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Clean Techn Environ Policy DOI 10.1007/s10098-013-0628-0 Cadmium removal from aqueous solutions using hybrid eucalyptus wood based activated carbon: adsorption batch studies G.Venkatesan, U.Senthilnathan & Shameela Rajam 1 3 Your article is protected by copyright and all rights are held exclusively by Springer- Verlag Berlin Heidelberg. This e-offprint is for personal use only and shall not be self- archived in electronic repositories. If you wish to self-archive your article, please use the accepted manuscript version for posting on your own website. You may further deposit the accepted manuscript version in any repository, provided it is only made publicly available 12 months after official publication or later and provided acknowledgement is given to the original source of publication and a link is inserted to the published article on Springer's website. The link must be accompanied by the following text: "The final publication is available at link.springer.com. ORI GI NAL PAPER Cadmium removal from aqueous solutions using hybrid eucalyptus wood based activated carbon: adsorption batch studies G. Venkatesan
U. Senthilnathan
Shameela Rajam Received: 5 November 2012 / Accepted: 25 April 2013 Springer-Verlag Berlin Heidelberg 2013 Abstract Activated carbon has been equipped from wood of Hybrid Eucalyptus. Its adsorption capacity in elimination of cadmium from wastewater has been examined during batch adsorption experiments. The adsorption kinetics of this particular carbon for several factors such as adsorbent dosage and contact time of the cadmium were identied. The cadmium adsorption characteristics and the effect of the initial cadmium concentration on elimination capability were also studied. The optimum dosage of Hybrid Euca- lyptus wood based activated carbon to remove 80 mg/L of cadmium from aqueous solution was 1.0 g/150 mL and the optimum contact time was 30 min. The isotherm data t with both Langmuir and Freundlich isotherm models. Keywords Adsorbents Wastewater treatment Cadmium Hybrid Eucalyptus Langmuir and Freundlich isotherms Introduction The heavy metals such as Cadmium, Chromium, Lead, Arsenic, Cobalt, etc. are the major poisonous substances that are present in water bodies (Gardea-Torresdey et al. 2000). Industries like electroplating industry, dye industry, metal nishing industry, and chemical manufacturing units are the major principal sources of discharging the poison- ous heavy metals into the water bodies (Bishnoi et al. 2004). Moreover, heavy metals are biologically nonde- gradable and remain on earth for a long time (Low et al. 1999). The concentration of the heavy metals must be lessened to permissible limits before they are discharged into environment or else it will cause danger to the health of human beings, animals, and plants when they consume the polluted water (Babel and Kurniawan 2000). The ill effects of the heavy metals on human beings, animals, and plants vary from time to time depending on the concen- tration and individual tness. Human beings take the poi- sonous metals by contaminated food and drinking the contaminated water (Hamadi et al. 2001). Large number of treatment methods are available for the removal of Cad- mium from industrial wastewater. They are Chemical Precipitation, Ion Exchange, Filtration, Membrane Sepa- ration, Adsorption, Oxidation, and Reduction. Of all the methods, Adsorption is found to be effective and has low cost (Nomanbhay and Palanisamy 2005; Chuah et al. 2005; Bayrak et al. 2006; Mahvi et al. 2005). So far, many agricultural waste materials such as Waste Tea fungal biomass (Murugesan et al. 2006), Tamarindus Indica seeds (Agarwal et al. 2006), Terminalia Arjuna nuts with Zinc Chloride (Mohanty et al. 2005), Macadamia Nut Shell (Wang et al. 2002), Fruit shell of T. Catappa (Ste- phen Inbaraj and Sulochana 2006), Bagasse-Fly ash (Gupta and Imran Ali 2004; Mohan and Singh 2002), Oat nut