ISSN: 1579-4377

ADSORPTION OF INDIGO BLUE DYE AND SOME TOXIC METALS BY ACTIVATED CARBONS FROM COCONUT SHELLS
C.E. GIMBA*1 MUYIWA TUROTI2 , P.A EGWAIKHIDE3 AND E.E AKPORHONOR4 Department of Chemistry, Ahmadu Bello University, Zaria, Nigeria. Department of Chemistry, Federal College of Education, Zaria, Nigeria. 3 Department of Chemistry and Centre for Biomaterials Research, University of Benin, Nigeria 4 Department of Chemistry, Delta State University, Abraka, Nigeria gimbace @ yahoo.com
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ABSTRACT At the activation temperature of 8000C, activated carbons of different particle sizes were produced from carbonized carbon that was previously obtained from coconut shells at carbonization temperature of 5000C. The activating salts were anhydrous FeCl3, ZnCl2, CaCl2 and K2CO3 at varying concentrations. Samples of a textile effluent containing indigo blue dye were used and the levels of dye adsorption were determined by colorimetry. Amongst the activated carbons the results showed that the particle size of 250m of ZnCl2 activated carbon was most effective adsorbing the dye up to 98%. The adsorption of lead (II), cadmium (II) and mercury (II) by the activated carbons was determined using atomic absorption spectrometry (AAS). The results show that the FeCl3 activated carbon was most effective in adsorbing 70% Pb while the K2CO3 activated carbon was most effective in adsorbing 81 and 83% of Cd and Hg respectively. KEYWORDS Adsorption, Activated Carbon, Indigo blue dye, colorimetry, atomic absorption spectrometry (AAS).

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INTRODUCTION The use of dyes in the textile industries is mandatory. The effluents containing the excess dye are finally discharged into soils and rivers constituting pollution particularly to the aquatic lives. It is therefore very important to reduce or remove the level of dyes in such effluents before discharge. Gimba,et al, [1] gave an estimate of colours of effluents and showed that this dye can be adsorbed unto activated carbons from coconut shell. The present work reports on the quantitative determination of the concentration of indigo dye adsorbed onto four different activated carbons each of eight different particle sizes unlike the two sizes used in the earlier study [2]. The adsorption of dyes, such as indigo blue, from textile effluents, would not only reduce the level of hazards but the recovery of the dye after adsorption will enhance recycling of the dye in such textile industries. It is envisaged that the procedure used to adsorb indigo dye in this study can be effective in reducing the amount of the dye from the effluent of any textile industry using indigo blue. Lead (II), Cadmium (Cd) and mercury (Hg) are soil and water pollutants arising from waste waters, industrial processes and their emissions, road traffic with leaded petrol, and dissolved food substances containing these toxic metals. Lead and cadmium are typical cumulative [3] poisons. Lead accumulation yields chronic intoxication manifesting in encephalopathies in the central nervous system (CNS), disturbance in kidney and liver functions progressing as far as necrosis, damage of the reproductive systems as well as anaemias and many metabolic deficiency symptom [4,5,6]. Access of cadmium into animals and human beings through feeding on plants containing absorbed Cd causes stomach irritation resulting in vomiting and diarrhea [7]. According to a recent report, bacteria present in water convert organometallise mercury into dimethyl mercury compounds which bind tenaciously to the proteins in fish tissue [4]. The highly toxic organomercury compounds eventually reach the higher animals and human beings through the food chain. A certain level of Hg can damage the CNS causing memory loss, slurred speech, hearing loss, lack of coordination, loss of sensation in fingers and toes, reproductive problems, coma and possibly death [8,9,10]. Therefore the major objective of this work is to find out the adsorption capacity of the activated carbons for Pb, Cd and Hg from contaminated waters. An important extension of this study, in future, would be in the selective recovery of the adsorbed metals for industrial and laboratory uses. These could include lead productions for vehicle batteries and solder, cadmium for production of pigments e.g. cadmium yellow 37 and metal coatings as well as mercury used in electrical engines and production of pigments. MATERIALS AND METHODS Materials Coconut shells were obtained locally, prepared and carbonized at 5000C as previously described by Gimba [1]. With appropriate sieves, different particle sizes, 150, 250, 355, 425 500, 850, 1400 and 2000m of the activated carbon were obtained. Anhydrous ZnCl2, FeCl3, CaCl2, K2CO3, Pb (NO3) 2, Cd(NO3) 2 and Hg (NO3)2, were of analytical grade. Muffle furnace model GLM 3 + PD/ND manufactured by Carbolite, BamfordSheffield, England. CORNING252 digital colorimeter. Porcelain crucible, sintered glass crucible and other glass wares were thoroughly washed with distilled water and dried in the oven at about 1050C. Indigo blue dye, referred to herein as IB, was obtained as an industrial chemical from a chemical company in Kaduna, Nigeria. 1195

