Bioresource Technology 97 (2006) 1520

Removal of chromium from industrial waste by using eucalyptus bark

Vikrant Sarin, K.K. Pant
*
Department of Chemical Engineering, Indian Institute of Technology, Hauz Khas, New Delhi 110 016, India Received 16 November 2004; received in revised form 31 January 2005; accepted 18 February 2005 Available online 7 April 2005

Abstract Several low cost biomaterials such as baggase, charred rice husk, activated charcoal and eucalyptus bark (EB) were tested for removal of chromium. All the experiments were carried out in batch process with laboratory prepared samples and wastewater obtained from metal nishing section of auto ancillary unit. The adsorbent, which had highest chromium(VI) removal was EB. Inuences of chromium concentration, pH, contact time on removal of chromium from euent was investigated. The adsorption data were tted well by Freundlich isotherm. The kinetic data were analyzed by using a rst order Lagergren kinetic. The Gibbs free energy was obtained for each system and was found to be 1.879 kJ mol1 for Cr(VI) and 3.885 kJ mol1 for Cr(III) for removal from industrial euent. The negative value of DG0 indicates the feasibility and spontaneous nature of adsorption. The maximum removal of Cr(VI) was observed at pH 2. Adsorption capacity was found to be 45 mg/g of adsorbent, at Cr(VI) concentration in the euent being 250 mg/l. A waste water sample containing Cr(VI), Cr(III), Mg, and Ca obtained from industrial unit showed satisfactory removal of chromium. The results indicate that eucalyptus bark can be used for the removal of chromium. 2005 Elsevier Ltd. All rights reserved.
Keywords: Adsorption; Eucalyptus bark (EB); Hexavalent chromium; Lagregren kinetic; Freundlich isotherm

1. Introduction Water pollution by chromium is of considerable concern, as this metal has found widespread use in electroplating, leather tanning, metal nishing, nuclear power plant, textile industries, and chromate preparation. Chromium exists in two oxidation states as Cr(III) and Cr(VI). The hexavalent form is 500 times more toxic than the trivalent (Kowalski, 1994). It is toxic to microorganism plants, animals and humans. Human toxicity includes lung cancer, as well as kidney, liver, and gastric damage (US Department of Health and Human Services, 1991; Cieslak-Golonka, 1995). The tanning process is one of the largest polluters of chromium all

Corresponding author. Tel.: +91 11 26596172; fax: +91 11 2652 1120. E-mail address: kkpant@chemical.iitd.ac.in (K.K. Pant). 0960-8524/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2005.02.010

over the world. Most of the tanneries in India adopt the chromium tanning process because of its processing speed, low costs, and light color of leather and greater stability of the resulting leather. In the chromium tanning process, the leather takes up only 6080% of applied chromium, and the rest is usually discharged into the sewage system causing serious environmental impact. Chromium ion in liquid tanning wastes occurs mainly in trivalent form, which gets further oxidized to hexavalent Cr(VI) form, due to the presence of organics. The maximum levels permitted in wastewater are 5 mg/L for trivalent chromium and 0.05 mg/L for hexavalent chromium (Acar and Malkoc, 2004). With this limit, it is essential for industries to treat their euents to reduce the Cr to acceptable levels. Due to more stringent environmental regulations, most of the mineral processing plants, metal-nishing industries are facing nowadays the dicult problem of disposal of wastewater produced in huge quantities, laden with Cr.