shells (Chuang et al. 2005), Coconut coir pith (Anirudhan and Unnithan 2007), Candida Utilis (Kujan et al. 2006), Fucus Spiralis (Cordero et al. 2004), Platanus orientalis (Mahvi et al. 2007), palm fruit seed (Kannan and G. Venkatesan Department of Civil Engineering, University College of Engineering (BIT Campus), Tiruchirapalli, India e-mail: gvenkat1972@gmail.com U. Senthilnathan (&) Department of Civil Engineering, M. A. M. College of Engineering, Tiruchirapalli, India e-mail: usmamce@gmail.com S. Rajam Department of Chemistry, Bishop Heber College, Tiruchirapalli, India 1 3 Clean Techn Environ Policy DOI 10.1007/s10098-013-0628-0 Author's personal copy Thambidurai 2007), apple residues (Lee et al. 1998), Water Hyacinth (Lee and Hardy 1987), Rice Husk (Ajmal et al. 2003; Kumar and Bandyopadhyay 2006), Maple sawdust (Li et al. 2003), Neem Leaf powder (Bhattacharyya and Sharma 2004), Pine Wood (Tseng et al. 2003), and Cocoa Shells (Meunier et al. 2003) had also been tried to remove heavy metals. Throughout the world commercial activated carbon is used for the removal of heavy metals. The rate of commercial activated carbon stays the industrialist away from the treatment of the same, which occurs mainly is developing countries and under developing countries. So there is a need to derive an activated carbon which is economically cheaper in cost and should be easily avail- able. Though different researchers proposed several low cost adsorbents, still there is a need to nd a suitable adsorbent for the removal of Cadmium from wastewater. Experiments were carried out to remove 80 mg/L of Cadmium concentration from aqueous solutions using activated carbon derived from Hybrid Eucalyptus, which is available in the rural areas of Tamilnadu, South India. The main objective of this study is to explain the ability of using Hybrid Eucalyptus based activated carbon for the removal of Cadmium from the aqueous solution. Materials and methods Preparation of activated carbon The plant material Hybrid Eucalyptus was collected from the university campus and utilized for the study. The col- lected plant materials size was diminished by splitting into small pieces; it was then dehydrated in an oven at a tem- perature of 170 C for 24 h. It was then kept in an air tight cylindrical iron container with top completely covered with iron cover to avoid the entry of air during charring. The sealed iron container was heated in a Mufe Furnace by slowly increasing the temperature up to 600 C and maintained at the same temperature for 1 h. During this process, wood of Hybrid Eucalyptus was converted into its carbon. The activated carbon prepared in such a manner was crushed and sieved using 710500 lm sieve. Carbon of intermediate size was soaked in distilled water; oven dried and packed in an air tight container for further experiments. Preparation of synthetic solution Synthetic solution of 80 mg/L cadmium concentration was made by dissolving 143.27 mg of Cd 2 Cl 2 H 2 O in 1 L of distilled water. Synthetic solution of 80 mg/L cadmium concentration thus prepared was utilized for all experiments. Experimental procedure To study the optimum dosage and optimum contact time for the elimination of cadmium using wood of Hybrid Eucalyptus, eight conical asks having 150 ml of 80 mg/L cadmium solution were taken. 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, and 1.6 g of wood of Hybrid Eucalyptus activated carbon was added in each ask. These conical asks were kept in magnetic stirrer for continuous agitation. Samples was taken out at the period of 1060 min. Samples were taken out from each conical ask and were kept in the test tubes after ltering that samples using Whatman lter paper No. 41. The remaining metal ions concentration was estimated by UV Spectrophotometer. Experiments were carried out to nd the optimum pH by varying the pH with sodium hydroxide and concentrated hydrochloric acid. Experiments were done to nd out the highest