Dec. 2010, Volume 4, No.12 (Serial No.

37) Journal of Environmental Science and Engineering, ISSN 1934-8932, USA

Utilization of Chemically Activated Coconut Shells for Removal of Chromium (VI) from Aqueous Solution
K. Qureshi1, I. Bhatti1 and R.F. Ashraf2
1. Chemical Department, Mehran University of Engineering and Technology, Jamshoro 76062, Pakistan 2. Textile Engineering Department, Mehran University of Engineering and Technology, Jamshoro 76062, Pakistan

Received: September 10, 2010 / Accepted: November 3, 2010 / Published: December 20, 2010. Abstract: The purpose of this study is to develop low cost adsorbing materials to remove the heavy metals from waste waters. The outer covering of coconut, coconut shell, is the most abundant in the countries of its plantation and enormous use. Utilization of agricultural waste (coconut shell) in the production of activated carbon potentially leads to produce a highly effective adsorbent generated from low cost raw materials that are available in huge quantity as renewable resources. At present coconut shell is not in use as valuable entity due to which disposal and ultimate environmental problems are faced. In this study coconut shells were impregnated with phosphoric acid and chemically activated at 450 C. The potential to remove chromium (VI) from aqueous solution by using activated coconut shells was investigated by batch experiment. The various sorption parameters i.e pH, sorbent dose, sorbate concentration, agitation time and agitation speed were optimized. The sorption of Cr (VI) onto activated carbon, developed from coconut shell, at pH 2 was achieved 81.25%. The best optimum conditions were obtained when 0.75 gm of sorbent was agitated at 150 rpm with 60 mg/L of sorbate for 40 min. Activated coconut shells has potential to be a good resource material for effective removal of chromium (VI) of low concentration from wastewater. Key words: Adsorption, sorption, sorbate, sorbent, activated carbon, activation.

1. Introduction
The USA EPA has defined chromium on the top priority list of toxic pollutants. Industries such as electroplating, leather tanning, textile and metal finishing are all contributing to Cr(VI) in the form of oxyanion such as chromates, dichromates and bichromates. Chromium is very toxic causing health disorders, such as hemorrhage and vomiting [l]. The wastewater should be treated prior to discharge in order to avoid these effects. Different techniques have been adopted for the removal of chromium from wastewater such as precipitation, membrane technology,

Corresponding author: K. Qureshi, female, associate professor, main research field: water treatment. E-mail: qureshi.khadija@yahoo.com. I. Bhatti, male, assistant professor, main research field: liquid membrane. E-mail: bhatti_inam@yahoo. com. R.F. Ashraf, male, assistant professor, main research field: water treatment. E-mail: raja_fahad07@hotmail.com.

ultrafiltration and ion exchange etc. The major problem with these methods precipitation generates high sludge causing disposal problems, whereas the other methods require high operational and capital cost. In the past decade emphasis is on treatment of waste water by the process of adsorption, using different adsorbent. Different researchers have worked on the production of granular activated carbon from agriculture waste and have used for the removal of chromium (VI). Materials like walnut shells [2], rice husk [3], sugarcane waste [4], tea waste [5], coconut shells [6], rice bran, rice hull, soybean hull cotton seed hull [7], their availability and cost effectiveness make them good candidates for the use for removal of Cr (VI). The Coconut Palm (Cocs Nucifera) gives us coconut, a dry nut. The husk is composed of fiber called coir, inner stone or endocarp is the hardest part of the nut commonly called as coconut shell. In India,

Utilization of Chemically Activated Coconut Shells for Removal of Chromium (VI) from Aqueous Solution

the coconut shell are used as bowls in the manufacture of various craft product they are also burned for smoke to repel mosquitoes, but in Pakistan these shells have no usage. In the present study coconut shells were crushed and sieved to reduce their size. They were pyrolised at 170 C and activated at 450 C to produce granular activated carbon. The activated carbons were used for the sorption of Cr(VI) from aqueous solution. The various operating parameters pH, sorbent dose, sorbate concentration, shaking speed, and shaking time were optimized.