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Activation of Carbonised Carbon About 2.0M solution of ZnCl2 was prepared and appropriate aliquots were diluted with distilled water to give a range of 0.025 2.0M solutions. 2.0cm3 of the 0.025M solution were measured into a glass crucible using a pipette. 2.0g of the carbonized carbon of a particular particle size (150- 2000m) were weighed into the crucible and mixed thoroughly with the ZnCl2 solution to form a paste and then allowed to dry up at room temperature to constant weight. Thereafter, the dry samples was heated in the Muffle furnace for 5 min at 8000C. The activated product was allowed to cool and then washed with 0.5M solution of ethanoic acid, rinsed several times with distilled water and dried in an air circulated oven. The activated product was kept in a dessicator. This procedure was repeated with each of 2.0cm3 of 0.05, 0.075, 1.0, 0.2, 0.50, 1.0, 1.5 and 2.0M solutions of ZnCl2 separately with 2.0g of the carbonized carbon. The above procedure was repeated using the same volume and concentrations as well as 2.0g of the carbonized product and activated with the other activating salts, FeCl3, CaCl2 and K2 CO3. Determination of Ash, Metal and Moisture content in activated carbons These parameters were determined for the activated carbons using the same procedure described for the carbonized product elsewhere [11]. Determination of the Amount of Adsorbed Indigo Blue Dye The method described by Mkayula and Matumbo [12] was used. 1.0g of the carbonized product and the different particle sizes of the activated carbons were dispensed into 250cm3 conical flask followed by 50cm3 of standard indigo blue solution in chloroform (5%v/v). This was stoppered and agitated at a fast speed of 5 rev. per sec. using an electric shaker for 1 hour each at room temperature. Thereafter the mixture in each flask was filtered by sunction through sintered glass crucible and the different filtrates were collected and analysed. Absorbances of standard solutions of indigo blue were used for the calibration curve. The concentrations of the indigo blue filtrates were determined photometrically at max of 602nm against pure chloroform using a digital CORNING 252 colorimeter. Determination of the Amount Lead (Pb), Cadmium (Cd) and Mercury (Hg) Adsorbed. The standard solution of lead (II) containing 2x103ppm was agitated with the activated carbon of 500 m particle size for 1h using an electric shaker. This was followed by filtration through a glass crucible of porosity 4. The filtrate was then analysed for Pb using AAS so as to obtain the quantity of metal adsorbed unto each activated carbon by difference. The above procedure was repeated using standard solution of 2x103ppm each of Cd (II) and Hg (II) salts. RESULTS AND DISCUSSION Preliminary investigation (Table 1) showed that the most effective activation temperature is 8000C.
Table 1;Effect of Activation Temperature on Adsorption (%) of indigo blue dye onto Activated Carbons. Activation Temperature, 0C % Indigo blue adsorbed 500 60 600 65 700 75 800 78 900 62

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This is the optimum activation temperature for adsorbing this dye for all the different activated carbons used in this study. Table 2 shows that both the ash and metal contents of the activated carbons are higher than those of the precursor (carbonized carbons).
Table 2: Ash, Metal and Moisture Content (%) of Different Activated Carbons (AC) at 150m particle size. Activating salts Parameters Ash content of carbonized carbon Ash content of Activated carbon Metal content of carbonized carbon Metal content of Activated carbon Moisture content of carbonized carbon Moisture content of Activated carbon FeCl3 2.49 5.8 0.11 9.70 10.01 5.54 CaCl2 5.90 0.27 10.25 4.93 ZnCl2 8.25 0.05 5.42 5.01 K2CO3 5.91 3.71 5.35 3.35

