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Biosorption of basic dye using industrial waste spent brewery yeast

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Abstract In the present work the brewery industry waste is taken as a low cost biosorbent for the removal of dyes from the aqueous solution. Biosorption of dye (Basic blue 41) onto spent brewery yeast (SBY) was investigated. The biosorbent material is characterized using scanning electron microscopy, FT-IR spectroscopy and XRD. Factors affecting the biosorption process initial pH, temperature, initial dye concentration, biosorbent dosage and contact time was investigated. It was found that increase in pH results in higher dye loadings per unit weight of the biosorbent. Colour removal was found to decrease with initial dye concentration and increase with time. Increase in temperature and dosage increase dye removal performance. The equilibrium data fitted very well to Langmuir adsorption model. The results showed that the uptake processes followed the second-order rate expression. The study confirms that the spent brewery yeast can be used as low cost eco-friendly biosorbent for the removal of dyes from its aqueous solution.

Keywords: Biosorption, Basic Dye, Spent brewery yeast, Isotherm, Kinetics.

1. Introduction Dyes are synthetic aromatic water-soluble dispersible organic colorants, having potential application in various industries [1]. Textile and dyeing industry are among important sources for the continuous pollution of the environment. The effluents of these industries are highly coloured and disposal of these waste into environment can be extremely deleterious. It is reported that there are over 100,000 commercially available dyes [2] most of them are difficult to decolorize due to their complex aromatic molecular structure and they are also stable to light, water, heat and oxidizing agents. There are many structural varieties of dyes such as acidic, basic, reactive, azo, disperse, direct, vat and metal complex dyes. All of these dyes are harmful, when in contact with living tissues for a long time. The discharge of these dye bearing effluents to the river stream without proper treatment causes severe irreparable damage to the living beings and crops, both aquatic and terrestrial. The most widely used methods of dye removal from dye containing industrial effluents are categorized into chemical, physical and biological. Currently chemical and physical methods are used in industries for their treatment of effluents with research concentrating on biomaterials cheaper and effective alternatives. In physical treatment, adsorption technique has gained more importance due to their high efficiency in the removal of dyes from effluents and it is a process which is economically feasible compared to membrane filtration, ion exchange, irradiation and electro chemical methods. Activated carbon is the most widely used adsorbent for the removal of colour and treatment of textile effluents but due to its high price it is not used on a great scale [3]. This has led researchers to search for the use of cheap and efficient alternative material from various natural [4-10] and industrial waste products or biomass [11-12]. The industrial wastes that are available may be either organic or inorganic in nature. The survey of literature shows that various industrial waste or biomass from various industries such as sugar, fermentation, fertilizer, steel, pharmaceutical industries have been tried as biosorbent but not much work is done using spent waste yeast a brewery industry waste as biosorbent for the removal of dyes from aqueous solutions. Due to the prosperous market of the brewing industry, the production of this material has steadily increased in the last years. Few studies have been conducted on spent waste yeast potential as adsorbent for heavy metal removal cadmium, copper and lead from aqueous solutions [13]. The purpose of this study is to investigate the removal of basic dye by spent waste yeast a cheap and abundant biomass obtained from brewery industry.