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Chromium metal ions are usually removed by precipitation (Patterson, 1977), although ion exchange (Tiravanti et al., 1997) and adsorption (Dahbi et al., 1999; Orhan and Buyukgangor, 1993) are also used for its removal. The hydroxides of heavy metals are usually insoluble, so lime is commonly used for precipitating them. The most important factor in precipitation of heavy metal is the valence state of metal in water. Cr whose hexavalent form, chromate CrO2 4 , is considerably more soluble than trivalent form, Cr(III). In this case, the chromate, in which Cr is present as Cr(VI) must be reduced usually with SO2 available from sodium metabisulphite at low pH for removal of chromium as Cr(III) by precipitation process. Another aspect of precipitation process is the zeta potential of the initial heavy metal colloidal precipitate. In many plants where heavy metals are being removed, one of the principal problems in reaching the desired euent limits is the colloidal state of precipitated materialsthey have not been properly neutralized, coagulated and occulated. A nal aspect of heavy metals is the possible formation of complex ions, which is common when dealing with wastewaters containing ammonia, uoride, or cyanide ions along with heavy metals. Because of these important aspects in the precipitation of heavy metals, there is no way to predict the best solution of a specic problem without undergoing a series of bench tests to evaluate the alternative available (Kemmer, 1988). The present study is aimed at selection of a low cost biosorbent, which can adsorb chromium from the wastewater. Detailed batch studies with the selected adsorbent, eucalyptus bark has been carried out in the present investigation. The eect of pH, contact time, adsorbent concentration, thermodynamics study, and metal ion/adsorbent ratio were also investigated.

grounded to small particles of size 120 < dp < 500 lm. It was washed with deionized water and then dried. To avoid, the release of color by bark in to the aqueous solution during adsorption, it was treated with formaldehyde (Randall et al., 1976). For this 5 mL of aqueous formaldehyde was added to 100 mL of 0.1 M H2SO4 and then 10 g of grounded and washed bark was added to this solution. The nal mixture was stirred and heated at 50 C for 2448 h till the mixture became thick slurry. The slurry (treated bark) was washed with deionized water until the pH of the ltrate was more than 4.5. Finally the bark was air-dried and sieved. Particles in the range of 120500 lm size were collected as the nal adsorbent. Surface area of the sorbent was determined, using BET apparatus, using liquid nitrogen as adsorbent. Further, ultimate and proximate analysis of the EB adsorbent was also carried out. The detailed characteristics of EB obtained are shown in Table 1. 2.3. Determination of chromium content The chromium concentration in raw and treated euent was determined by UV (Varian, Australia) spectrophotometer. The wavelength of operation was kept at 540 nm. For this purpose, K2Cr2O7 solutions of dierent concentrations were prepared and their absorbance recorded by using a UV-spectrophotometer. A calibration plots for Cr(VI) were drawn between % absorbance and standard Cr(VI) solutions of various strengths (APHA, 1992). Runs were made in triplicate. Cr(III) concentration was determined by measuring the dierence between total chromium concentration and Cr(VI) concentration. Total Cr concentration was determined by oxidizing Cr(III) to Cr(VI) using KMnO4 and then determining nal Cr(VI) content in the sample (APHA, 1992). 2.4. Experimental

2. Methods 2.1. Materials All the chemicals used were of analytical grade. K2Cr2O7, HCHO, NaOH, diphenyl carbizide, KMnO4, HNO3 and H2SO4 were procured from Merck. The adsorbents selected for the preliminary study were baggase, charred rice husk, activated charcoal, and eucalyptus bark (EB). These were grounded and washed with deionized water. The adsorbents were dried at room temperature, (32 1 C) till a constant weight of the adsorbent was achieved. A uniform particle size of the adsorbent was maintained between 120 and 500 lm. 2.2. Preparation of eucalyptus bark adsorbent Eucalyptus bark of Eucalyptus globulus tree species was collected from the local area. The bark was Stock solution of 1000 ppm of Cr(VI) was prepared by dissolving K2Cr2O7 (AR grade), in deionised, double-distilled water. All the batch adsorption studies
Table 1 Characteristics of eucalyptus bark (EB) adsorbent Characteristics Surface area (m /g) Bulk density (g/cm3) Moisture content (%) Ash content (%) Volatile matter (%) Fixed carbon (%) Carbon (%) Hydrogen (%) Nitrogen (%) Oxygen (%)
2

Values 0.59 0.05 0.25 0.02 10.1 0.3 19.0 0.5 65.7 2.0 15.3 0.5 43.68 1.3 8.14 0.25 0.43 0.01 47.75 1.4