This suggests that the activating salts were bonded to the activated carbons. The order of ash content is ZnCl2 - > FeCl3 - > K2CO3 - > CaCl2 activated carbons at 150m particle size. With respect to metal content the percent metal content follows the order CaCl2 - > FeCl3 - > ZnCl2 -> K2CO3 activated carbon. The order of these two parameters (ash content and metal content) did not follow a particular trend (that is either increasing or decreasing) based on the physical constants of the Mn+. This tends to suggest that the total ash content and metal content depends on the specific chemical interaction of the activating salt and the carbonized carbon during the activation process. The moisture contents of the activated carbons are much lower than that of the carbonized product as can be seen in Table 2. This should be expected since the activation temperature (8000C) was higher than the carbonization temperature (5000C) and could have led to further removal of chemisorbed water in the carbonized product during the activation process. The order of moisture content is FeCl3 - > ZnCl2 -> CaCl2 - > K2CO3 activated carbon. Interestingly, ionic size increases as Fe3+< Zn2+< Ca2+< K+ while ionic charge follows as Fe3+> Zn2+= Ca2+> K+ in the activating salts. This is not surprising as the intermolecular association between water and M n+ depends on the polarizing power of the latter. This power depends directly on magnitude of the ionic charge and indirectly on the size of M n+ [13]. This explains why the tripositively charged and smallest Fe3* in FeCl3 has the highest moisture content and least for K2* in K2CO3 . Figures 1 4 show the percent adsorption of the indigo blue dye with varying concentrations of the salts used for the adsorptions.

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As it can be seen, there are optimum adsorption occurring at a particular particle size of each of the different activated carbons using particular concentrations of the activating salts. These are summarized in Table 3.
Most Effective particle size (m) 150 150 250 250 Table 3:Adsorption Characteristics of Indigo blue Most Effective concentration (mol dm-3 Activated Carbon type )of Activating salts) FeCl3 - activated CaCl2 - activated ZnCl2 - activated K2 CO3 - activated 1.0 0.5 1.0 2.0 Maximum Adsorption of IB (%) 92 93 98 97

It is now probably clear that ZnCl2 activated carbon at 250m particle size is most effective in adsorbing 98% of IB when 1.0mol dm-3 of ZnCl2 is employed, The K2CO3 activated carbon at 250m particle closely followed with 97% IB adsorption but at 2.0 mol dm-3 concentration of the activating agent. From the trend of the curves (Fig..4) there could be higher adsorption for the dye at higher concentrations of K2CO3 which might not be economically viable due to larger amount of the salts that will be needed. The effectiveness of the ZnCl2 activated carbon for IB could be attributed to the well recognized fact that ZnCl2 is a good dehydrating agent [14,15]. The coconut shell is a cellulosic material containing bonded OH group and H atom which can easily be removed as water by ZnCl2 particularly at the high activation temperature (8000C). The presence of ZnCl2 will therefore enhance activation process and increase the adsorption efficiency of the ZnCl2-activated product. The concentration dependent effectiveness of K2CO3-activated carbon (AC) could be explained from the redox reaction producing carbon (II) oxide (CO) as earlier recognized [8]. K2 CO3(s) + 2C(s) 2 K(s) + 3CO (g) The hot CO generated during the activation process would aid the formation of porous structure by burning the byproduct blockages in the precursor. In addition, the reduced product, potassium metal, is capable of penetrating in between the hexagon plates of the crystallites normally found in the carbonized product of most cellulosic materials [16]. The K in this position could spread the crystallites apart thereby aiding surface erosion of the unexposed carbonized product (due to closed pores) at the end of carbonization. This view is in agreement with the findings of [17,1] that oxidation (as in the above reaction) selectively erodes the surface of carbonized carbon. This, according to these authors, increases the surface areas, develop greater porosity and leave the remaining atoms of the carbon matrix in a configuration that has specific affinities for particular adsorbates. The increasing consumption of K2CO3 demands higher concentration of the salt resulting into greater effectiveness as more CO would be produced. This may explain why the highest concentration of 2.0 mol dm-3 of k2CO3 used in this work resulted into high adsorption efficiency for IB. It is most probable that the hot CO enhances removal of moisture from the K2CO3-activated carbon. This is coupled with the fact that less moisture associates with K + due to its relatively big size and small positive charge.. From the results obtained using the ZnCl2 and K2CO3 - activated carbons, the high ash content and low moisture content should be considered for effective adsorption of dyes, such as indigo blue, unto the activated carbons at 250m particle size.