2. Experimental 2.1 Materials Spent Waste Yeast (SWY) obtained from M/s Mohan Breweries and Distilleries Limited, Chennai, India, was in suspended in 1% (v/v) hydrochloric acid for an hour. This process removed the adsorbed nutrient ions. Then it was centrifuged and the acid solution was discarded. The acid-washed biomass was rinsed using distilled water. This process was repeated three times and the rinsed yeast was again centrifuged and the remaining biomass was dried at 60C for five hours. The dried biomass was ground, sieved and stored for further use in the experiments. SWY with a particle size of less than 100 mesh size was used in the experiments. The adsorbate BB 41 dye (C.I. = 11105, Chemical formula = C20H26N4O6S2, F.W = 482.57, nature = basic blue 41) was supplied by Sigma-Aldrich Chemicals Ltd., India. The structure of BB 41 is given in Fig. 1. An accurately weighed quantity (1 g) of BB 41 was dissolved in double distilled water separately to prepare stock solution of 1000 mg/L each. Experimental solutions of the desired concentrations were prepared by dilution with double-distilled water. 2.2 Physical characterization The physical properties of SWY relating to Brunauer-Emmett-Teller (BET) surface area and total pore volume were obtained by measuring their nitrogen adsorption isotherm at 77 K in a surface area and porosity analyzer (Model ASAP 2020 Micromeritics Co., USA). The surface morphology of SWY is characterized by scanning electron microscope (SEM) (JEOL JSM Model 6360). The SEM images of various magnifications are given in Fig. 2a, and 2b. The Fig. 3 shows FT-IR of the material recorded on Perkin Elmer FT-IR Model RX1 with KBR pellets for solid samples and XRD patterns were taken on a Rich Seifert (Model 3000) X- ray diffractometer using Cu-K radiation. 2.3. Analytical measurements The concentration of the dye BB 41 were determined using a UV-vis spectrophotometer (HITACHI U 2000, spectrophotometer) at a wavelength corresponding to the maximum absorbance of the dye (max = 617 nm). Calibration curves were plotted between absorbance and concentration of the dye solution. 2.4. Batch experiments

Batch experiments were conducted using 250 mL Erlenmeyer flasks to which 50 mL of dye containing waste water and biomass were added. These flasks were agitated in an orbital shaker at a constant speed of 150 rpm to study the effect of important parameters like pH, temperature, contact time, initial dye concentration and adsorbent dosage. Samples were withdrawn at appropriate time intervals and these samples were centrifuged (Research centrifuge Remi scientific work, India) at 4000 rpm. The supernatant was used for analysis of the residual dye concentration. The effect of pH on dye removal was studied over a pH range of 2-9. pH was adjusted by addition of dilute aqueous solutions of 0.1N HCl or 0.1N NaOH. For the optimum amount of adsorbent per unit mass of adsorbate, a 50mL dye solution was contacted with different amounts of SWY till equilibrium was attained. The kinetics of adsorption was determined by analyzing adsorptive uptake of the dye from the aqueous solution at different time intervals. The adsorption isotherm was found by agitating BB 41 solution of different concentrations with the known amount of SWY till the equilibrium was achieved. The studies were performed at room temperature of around 303 K. 3. Results and discussion 3.1 Physical characterization of SBG The data in Table 1 indicates the BET surface area, total pore volume and average pore width of SWY biosorbent. The results show that the pores of SWY are macroporous and possess fewer adsorption properties but have great ability to trap suspended solids for separation from liquid solutions [14]. The textural structure examination of SWY can be observed from the SEM photographs. It could be seen that the observation was consistent with the results from the measurements of physical properties given in Table 1. The IR Spectrum of SBG shown in Fig. 3 exhibited broad adsorption bands in the region of 3400 cm-1 that represent bounded OH and NH groups. The bands at 1382 cm-1 and1044 cm-1 represents carbonate and carbohydrates. CH stretch could be ascribed to the band that appeared at 2924 cm-1. The carboxyl ions give rise to two bands: a strong asymmetrical stretching band at 1635 cm-1and a weaker symmetrical band at 1449 cm-1. Wide angle X-ray spectra were obtained using a Rich Seifert (Model 3000) diffractometer with Cu K radiation ( = 1.5418 A0) ( = 30) for the ground powder of SWY found to be 1.4722 nm.

