 979-987. [12] Aksu, Z. Ozer, D. Ekiz H, Kutsal, T. and Calar, A. 1996. Investigation of biosorption of chromium(VI) on C. crispate in two staged batch reactor. Env. Technol., 17, 215-220. [13] Standard methods for examination of water and wastewater, 1998. 20th edition, APHA, AWWA. Washington D.C., New York. [14] Lagergren, S. 1898. Zur theorie der sogenannten adsorption geloster stoffe. Kungliga Sevenska Vetenskapasakademiens. Handlingar, 24, 1-39. [15] Ho, Y. S. McKay, G. Wase, D. J. and Foster, C. F. 2000. Study of the sorption of divalent metal ions on to peat. Ads. Sci. and Tech., 18, 639 650. [16] Langmuir, I. 1918. The adsorption of gases on plane surfaces of glass, mica, and platinum. J. Am. Chem. Soc., 40, 1361-1368. [17] Freundlich, H. 1906. Adsorption in solution. Phy. Chem. Soc., 40, 1361-1368. [18] Dubinin, M.M., Zaverina, E.D., Radushkevich, L.V., 1947. Sorption and structure of active carbons I. Adsorption of organic vapors. Zhurnal Fizicheskoi Khimii 21, 1351-1362. [19] Polanyi, M.,1932. Theories of the adsorption of gases. A general survey and some additional remarks, Transactions of the Faraday Society. 28, 316-333.

[20] Malik, U.R., Hasany, S.M., Subhani, M.S., 2005. Sorptive potertial of sunflower stem for Cr(III) ions from aqueous solutions and its kinetic and thermodynamic profile. Talanta 66, 166-173

Table 1 Rate Kinetics for the adsorption of Cr(VI) ion onto hyacinth roots Lagergren 1st order model Kad r2 (min-1) 0.02655 0.87512 Pseudo 2nd order model K2 r2 [(mg/g)min] 0.01238 0.99728

Table 2 Langmuir and Freundlich adsorption isotherm constants for Cr(VI) removal Langmuir constants qmax mg/g 14.3575 b L/mg 0.2268 0.9659 2.923 5 3.0262 0.9927 r2 Kf Freundlich constants n r2

Table 3 Dubinin-Radushkevich (D-R) isotherm parameter and activation energy for the removal of Cr(VI) D-R constant Activation energy KJ/mol 11.5942 0.9759 r2

-0.00372

Table 4 Thermodynamic parameters for the sorption of Cr(VI) onto adsorbents Thermodynamic parameters Temperatur e K 303 313 328 - G KJ/mol 5.2345 7.2084 9.8501 48.874 0.2835 H KJ/mol S KJ/mol

100

90

80

% removal of Cr(VI)

70

60

50

40

30

10

Initial pH

Fig.2. Effect of pH on Cr(VI) adsorption

Fig. 1. Scanning Electron Micrograph (SEM) of hyacinth roots

100

100

Percentage removal of Cr(VI), %

90

80

% removal of Cr(VI)

80

60

40

70

60

20 0.0

3.5

7.0

10.5

14.0

70

140

210

280

350

Adsorbent dosage, g/L

Contact time, min

Fig. 4. Effect of adsorbent dosage on Cr(VI) adsorption

Fig. 3. Effect of contact time on Cr(VI) adsorption

0.6

0.0

-0.6

log(qe-qt)

-1.2

-1.8

-2.4

-3.0

60

120

180

240

300

Contact time, min

Fig. 6. Lagergren plot for Cr(VI) adsorption

125
1.2

100

1.0

0.8

75
0.6

t/q

50

log qe
0 70 140 210 280 350

0.4

0.2

25
0.0

-0.2

Time, min Fig. 7. Pseudo second-order plot for Cr(VI) adsorption

-2

-1

log Ce

Fig. 8. Freuindlich plot for adsorption of Cr(VI)