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were carried out using 100 mL of solution of appropriate concentration as desired by dilution of the stock solution. Requisite quantity of adsorbent was added to 250 mL plastic reagent bottles containing 100 mL of synthetic euent of Cr(VI). The bottles were placed in a shaker at 32 1 C, for 24 h. The speed of shaker was kept at 100 rpm. After 24 h the bottles were removed and the content of the bottles was ltered through a lter paper. The ltrate was analyzed for pH and nal chromium concentration using UV Spectrophotometer. The removal of Cr(VI) was studied by using various adsorbents such as baggase, charred rice husk, activated charcoal, and eucalyptus bark. For all these runs the adsorbent dose was kept at 5 g L1 of synthetic euent of Cr(VI) and Cr(VI) concentration was kept at 50 ppm at pH of 5.2. Further studies on chromium removal were carried out using adsorbent as EB. This involved, varying initial Cr(VI) concentration ranging from 50 to 250 ppm. The pH was varied from 1.5 to 9 of with dierent initial concentrations. The contact time in batch was varied from 0.25 h to 24 h. The studies were also carried with industrial euent obtained from metal nishing industry (Automobile ancillary unit, manufacturing brake shoes, Sahibabad, U.P). The characteristics of industrial euent is as follows: Cr(VI) concentration 200 mg/L, Cr(III) concentration 44.5 mg/L, total dissolved solids 780 mg/L, Ca concentration 135 mg/L and Mg concentration 92 mg/ L. The samples were characterized by standard APHA method (APHA, 1992).

The adsorptive properties of activated carbon are due to its porous nature. Over 99% of the active sites for adsorption in GAC are located in the interior of the particle. Activated carbon particles have macropores and the micropores having diameters 30 to 100,000 A (Weber, having diameters in the range of 10 to 30 A 1967). Results of our investigation revealed that eucalyptus bark has highest percent removal and sorption capacity. Further investigations were made with this sorbent. A comparison of the sorbent capacity with various sorbents studied in literature is given in Table 2 and compared with EB. 3.2. Eect of pH Eect of solution pH on removal of Cr was studied using EB as sorbent. As the pH of the solution was increased from 1.5 to 9 the adsorption of Cr(VI) decreased. Increasing pH from 1.5 to 5, percent removal of Cr(VI) decreased 99 to 93, whereas as the pH was increased from 5 to 9 the % removal decreased signicantly from 93 to 63. It was observed that the maximum percentage of removal of Cr(VI) was at pH 2. Almost 100% of Cr(VI) removal was observed at this pH at 50 ppm Cr(VI) concentration. Dominant form of Cr(VI) at initial pH of 2 is HCrO 4 (Namasivayam and Yamuna, 1995). Increase in pH shifts concentration of 2 HCrO 4 to other forms, CrO4 and Cr2 O7 . It can be concluded that the active form of Cr(VI) that can be adsorbed by EB was HCrO 4 . Further it was observed that there was an increase in pH during adsorption. The increase in pH with contact time explained by hydrolysis of the adsorbent in water, which will create positively charged sites. Upon adsorption of HCrO 4 , a net production of hydroxide ions will occur as shown below (Saliba et al., 2002).
 OH 2 HCrO4 $ OH2 HCrO4

3. Results and discussion 3.1. Performance of various adsorbents for Cr removal The performances of these sorbents were evaluated for the percent removal of chromium. The maximum (87.4%) removal of chromium was achieved with EB. The percent chromium removal with other three sorbents were signicantly low as compared to EB (charred rice husk 36%, activated carbon 9% and bagasse 35%) therefore not considered for further investigations. The variation in the sorption capacity between the various adsorbents could be related to the nature and concentration of surface groups responsible for interaction with the metal ions. The selected adsorbents were cellulose based plant bers having many hydroxyl groups that may bind the Cr(VI) ion. Formaldehyde pretreatment of eucalyptus bark led to crosslinking of compounds in the bark to form a phenolformaldehyde copolymer that preserved high capacity of the support towards the adsorption of cations. This can be explained by the interactions in the solutions between the cations and the water extracted moieties, leading to complexities that precipitate on the support surface (Saliba et al., 2002).