concen- tration that can be eliminated at optimum dosage. Optimum carbon dosage, optimum contact time, optimum pH for the removal of cadmium using Hybrid Eucalyptus. All the adsorption tests were done in 2022 C. Instrumentation Systrons 2202 double beam PC based spectrophotometer was utilized to nd out the concentration of heavy metals. The minimum detection value was within EPA requirement. Fig. 1 Dosage against percentage removal of cadmium G. Venkatesan et al. 1 3 Author's personal copy Standard solution with various cadmium concentrations was employed to standardize the instrument. The pH meter was adjusted using buffer solutions of values four and seven. Magnetic stirrer (KMS 450) was used for stir up all samples for needed time. Chemicals Chemicals such as concentrated hydrochloric acid and Sodium Hydroxide (Madras Scientic Company) were used in adjusting the pH of the sample. Double distilled water is used in all experiments. Adsorption isotherms For the present study the equations used (Saseetharan and Isaac Solomon Jebamani 2005) are a) Freundlich Isotherm b) Langmuir Isotherm The general form of Freundlich isotherm is Log X=m logK F 1=n Log C e 1 where X/m is amount adsorbed per unit weight of adsorbent (g/kg). C e is equilibrium concentration of adsorbate in solution after adsorption (mg/L). K F , n is empirical constants. The general form of Langmuir isotherm is 1= X=m 1=q m 1=K a q m 1=C e 2 where X/m is amount adsorbed per unit weight of adsorbent (g/kg). K A , q m is constants. C e is equilibrium concentration of adsorbate in solution after adsorption (mg/L). Result and discussion Effect of dosage Figure 1 shows the effect of dosage for the removal of Cadmium concentration of 80 mg/L. From the gure, it is apparent that the Cadmium removal percentage rises by increasing the dosage of Hybrid eucalyptus carbon. After some time it is observed that the percentage removal reaches the steady state and it is illustrated in the Fig. 2. Data obtained was presented in Tables 1 and 2. It was observed that optimum dosage of Hybrid Eucalyptus wood based activated carbon for the removal of cadmium ion concentration of 80 mg/L was 1 g/150 mL and the opti- mum time was 30 min. Effect of pH pH is one of the most important factor which controls the removal of cadmium from aqueous solutions. Figure 3 indicates the effect of pHon cadmium(II) removal byHybrid Eucalyptus. The study was conducted at 80 mg/L cadmium concentration on adsorbent dose of 1 g/150 mLwith varying pH from 1 to 8. From the gure it is understood that the removal percentage increases with increase of pH and at Fig. 2 Dosage versus percentage removal of cadmium at optimum time30 min Fig. 3 pH against percentage removal of cadmium Cadmium removal from aqueous solutions 1 3 Author's personal copy certain point removal percentage comes to steady state. At pH 38 adsorption of cadmium takes place around 85 %. It was found that optimum pH for the removal was 7.37 (Ori- ginal pH) at optimum contact time of 30 min. Hence all the experiments were conducted at original pH itself. Effect of initial concentration To illustrate the Cadmium adsorption at different concen- trations of Cadmium, 1080 mg/L was utilized. Hybrid Eucalyptus wood based activated carbon of 1 g/150 mL Fig. 4 Optimum concentration against percentage removal of cadmium Table 1 Effect of dosage on cadmium removal Sl. no. Contact time (Min) Percentage removal of Cd removal for 150 mL 0.2 g 0.4 g 0.6 g 0.8 g 1.0 g 1.2 g 1.4 g 1.6 g 1 10 18.38 40.38 66.63 81.38 83.25 84.25 85.25 86.63 2 20 31.38 47.38 71.13 82.75 84.63 84.88 87.88 88.88 3 30 33.50 47.75 71.75 84.13 85.13 85.13 88.00 90.25 4 40 33.75 48.38 72.25 84.88 85.50 86.13 88.25 90.63 5 50 34.00 49.75 73.25 85.75 86.88 87.00 89.38 91.00 6 60 34.88 50.00 74.38 86.25 87.25 87.50 89.88 91.50 Table 2 Effect of dosage on cadmium removal at equilibrium (30 min) Weight of adsorbent added in g/150 mL 0.2 g 0.4 g 0.6 g 0.8 g 1.0 g 1.2 g 