2. Materials and Method

Coconut shells agriculture waste was used for the production of activated carbon by chemical activation. The activated carbon was then used for the sorption of chromium from aqueous solution. 2.1 Production of Activated Carbon Coconut shells were first washed with double distilled water to remove dirt particles. The shells were dried overnight at 50 C in the oven. The size of the shells was reduced by crushing in the jaw crusher. Hammer mill was further used for grinding the sample to particle size of 4 to 1.68 mm. The sample was sieved and particle of 380 m was used for production of activated carbon. The sample was prepared by soaking the crushed shells in phosphoric acid (1:1 wt%). The sample was pyrolyzed at 170 C for 0.5 hr in N2 atmosphere and activated at 450 C for 1 hr in N2 atmosphere. The sample was cooled overnight in N2 atmosphere. The sample was washed in the Soxhlet extraction for the removal of acid. The carbon was dried in oven at 110 C for 3 hr. 2.2 Adsorption Studies All the chemicals used were of Merck Company. 1000 mg/L stock solution of chromium was prepared by using potassium dichromate in double distill water. Concentration of 60, 70, 80, 90, and 100 mg/L were

prepared from this stock solution. Buffers of pH 2-9 were also prepared by mixing appropriate volume of 0.1 M solution of HCI-KCI, CH3COONa and H3BO3 and NaOH respectively [8]. In order to determine the sorption capacity, various concentration of sorbate ranging from 60-100 mg/L were contacted with 0.25-1.25 gm sorbent. 100 mL of the sorbate was shaked with the sorbent in the Rotary shaker at 90-200 rpm for 20-100 min aqueous solutions of different pH 2-9 were used. The sample was then filtered through Watman Filter Paper NO. 1. The residual metal Cr (VI) concentration after adsorption was directly measured by flame atomic absorption spectrophotometer (AAS) (Varian spectra, AA240) with an air-acetylene each experiment was conducted three times and the average results are reported. The sorption efficiency (%) was calculated according to the Eq. (1). Where Co and Ce are the initial and equilibrium concentration (mg/L), V is the volume of solution (L), m is the weight of activated coconut shells (g) and C is the solution concentration at the end of the sorption process (mg/L) [9]. Sorption efficiency (%) = (Co-Ce)/Co 100 (1)

3. Results and Discussion

3.1 Effect of pH The pH effects the degree of ionization and surface speciation of adsorbate during reaction. pH is very important parameter because it affects the surface charge of adsorbate. To examine the effect of pH on the Cr removal efficiency, the solutions pH was varied from 2 to 9 as shown in Fig. 1. 1 gm of activated coconut shell was shaked with 100 mL of sorbate at 100 rpm for 50 min. The temperature was maintained at 30 C. It was observed that acidic condition favored the sorption. Maximum sorption 79% was achieved at pH 2, at pH 2 highest sorption have been reported by various researchers [2, 3, 6]. The functional group on the surface of the sorbent carry positive charge and negatively charged chromium species bind to the surface of sorbent due to increase of electrostatic force

Utilization of Chemically Activated Coconut Shells for Removal of Chromium (VI) from Aqueous Solution

Fig. 1

Effect of pH on sorption of chromium onto activated carbon.

Fig. 2 Effect of shaking time on sorption of chromium onto activated carbon.

of attraction. At pH greater than 5 there is decrease in sorption due to increase of the negative charge on the adsorbent thus decreasing the electrostatic force of attraction between the sorbent and sorbate. 3.2 Effect of Shaking Time In this study the shaking time varied from 10 to 70 min while keeping the pH and temperature constant. 1 gm of sorbent was shaked with 100 mL of sorbate (100 mg/L) at 100 rpm. Fig. 2 illustrates the effect of shaking time on chromium removal efficiency of activated carbon. As can be seen from Fig. 2, the Cr removal efficiency of activated carbon became highest 69% at 40 min. Hence the optimum shaking time is 40 min which is less when compared with previous work

in literature which reports optimum shaking time of coconut shells charcoal 180 min [6]. Less shaking time is favorable for an economic wastewater treatment plant. 3.3 Effect of Amount of Sorbent The dependence of chromium sorption on the sorbent was studied by varying the amount of sorbent from 0.25 gm to 1.5 gm as shown in Fig. 3. The optimized pH and shaking time were used, six samples of different amount of sorbent 0.25 to 1.5 gm were shaked with 100 mL of 100 mg/L of chromium. It was observed that with increasing the sorbent dose up to a certain value and then, there was no further increase of adsorption. The chromium removal efficiency

Utilization of Chemically Activated Coconut Shells for Removal of Chromium (VI) from Aqueous Solution

Fig. 3 Effect of sorbent dose on sorption of chromium.