Every mole of HCrO 4 adsorbed results in the release of two moles of hydroxyl ions in the solution, which raises the solution pH (Namasivayam and Yamuna, 1995). This change in pH at lower initial pH is very small since the solutions at lower pH are well buered by the acids used in this pH range. 3.3. Eect of contact time Fig. 1 shows the eect of contact time. Increasing contact time from 0.25 h to 3 h increases % Cr removal. Maximum Cr removal was observed with in rst 2 h. The kinetic data was tted to the Lagergren equation (Singh and Pant, 2004). logxe x log xe K ads t=2:303 2 x = the amount of solute, Cr(VI), (mg/g of adsorbent) removed at time t, xe = amount removed at equilibrium

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Table 2 Adsorption capacity of various adsorbents as reported in literature Adsorbent Maximum adsorption capacity (mg/L) 39.7 29.0 13.4 17.2 15.0 57.7 5.87 8.66 5.36 45.00 Optimum pH Maximum concentration C0 (mg/L) 1000 500 500 40 100 100 250 References

Saw dust Coconut husk bers Sugar cane bagasse Sugar beet pulp Palm pressed bers Activated carbon (Filtrasorb-400) Biogas residual slurry Wool Pine needles Eucalyptus bark

2.0 2.05 2.0 2.0 2.0 2.0 2.0 2.0 2.0

Sharma and Foster (1994) Huang and Wu (1977) Sharma and Foster (1994) Sharma and Foster (1994) Tan et al. (1993) Huang and Wu (1977) Namasivayam and Yamuna (1995) Dakiky et al. (2002) Dakiky et al. (2002) Present study

120 100 80 60 40 20 0
I.E., Cr(VI), at pH - 3.41 I.E., Cr(III), at pH - 3.41 pH - 2 pH - 3 pH - 4.7

2.5

Chromium(VI) removal (%)

log(Xe - X)

1.5

1
pH - 2 pH - 3 pH - 4.7 I.E., Cr(VI), at pH - 3.41 I.E., Cr(III), at pH - 3.41

0.5

15

30

45

60

75 90 105 120 150 180 210 Time (min)

20

40

60 Time (min)

80

100

120

Fig. 1. Eect of contact time on removal of Cr(VI) by eucalyptus bark from synthetic euent (S.E.) having Cr(VI) 200 ppm, pH 4.7 and industrial euent (I.E.) having Cr(VI) 200 ppm, Cr(III) 44.5 ppm and pH 3.41. Adsorbent dosage was 5 g/L.

Fig. 2. Lagergren plot for the adsorption of Cr(VI) by eucalyptus bark adsorbent from synthetic euent having Cr(VI) 200 ppm, pH 4.7 and industrial euent having Cr(VI) 200 ppm, Cr(III) 44.5 ppm and pH 3.41. Adsorbent dosage was 5 g/L.

and Kads = the rate constant of adsorption (1/min). The eect of contact time was studied for removal of Cr from euent containing 200 ppm of Cr(VI) at 32 1 C, pH 2, pH 3, pH 4.7. Experiments were also carried out industrial euent containing Cr(VI) 200 ppm and Cr(III) 44 ppm. For EB the contact time of 3 h was needed to establish equilibrium. The kinetic on dierent solution of Cr(VI) at dierent pH with EB as adsorbent was found to follow the rst order rate. Fig. 2 depicts the Lagergren plots with a regression coecient more than 0.9. Adsorption rate constant is given in Table 3. 3.4. Adsorption isotherm Adsorption isotherms, which are the presentation of the amount of solute adsorbed per unit of adsorbent, as a function of equilibrium concentration in bulk solution at constant temperature, were studied. The equilibrium data obtained were tted to Langmuir and Freundlich isotherms. Linear form of Langmuir equation, 1=X 1=X m 1=C e 10 =b X m 3

Table 3 Adsorption rates constant for EB for various systems Cr(VI) concentration (mg/L) 200 ppm 200 ppm 200 ppm 200 ppm 200 ppm Cr(VI) Cr(VI) Cr(VI) (Ind euent) Cr(VI) (Ind euent) Cr(III) pH 2.0 3.0 4.7 3.41 3.41 Particle size (lm) 120500 120500 120500 120500 120500 Rate constant kads (min1) 1.9806 102 1.2206 102 1.0133 102 5.758 103 1.4040 103 R2 0.9723 0.9718 0.9640 0.9662 0.9723

