ACTIVATED CARBON FROM CORN COBS AND COCONUT SHELL FOR HEAVY METAL IONS ADSORPTION

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ABSTRACT Heavy metal ions removal has received considerable attention due to their toxicological affects on ecosystem, agriculture and human health. Commercial activated carbon is widely used as an adsorbent for the removal of heavy metal ions from industrial wastes. Its high cost is, however, a restricting factor to its wider application. The present study explores the effectiveness of activated carbon obtained from corn cob and coconut shell for the removal of cadmium and chromium from aqueous wastes. Batch scale equilibrium adsorption studies carried out for various pH values and a range of initial concentrations of cadmium and chromium on the activated carbon prepared at different temperatures by pyrolysis process. Higher iodine value for coconut shell compared to corn cob at 8000C indicates that activated carbon obtained from coconut shell should be used preferably. Keywords: Coconut shell; Corn cob; Carbonization temperature; Heavy metals NOMENCLATURE Qe,= Amount of metal ion adsorbed, mg/gm Ce,= Equilibrium metal ion concentration in solution, mg/liter Co,= Initial metal ion concentration in solution, mg/liter m = Amount of adsorbent, gm V= volume of solution, liter Qo= Langmuir constant related to maximum sorption capacity, mg/gm b= Langmuir constants that relate energy of adsorption,l/mg. k= Freundlich constant representing adsorption capacity (mg/g), n= Freundlich constant representing intensity of adsorbent INTRODUCTION Industrial modernization has increased the production and discharge of heavy metal ions into the environment. These metals are toxic in nature and generate various disastrous risks to human health. For removal of hazards associated with water have played an important role in development of various technologies for wastewater purification namely filtration, ion exchange, precipitation and adsorption. Although these methods are effective for removing metals from contaminated water but they are expensive or time consuming and their inherent limitations also have proved to be less efficient than adsorption process based on low cost activated carbon [1].Throughout the world non conventional agricultural by product such as Coconut shell[2], coconut jute carbon[3],Coconut tree saw dust carbon [4], Sawdust and used Tyres carbon [5],

Rice husk carbon , Coconut fibre compost, Maize cob, Sugar beet pulp and Cane Bagasse, Hazelnut shell [6], Almond shell , Corncob, Stones of Apricot, Date, Peach, Olive and shell of Walnut & Coconut[2], Peanut husk[7] , Hazelnut husk[8], Olive stones & Almond shell ,Casurina equisetifolia Leaves[9], Bagasse[10], Rice hulls, Rice straw, Apricot Stone, peach stones and Eucalyptus globulus chips and Rice husk[11] are some of the raw materials for activated carbon production which has been reported to be an important adsorbents for the removal of heavy metals and organics from municipal and industrial waste water. Coconut shell is mostly used for preparing microporous activated carbon due to its excellent natural structure and low ash content [12,13]. There are two methods for manufacture of activated carbon: physical and chemical activation. In chemical activation the activating agent functions as a dehydrating agent inhibiting the formation of tar [12]. However the product needs washing to remove residual inorganic, which causes a serious pollution problem. Physical activation uses gaseous activation agent [14] and does not produce waste water, therefore is considered to be an environmentally benign technology. In the present study agricultural waste materials like coconut shell and corncob are used for preparation of activated carbon followed by removal of cadmium and chromium ions from synthetic waste water to establish equilibrium characteristics. MATERIALS AND METHODS Chemicals All the chemicals used in this study are of AR grade obtained from CDH,India. Water used in this study is double distilled water. Activated carbon preparation Coconut shell and corncob are used as raw materials to produce activated carbon are obtained from Modinagar local vendor. The starting materials are cleaned and dried at 1100C for 48 hrs and then broken into 2 to5 inches pieces with the help of hammer. The Characteristics of biomass are given in Table 1. The broken biomass is pyrolysed at 3500C for 1.5-2 hours followed by size reduction to 1-3 mm size and Physical activation in a Microprocessor controlled Tube furnace. The Physical activation is done at three different temperatures of 600 0C, 7000C and 8000C for 30min in each case with inert atmosphere of nitrogen. Table 1 :Characteristic of Biomass Property Coconut shell Calorific value ( kcal/kg) 5967.92 Moisture content(%) 6.54 Volatiles matter(%) Fixed carbon Ash content(%) Bulk density(kg/l) (%) 65.05 27.0 1.54% 1.025 Corn Cob 4153.79 7.08 71.2 20.9 1.85 0.39