Fig. 4 Effect of shaking speed on sorption of chromium onto activated carbon.

significantly increased from 46% to 74% when the dose of sorbent was increased from 0.25 to 0.75 g and then remained contant. 0.75 gm of sorbent was used for the further sorption experiments. 3.4 Effect of Shaking Speed Agitation speed is an important parameter during sorption to maximize proper interaction between metal ions and adsorption sites of adsorbent in the solution. Fig. 4 shows the sorption of chromium at different shaking speed (i.e. 90, 100, 120, 150 and 200 rpm). 0.75 gm of sorbent was shaked with 100 mL of 100 mg/L sorbate for 40 min. The sorption increased from 60.3% to 80.3%, highest sorption of chromium was achieved at 150 rpm. The optimum shaking speed is

150 rpm, which was selected as the optimum speed for remaining adsorption studies, which is same in previous work also [6]. 3.5 Effect of Adsorbate Concentration Various sorbate concentrations from 60 mg/L to 100 mg/L were agitated with sorbent to see the sorption efficiency as shown in Fig. 5. 0.75 gm of sorbent was shaked with 100 mL of sorbate for 40 min at 150 rpm. The highest sorption 81.25% was achieved at low concentration. This appears to be due to the increase in the number of ions competing for the available binding sites in the activated carbon and also due to the lack of binding sites for the complexation of Cr ion at higher concentration levels [5].

Utilization of Chemically Activated Coconut Shells for Removal of Chromium (VI) from Aqueous Solution

Fig. 5 Effect of sorbate concentration on sorption of chromium onto activated carbon.

4. Conclusions
It was found that activated carbon produced from coconut shells has good sorption efficiency 81.25% for the removal of chromium. The optimum conditions were obtained when 0.75 gm of sorbent was agitated at 150 rpm with 60 mg/L of sorbate for 40 min. Activated coconut shells has potential to be a good resource material for effective removal of chromium (VI) of low concentration from wastewater.
[4]

[5]

[6]

References
[1] S.B. Lalvani, T. Wiitowski, A. Hugner, A. Weston, N. Mandich, Removal of hexavalent chromium and metal cations by a selective and novel carbon, Carbon 36 (1998) 1219-1226. X.S. Wang, Z.Z. Li, S.R. Tao, Removal of Chromium (VI) from aqueous solution using walnut hulls, Journal of Environmental Management 90 (2009) 721-729. K. Qureshi, R.A. Kazi, A.K. Ansair, Preparation of activated carbon from rice husk and optimization of

[7]

[8] [9]

[2]

[3]

adsorption parameters for Cr (VI) removal from aqueous solution, Mehran University Research Journal of Engineering and Technology 26 ( 2007) 261-266. A.K. Rai, S.K. Upadhe, Y.D. Upadhe, Heavy metal pollution and its control through cheaper method, A Review, J IAEM 25 (1998) 220-251. K. Qureshi, I. Bhatti, A.K. Ansair, Chemical activated of tea waste and use for the removal of chromium (VI) from aqueous solution, Mehran University Research, Journal of Engineering and Technology 28 (2009) 199-204 S.Babel, T. A. Kurniawan, Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents/or chitosan, Chemosphere 54 (2004) 951-967. T. Tarley, C. Richard, Z. Arruda, M. Aurelio, Bio sorption of heavy metals using rice milling byproducts characterization and application for removal of metals from aqueous solution, Chemosphere 54 (2004) 905-915. D. Perin, B. Dempsey, Buffers for pH and Metal Ion Control, John Wiley and Sons Inc, New York, 1974. E.A. Oliveria, S.F. Montanher, A.D. Andrader, J.A. Nobrega, M.C. Rollemberg, Equlibrium studies for the sorption of chromium and nickel from aqueous solution using rice bran, Process Chemistry 40 (2005) 3485-3490.