X = x/m, where x is in mg the amount of solute adsorbed, m is unit gram of adsorbent, Ce is the equilibrium concentration of solute (mg L1); Xm is the amount of solute adsorbed per unit weight of adsorbent required for monolayer coverage of the surface also called monolayer capacity and b is a constant related to the heat of adsorption. Freundlich equation indicates the adsorptive capacity or loading factor on the adsorbent, x/m is a function of the equilibrium concentration of the solute. It can be

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used for calculating the amount of adsorbent required to reduce any initial concentration to predetermined nal concentration. The Freundlich equation is expressed linearly as: log x=m log K f 1=n log C e K 0 c 4 The thermodynamic equilibrium constant for various systems using EB as adsorbent was obtained at 32 1 C. K0 c Ca ; Ce 5

Table 4 Thermodynamic parameters for the adsorption of Cr(VI) by EB Euent Euent concentration of Cr 250 200 200 200 Cr(VI) Cr(VI) Cr(VI) Cr(VI) pH Equilibrium constant Kc 9.0 4.95 1.36 2.10 4.60 Gibbs free energy DG0 kJ mol1 5.572 4.057 0.795 1.884 3.872

Pure solution Pure solution Pure solution Industrial euent Industrial euent

2 3 4.7 3.41 3.41

44.5 Cr(III)

where Ca is concentration of Cr(VI) on the adsorbent at equilibrium in mg L1 and Ce is the equilibrium concentration of Cr(VI) in solution in mg L1. The initial Cr(VI) concentrations tested were 200 ppm of synthetic euent and true industrial euent having Cr(VI) as 200 ppm and Cr(III) as 44.5 ppm at an adsorbent dosage of 5 g L1. The adsorption followed Freundlich isotherm. Freundlich plot is shown in Fig. 3. Linearity of these plots shows that rst order mechanism is followed in this process. The Kf and n values as calculated from the Fig. 3 for synthetic euent having 200 ppm of Cr(VI) and pH 4.7 was found out to be as 6.74 mg/g and 4.66, respectively. Industrial euent having 200 ppm of Cr(VI) and 44.5 ppm of Cr(VI) at 3.41 pH had Kf and n values as 21.69 mg/g and 9.8 for Cr(VI), and 18.26 mg/g and 7.88 for Cr(III), respectively. A higher than 1 value of n indicates that the adsorption on EB is favorable and capacity is only slightly reduced at the lower equilibrium concentrations. These values are comparable with several published literature reported for various sorbents (Sharma and Foster, 1994; Namasivayam and Yamuna, 1995; Dakiky et al., 2002). Signicantly higher values of adsorption capacity obtained with eucalyptus bark indicate that it can be used for the treatment of chromium waste.
1.6 1.4 1.2 1 log x/m 0.8 0.6 0.4 0.2 0 -3 -2 -1 0 log Ce 1 2 3
Cr(VI) of I.E. Cr(III) of I.E. S.E. of Cr(VI)

The Gibbs free energy (DG0) for the adsorption process for each euent was obtained using the formula: DG0 RT ln K 0 c
0

6 K 0 c

Values of DG and thermodynamic constant for various systems are shown in Table 4. The Gibbs free energy indicates the spontaneity of the adsorption process, where higher negative values reect a more energetically favorable adsorption process. The negative DG0 values obtained for various systems in this study conrm the feasibility of the adsorbent and spontaneity of adsorption. The studies further conrm that as the pH of the system is reduced the adsorption of Cr increases. With all the industrial samples there was more than 90% of Cr removal without any signicant interference of other metal ions. This indicates that EB has higher anity towards Cr adsorption. 4. Conclusion Removal of poisonous hexavalent form of chromium from solutions was possible using selected adsorbents. Eucalyptus bark (EB) was the most eective for which the removal reached more than 99% for Cr(VI) at concentration of 200 ppm and at pH 2. Increase in the dose of adsorbent, initial concentration of Cr(VI) and increase in contact time upto 2 h are favorable for all increase the adsorption of Cr(VI). The kinetic of the Cr(VI) adsorption on EB was found to follow rst order mechanism. The Gibbs free energy was obtained for each system. It was found to be 1.884 kJ mol1 for Cr(VI) and 3.872 kJ mol1 for Cr(III) for removal from industrial euent. The adsorption data can be satisfactorily explained by Freundlich isotherm. Higher sorption capacity of this sorbent indicates that eucalyptus bark can be used for the treatment of chromium euent.