Equilibrium experiments: Batch adsorption experiments are carried out in 100 ml conical flask. 50 ml of metal ion solution of known concentration (10-100 ppm) and adjusted pH by acetate buffer is poured into flask containing accurately weighed amount of the adsorbents. The adsorbent weight ranged from 0.120-0.310gm per 50 ml of solutions. The flasks are shaken at 150-200rpm using an electric shaker (DK-S1020 DAIKI) for about 24hrs to attain equilibrium. After 24 hours the content of

flask are filtered thorough the filter paper. Clear filtrate are analyzed for metal ion concentration (Ce) by AAS model-EC4141(make ECI). Amount adsorbed (Qe) in the adsorbent is determined by metal ion balance using following equation. ( Co Ce )V Qe = - - - - - (1) m RESULT AND DISCUSSIONS Characterization of activated carbon The activated carbon are analyzed in terms of their iodine number bulk density, moisture content and pH. The iodine number is determined according to ASTM procedure D4607-94 (ASTM Directory, 1986)[15]. Greater iodine value of coconut shell activated carbon indicates that coconut shell activated carbon have less ash content as shown in Table 2. Other characteristics are given in Table3. Table 2 : Iodine values of Activated carbon Temp of activation Corn cob 8000C 700 C 6000C
0

Type of biomass Coconut shell 926.35 800.56 649

786.85 780 700

Table3: Characteristics of activated carbons Property Coconut shell activated Corn cob activated carbon Bulk Density Moisture pH carbon 0.5906kg/l 1.3% 7.26 0.1863kg/l 2.58% 5.89

Effect of pH The mechanism of adsorption at the carbons surface reflects the nature of physicochemical interaction of the metal ions in the solution and the active sites of the carbons. One of the most important parameters that affect this mechanism is the pH of the solution. It is, therefore planned to conduct adsorption experiments at different pH values of the solution. The pH is varied from 210 for chromium and cadmium solution for both type of biomass at 250 C and 150 rpm. The effect of pH on the removal of chromium ions found to be max at pH 3.0 for corn cob and at pH 4.5 for coconut shell as shown in fig 1. The results indicate that the pH affects the Cr(VI) adsorption. An acidic solution at a pH value about 3-5 is an optimal condition for the adsorption of Cr(VI) and the reason may be due to the partial reduction of Cr(VI)-Cr(III) on the surface of the carbon and electrostatic attraction of the highly protonated carbon surface to the major chromium species(HCrO4-) in solution. The effect of pH on the removal of Cadmium ions found to be max at pH range 5for corn cob carbon and 6.0 for coconut shell carbon as shown in fig 2 . The metal adsorption found again max at pH >6.0 because of the formation of metal oxide precipitation.

Effect of adsorption temperature The effect of adsorption temperature on the uptake of chromium and cadmium, at the optimum pH is examined. Fig 3 and Fig 4 shows the temperature influence on the adsorption of chromium and cadmium simultaneously. The removal of metal ions increases with an increase in the temperature. For both type of metal ions with both type of adsorbents there is a substantial increase in the amount adsorbed when the temperature increases from 15oC-35o C. It can be easily inferred that the removal of metal ions increases with increase in temperature.
25

50

metal adsorbed (mg/gm)

corn cob

metal adsorbed (mg/gm)

20

coconut

45 40 35 30 25 20 15 10 5 0

coconut shell corn cob

1 5

1 0

0 0

ph Figure 1 : Effect of pH on Cr adsorbed,t=24hrs, CO=100ppm, m=0.120gm,

1 0

1 2

10

12

pH

Figure 2: Effect of pH on cd adsorbed, t=24 hrs,Co=100ppm,m=0.120gm

30

metal adsorbed (mg/gm)

metal adsorbed (mg/gm)

25 20 15 10 5 0 0

shell ac cob ac

6 5 4 3 2 1 0

shell ac cob ac

10

20

30

40

10

temp

temp

20

30

40

Figure3: Effect of temp for Cr, t=24hrs,100ppm,0.120gm,150rpm

Figure4: Effect of temp for Cd, t=24 hrs,100ppm,0.120 gm,150rpm

Effect of adsorbent dose The effect of amount of adsorbent on the uptake of chromium and cadmium, at the optimum pH is examined. Amount if carbon dosage versus % removal of chromium and cadmium ions

shows(in Fig 5&6) that the removal of metal ions increases with an increase in the amount of carbons. For chromium ions there is a substantial increase when the does of carbons increases from 0.1-0.2gm but not more increases for 0.3 gm for corn cob but for coconut shell activated carbons it found increase in good condition. So it can be easily inferred that the percent removal or metal ions increases with increasing weight of carbons.