3.2. Effect of pH To study the effect of initial solution pH on the percentage colour removal of BB 41onto SWY, experiments were carried out at various pH starting from 2 to 9. The effect of initial pH on the equilibrium uptake is given in Figure 4 at 100 mg/L initial dye concentration at the liquid to solid ratio of 50 mL solution / 0.2 g biosorbent for BB 41.As seen from the Figure 4, the biosorption of the dye was less at lower pH value. The maximum dye sorption occurred at pH 9. This may be due to high electrostatic attraction between the negatively charged surface of the SWY and cationic dyes. Basic dyes are also called cationic dyes because of the positive electrical structure of the chromophore group. As the initial pH increases, the number of negatively charged sites on the biosorbent surfaces increased the electrostatic interactions between biosorbent and dyes were enhanced. In general, the basic dye uptakes are much higher in basic solutions than those in neutral and acidic conditions [15]. 3.3. Effect of Temperature Investigation of temperature effect on the biosorption of basic dyes is very important in the real application of biosorption as various textile and other dye effluents are produced at relatively high temperatures. The biosorption of BB 41onto SWY was investigated as a function of temperature and maximum uptake value was obtained at 60 C as can be seen from Figure 5. Biosorption increased with increase in temperature due to the increased surface activity suggesting that biosorption between the dyes and SWY was an endothermic process and the mechanism was mainly chemical adsorption. 3.4. Effect of Biosorbent dosage The effect of biosorbent dosage on the removal of BB 41onto SWY at Co = 100 mg/L is shown in Figure 6. It can be seen that the colour removal increases up to a certain limit and then it remains constant. The increase in the biosorption with the biosorbent dosage can be attributed to greater surface area and the availability of more adsorption sites [16]. At biosorbent

dosage greater than 0.2 g for BB 41, the surface dye concentration and the solution dye concentration come to equilibrium with each other. 3.5. Effect of Contact time The effect of contact time on biosorption of BB 41onto SWY at Co = 100 mg/L for biosorbent dosage 0.2 g is presented in Figure 7. It can be observed from the figure that rapid biosorption of dye has taken place in the first 20 min and, thereafter, the rate of biosorption decreased gradually and reached equilibrium in about 30 minutes for BB 41, around 92 % of removal was obtained in about 40 minutes. This may be due to strong attractive forces between the dye molecules and the biosorbent [17]. 3.6. Effect of Initial dye concentration The effect of initial dye concentration on the biosorption of dye was investigated and shown in Figure 8. It provides an important driving force to overcome all mass transfer resistances of the dye between the aqueous and solid phases and thus increases the uptake. The removal yield of BB 41 increased from 84 to 98 %, from 20 to 80 mg/L initial dye concentration, and then started to decrease from 98 to 80 % for initial dye concentration of 100 to 600 mg/L. At lower dye concentrations solute concentrations to biosorbent sites ratio is higher, which cause an increase in color removal [18]. At higher concentrations, lower biosorption yield is due to the saturation of biosorption sites. 3.7. Adsorption Isotherm The equilibrium sorption isotherm is fundamentally important in the design of biosorption system. Equilibrium studies in biosorption give the capacity of the sorbent. Equilibrium relationships between sorbent and sorbate are described by adsorption isotherms, usually the ratio between the quantity sorbed and that remaining in the solution at a fixed temperature at equilibrium [19]. Langmuir and Freundlich isotherm constants were determined from the plots of Ce/ qe versus Ce and ln qe versus ln Ce respectively. It was found that the

Langmuir isotherm best represents the equilibrium adsorption of BB 41 onto SWY. 2 and 3. 3.8. Kinetics of biosorption


isotherm constants and the correlation coefficient, R2 with the experimental data is given in Table

The experimental kinetic data were applied to two kinetic models, namely pseudofirst order and pseudo-second order to evaluate the biosorption mechanism. Figure 11 represent the pseudo-first order model, for the biosorption of BB 41, onto SWY. The constants associated with this kinetic model are given in Tables 4. Figure 12 represent the pseudo-second order kinetic model, for the biosorption of BB 41 onto SWY. The constants associated with this kinetic model are given in Tables 5. The calculated correlation coefficients are closer to unity for pseudo-second-order kinetics than that for the pseudo-first-order kinetic model. Therefore, the sorption can be approximated more appropriately by the pseudo-second-order kinetic model for the biosorption of BB 41onto SWY. 4. Conclusions The present investigation clearly demonstrated the applicability of SWY as biosorbent for BB 41 dye removal from aqueous solutions. Experiments were carried out covering a wide range of operating conditions. The influence of time, pH, adsorbent dosage, temperature and initial dye concentration was critically examined. The solution pH, and initial dye concentration played a significant role in affecting the capacity of biosorbent. The increase in pH and temperature there was an increase in colour removal. Initial dye concentration of above 150 mg/L lead to decrease in colour removal. Optimum sorbent dosage was 0.2 g/L. The equilibrium between the adsorbate in the solution and on the adsorbent surface was practically achieved in 40 min and biosorption kinetics was found to follow pseudo-second-order rate expression. Equilibrium biosorption data were best represented by Langmuir isotherm. The present study concludes that spent waste yeast could be employed as a low-cost and eco friendly biosorbent and as an alternative to the current expensive methods of removing dyes from textile effluents. Acknowledgements The financial support for this investigation given by Council of Scientific and Industrial Research (CSIR), Ministry of Human Resources Development, New Delhi, India under the grant CSIR Lr. No. 9/468(371)/2007-EMR-1 dated 30.03.2007 is gratefully acknowledged.