References
Acar, F.N., Malkoc, E., 2004. The removal of chromium(VI) from aqueous solutions by Fagus orientalis L. Bioresource Technol. 94, 1315.

Fig. 3. Freundlich plot for the adsorption of Cr(VI) from synthetic euent having Cr(VI) 200 ppm and pH 4.7 and industrial euent (I.E.) having Cr(VI) 200 ppm, Cr(III) 44.5 ppm and pH 3.41 at 32 C. Adsorbent dosage was 5 g/L.

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V. Sarin, K.K. Pant / Bioresource Technology 97 (2006) 1520 Patterson, J.W., 1977. Waste Water Treatment. Science Publishers, New York. Randall, J.M., Hautala, E., Waiss, A.C., 1976. For. Prod. J. 26, 46. Saliba, R., Gauthier, H., Petit-Ramel, M., 2002. Adsorpt. Sci. Technol. 20 (2), 119129. Sharma, D.C., Foster, C.F., 1994. A Preliminary examination into the adsorption of hexavalent chromium using low-cost adsorbents. Bioresource Technol. 47, 257264. Singh, T.S., Pant, K.K., 2004. Equilibrium, kinetic and thermodynamics studies for adsorption of As(III) on activated alumina. Sep. Pur. Technol. 36, 139147. Tan, W.T., Ooi, S.T., Lee, C.K., 1993. Removal of chromium(VI) from solution by coconut husk and palm pressed bers. Environ. Technol. 14, 277282. Tiravanti, G., Petrluzzelli, D., Passino, R., 1997. Pretreatment of tannery wastewaters by an ion exchange process for Cr(III) removal and recovery. Water Sci. Technol. 36, 197207. US Department of Health and Human Services, 1991. Toxicological Prole for Chromium. Public Health Services Agency for Toxic substances and Diseases Registry, Washington, DC. Weber Jr., W.J., 1967. Sorption from solution by porous carbon. In: Faust, S.D., Hunter, J.V. (Eds.), Principles and Applications of Water Chemistry. John Wiley & Sons, New York (Chapter 5).

APHA, 1992. Standard Methods for the Examination of Water and Wastewater, 18th ed. APHA, Washington, DC. Cieslak-Golonka, M., 1995. Toxic and mutagenic eects of chromium(VI). Polyhedron 15, 36673689. Dahbi, S., Azzi, M., de la Guardia, M., 1999. Removal of hexavalent chromium from wastewaters by bone charcoal. Fresenius J. Anal. Chem. 363, 404407. Dakiky, M., Khamis, M., Manassra, A., Mereb, M., 2002. Selective adsorption of chromium(VI) in industrial wastewater using lowcost abundantly available adsorbents. Adv. Environ. Res. 6, 533 540. Huang, C.P., Wu, M.H., 1977. The removal chromium(VI) from dilute aqueous solution by activated carbon. Water Res. 11, 673 679. Kemmer, N.F., 1988. Precipitation, 10.1810.20, Nalco Water Handbook, Publisher McGraw Hill (Chapter 10). Kowalski, Z., 1994. Treatment of chromic tannery wastes. J. Hazard. Mater. 37, 137144. Namasivayam, C., Yamuna, R.T., 1995. Adsorption of Chromium(VI) by a low cost adsorbent: biogas residual slurry. Chemosphere 30, 561578. Orhan, Y., Buyukgangor, H., 1993. The removal of heavy metals by using agricultural wastes. Water Sci. Technol. 28, 247255.