25

12
shell ac

20

10

metal adsorbed (mg/gm)

shell ac cob ac

metal adsorbed (mg/gm)

0.3 0.4

cob ac 1 5

8 6 4 2 0
0 0.1

1 0

0 0 0.1 0.2

0.2

0.3

0.4

carbon dose (gm) Figure 5: Effect of carbon dose-Cr,

100ppm,150 rpm ,t=24hrs,pH-5

carbon dose(gm)

Figure6: Effect of carbon dose-cd,

t=24 hrs,100ppm,150rpm,pH-6

Effect of initial metal ion concentration The effect of initial ion concentration on the uptake of chromium and cadmium, at the optimum pH is examined and results are shown in Figure7. The percentage removal of chromium and cadmium ions increases with an increase in the initial ion concentration for fixed amount of adsorbent dose. For both metal ions the rate of percentage removal fast at low concentration and it becomes slow with increases in initial concentration which may be due to saturation of adsorbent Equilibrium Isotherms The equilibrium study is carried out for removal of Chromium and Cadmium by activated carbon. Equilibrium equation, commonly known as sorption isotherm, is basic requirement for the design of adsorption system. The isotherm provides information on the capacity of the adsorbent for removing a unit mass of pollutant under the operating conditions. Optimizing the design of adsorption system to remove Chromium and Cadmium from effluent requires appropriate correlation for the equilibrium data. Two isotherms have been tested in the present study, namely, Langmuir and Freundlich. The Langmuir isotherm represents one of the first theoretical treatments of non-linear adsorption, and has been successfully applied to a wide range of data that exhibit limiting or maximum adsorption capacities. It assumes uniform energies of adsorption onto the surface and no transmigration of the adsorbate in the plane of the surface. The Langmuir isotherm is represented by: QC Qe = o e - - - - - - - - - (2) 1 + bC e

100 90 80 70 60 50 40 30 20 10 0 0 20 40 60 conc(ppm)

% removal of metal ions

Cr ion Cd ion

80

100

120

Figure 7: Effect of initial ion conc, t=24hrs, pH 6.0 for Cd, pH 5.0 for Cr, m=0.220 gm

Linear form of equation (1) is

1 1 = Qe Qo 1 b C + Q o e - - - - - - - - - - - (3)

A plot of 1/Qe versus 1/Ce from the linear form of Eq. (2) can be used to determine the values of Qo and b. The calculated parameters are presented in Table3. The equilibrium data is also fitted to the Freundlich isotherm. Freundlich equation has the following linear form 1 log Qe = log k + log C Ae - - - - - - - - - - - -(4) n Where Qe is the amount of solute present in the adsorbent phase at equilibrium (mg/g), Ce is the equilibrium solute concentration in the solution phase (mg/l), and k and n are constant representing adsorption capacity (mg/g), and intensity of adsorbent respectively. The values of k and n obtained from the intercept ands slope of the plot between log Qe and log Ce are presented in Table3. Conclusions In the present study, the waste coconut shell and corn cob are used as a low cost source material for the preparation of activated carbons and the carbons activated at 8000C gives the highest iodine value. Lower Iodine value in case of corn cob compared to that for coconut shell

carbon indicates that coconut shell activated carbon is better. The optimum pH for cadmium adsorption is in the range 5-6 while that for chromium the range is 3-4. Metal removal increases with increase in the amount of activated carbon. Freundlich isotherm fits well in the equilibrium data for adsorption of chromium and cadmium on activated carbon.

Table 3 : Isotherms Parameters Isotherms Langmuir Freundlich Langmuir Freundlich Langmuir Freundlich Langmuir Freundlich Biomass coconut shell coconut shell Corn cob Corn cob coconut shell coconut shell Corn cob Corn cob Metal ion Cadmium Cadmium Cadmium Cadmium Chromium Chromium Chromium Chromium Experimental conditions pH=6.0 Ads.Temp.=250C Act.Temp.=8000C pH=6.0 Ads.Temp.=250C Act.Temp.=8000C pH=6.0 Ads.Temp.=250C Act.Temp.=8000C pH=6.0 Ads.Temp.=250C Act.Temp.=8000C pH=5.0 Ads.Temp.=250C Act.Temp.=8000C pH=5.0 Ads.Temp.=250C Act.Temp.=8000C pH=5.0 Ads.Temp.=250C Act.Temp.=8000C pH=5.0 Ads.Temp.=250C Act.Temp.=8000C Parameters Qo=1.045, b=0.015942 k = 6.931, n =0.2978 Qo=6.11, b=0.019511 k = 8.0634, n=0.24200 Qo= 1.078, b= 0.0375 k= 0.7374, n=3.16656 Qo=5.175, b= 0.09045 k= 1.8614, n=1.8148 R2 0.9464 0.9759 0.9226 0.9601 0.7423 0.9679 0.5612 0.9842

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