1.4 g 1.6 g Percentage removal of cadmium 33.50 47.75 71.75 84.13 85.13 85.13 88.00 90.25 Table 3 Data for Langmuir isotherm for cadmium removal Sl.no Weight of adsorbent added (m) (mg) Weight of cadmium adsorbed at equilibrium concentration (X) (mg) Equilibrium cadmium concentration (Ce) (mg/L) 1/Ce (L/mg) X/m (g/kg) [1/(x/m)] (kg/g) 1 200 2.01 53.2 0.0188 0.0100 100 2 400 2.86 41.8 0.0240 0.0071 140.8 3 600 4.31 22.6 0.0442 0.0072 138.9 4 800 5.05 12.7 0.0787 0.0063 158.7 5 1000 5.11 11.9 0.0840 0.0051 196.1 6 1200 5.11 11.9 0.0840 0.0043 232.6 7 1400 5.28 9.6 0.1042 0.0038 263.2 8 1600 5.42 7.8 0.1282 0.0034 294.1 G. Venkatesan et al. 1 3 Author's personal copy was added to different Cadmium concentrations and same was kept in a magnetic stirrer for continuous agitation. The samples were monitored for residual Cadmium concentra- tion at an interval of 10 min up to the contact time of 60 min. The data obtained are given in Fig. 4. To dem- onstrate the Cadmium adsorption at different concentra- tions, a graph is plotted between contact time and percentage removal of Cadmium (Fig. 4). From the graph it is observed that initial concentration has marked the inuence on adsorption potential. The percentage of Cad- mium removal increases up to initial concentration (70 mg/ L) and reaches equilibrium state. Isotherm study A xed volume (150 mL) of synthetic Cadmium solution was equilibrated with different dosages of Wood of Hybrid Eucalyptus based activated carbon (0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6 g) for 30 min. The equilibrium state for dif- ferent Cadmium concentrations were found out from each of the eight reactors. The data necessary for isotherm plot for wood of Hybrid Eucalyptus based activated carbon are given in Table 3 (Langmuir isotherm) and Table 4 (Fre- undlich isotherm). The isotherm test data were found to be t with Langmuir and Freundlich isotherm models (Figs. 5, 6). While readings were plotted in Langmuir isotherm model and Freundlich isotherm model it was found that R L value for Langmuir isotherm is 0.078 and 1/n value for Freundlich isotherm is 0.42, which indicates to be favor- able for adsorption of cadmium uptake. Conclusion Activated carbon was prepared using wood of Hybrid Eucalyptus. Experiments were conducted in batch reactors to evaluate the capability of this carbon to remove Cad- mium from wastewater. The following conclusions were drawn from the present studies on Cadmium removal efciency on wood of Hybrid Eucalyptus based activated carbon. 1) For the wood of Hybrid Eucalyptus activated carbon the percentage of cadmium removal was almost the same from pH 3 to 7.37 (original pH). Hence this carbon can be used to remove Cadmium even in acidic solutions and neutral solutions also. But the experi- ments were conducted in original pH itself. Table 4 Data for Freundlich isotherm for cadmium removal Sl. no Weight of adsorbent added (m) (mg) Weight of cadmium adsorbed at equilibrium concentration (X) (mg) Equilibrium cadmium concentration (Ce) (mg/L) X/m 9 10 -3 (g/kg) Log Ce Log (x/m) 1 200 2.01 53.2 0.0100 1.726 -2 2 400 2.86 41.8 0.0071 1.621 -2.15 3 600 4.31 22.6 0.0072 1.354 -2.14 4 800 5.05 12.7 0.0063 1.104 -2.2 5 1000 5.11 11.9 0.0051 1.075 -2.3 6 1200 5.11 11.9 0.0043 1.075 -2.4 7 1400 5.28 9.6 0.0038 0.982 -2.42 8 1600 5.42 7.8 0.0034 0.892 -2.5 Fig. 5 Langmuir isotherm for cadmium removal Fig. 6 Freundlich isotherm for cadmium removal Cadmium removal from aqueous solutions 1 3 Author's personal copy 2) Optimum dosage for the removal of 80 mg/L of cadmium in aqueous solution is 1.0 g/150 mL at an optimum contact time of 30 min. 3) From the isotherm study, it is observed that wood of Hybrid Eucalyptus based activated carbon conrms Langmuir isotherm models as the R L value for Langmuir isotherm lies between 0 and 1, conrming it to be an effective adsorbent. 4) No physical and chemical modication was done. 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