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Table 1 Main physical properties of Spent Waste Yeast (SWY) Table 2 Langmuir constants for the biosorption of BB 41onto SWY Table 3 Freundlich constants for biosorption of BB 41onto SWY Table 4 Pseudo First order kinetic parameters for the biosorption of BB 41onto SWY Table 5 Pseudo Second order kinetic parameters for the biosorption of BB 41 onto SWY

FIGURE CAPTIONS Figure 1 Chemical structure of BB 41 Figure 2a SEM image of SWY 500x Figure 2b SEM image of SWY 1000x Figure 3 FTIR spectra for SWY

Figure 4 Effect of pH for the biosorption of BB 41onto SWY

Figure 5 Effect of temperature for the biosorption of BB 41 onto SWY Figure 6 Effect of biosorbent dosage for the biosorption of BB 41 onto SWY Figure 7 Effect of contact time for the biosorption of BB 41 onto SWY Figure 8 Effect of initial dye concentration for the biosorption of BB 41 onto SWY

Figure 9 Pseudo-first order kinetic model for the biosorption of BB 41on SWY Figure 10 Pseudo-second order kinetic model for the biosorption of BB 41on SWY

Table 1 Main physical properties of Spent Waste Yeast (SWY) Sample SWY SBET (m2/g) BET Surface area 0.6025 Vt (cm3/g) Total pore volume 0.002171 Wav (Ao) Average pore width 144.68

Table 2 Langmuir constants for the biosorption of BB 41onto SWY Dye BB 41 Qm (mg/g) 68.49 KL (L/mg) 0.184 R2L 0.9896

Table 3 Freundlich constants for biosorption of BB 41onto SWY Dye BB 41 KF (mg/g) 4.24 n 4.860 R2F 0.9856

Table 4 Pseudo First order kinetic parameters for the biosorption of BB 41onto SWY

C0 (mg/L) 50 100 150

Pseudo-first order qs (mg/g) 3.66 3.33 2.47 kf (min-1) 0.0135 0.0126 0.0122 R2f 0.9544 0.9828 0.8447

Table 5 Pseudo Second order kinetic parameters for the biosorption of BB 41 onto SWY

C0 (mg/L) 50 100 150

Pseudo-second order qs (mg/g) 22.93 30.39 34.84 ks x 10-3 (g/mg/min) 0.757 1.723 4.446 R2s 0.974 0.9918 0.9993

Figure 1

Chemical structure of BB 41


(b) Figure 2 SEM images of SWY (a) 500 x (b) 1000 x

Figure 3 FT-IR spectra of SWY

Figure 4 Effect of pH for the biosorption of BB 41onto SWY

Figure 5 Effect of temperature for the biosorption of BB 41 onto SWY

Figure 6 Effect of biosorbent dosage for the biosorption of BB 41 onto SWY

Figure 7 Effect of contact time for the biosorption of BB 41 onto SWY

Figure 8 Effect of initial dye concentration for the biosorption of BB 41 onto SWY

Figure 9 Pseudo-first order kinetic model for the biosorption of BB 41on SWY

Figure 10 Pseudo-second order kinetic model for the biosorption of BB 41 on SWY