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Adsorption of Metals Our preliminary experiments involving the four activated carbons showed that 500m particle size is most effective for adsorption of the three toxic metals, lead (II) _ cadmium (II) and mercury (Hg) [18]. Table 4 shows that the order of adsorption of lead from the solution by the carbons is FeCl3 -AC > ZnCl2 -AC > CaCl2 -AC > K2CO3 -AC. The order of increasing size and decreasing charge follows (Fe3t < Zn2+<Ca2+ < K+ ) and (Fe3t > Zn2+>Ca2+ >K+ ) respectively. For both Cd (II) and Hg (II) the order of adsorption by the adsorbents is the same but the reverse is the case for Pb (II), that is, K2CO3 - > CaCl2 > ZnCl2 - > FeCl3 activated carbon. This probably suggests that the nature of the adsorption is dependent on the similarity of electronic structure of the Cd(II) and Hg(II) which are successive group II B transition metals In the periodic table. The bigger Hg2+ (0.110 nm) is slightly better adsorbed (83%) than the slightly smaller Cd2+ (0.097 nm) of 81% adsorption unto the same K2CO3 - activated carbon. The adsorption is different with Pb2+ a group IVA metal, which is better, adsorbed unto the activated carbon containing a transition metal ion, Fe3+.
Table 4:Concentration (percentage) of Lead, Cadmium and Mercury Adsorbed unto Activated carbons at 500m particle size. Metal Adsorbed Lead Cadmium Mercury Initial concentration (ppm) 2000 2000 2000 Concentration ( %) of each metal Adsorbed FeCl3 activated CaCl2 ZnCl2 K2CO3 activated carbon Activated activated carbon carbon carbon 70 57.7 63.8 45.2 50.3 80 75 81 60.1 82 68.1 83

CONCLUSION The results contained in this report showed that coconut shell previously carbonized at 5000C and subsequently activated using FeCl3, CaCl2 ZnCl2 and K2CO3 at activation temperature of 8000C have the following characteristics. 1. Greater ash and metal content as well as smaller moisture content than the carbonized form. The earlier work [1], showed that the highest adsorption of indigo blue by carbonized carbon at 500m particle size and carbonization temperature of 5000C was only 37%. The 250m particle size of the ZnCl2 activated carbon produced at 8000C had the highest IB adsorption of 98% using 1.0 mol dm-3 of the activating salt. The relatively high affinity for IB adsorption was generally dependent on high ash content and low moisture content of the activated carbons. 2. The smaller particle sizes of the activated carbons generally have higher adsorption propensities for IB. This shows that effective adsorption of indigo blue is generally dependent on the surface area of the activated carbons. Similar view had been recognised earlier [1]. Particle sizes 150 and 250 are required for IB adsorption of over 90% using any of the four activated carbons employed in this study. 3. Toxicity levels due to the presence of Pb(II), Cd(II) and Hg(II) in aqueous medium can be reduced using FeCl3-activated carbons for Pb(II), and K2CO3 for Cd(II) and/or Hg(II) adsorption at 500m particle size [19]. Some of these metals are very expensive and their adsorption from wastewaters, for example, using these activated carbons could be utilized for their recovery and sold as laboratory

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chemicals. Well articulated beds or columns of these effective activated carbons at various points of the exit pipes of the wastewaters could be arranged before the effluents containing indigo blue dye and toxic metals are discharged. This will reduce the level of water pollution. REFERENCES
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