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Biosorption of basic dye using industrial waste spent brewery yeast
Document by: Bharadwaj
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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.
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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.
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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 60 ºC 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 = C 20H26 N4O6S2, 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 RX 1 with KBR pellets for
solid samples and XRD patterns were taken on a Rich Seifert (Model 3000) X- ray
diffractometer using Cu-K α 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 (λ max = 617 nm). Calibration curves were plotted between absorbance and
concentration of the dye solution.
2.4. Batch experiments
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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 α radiation (λ = 1.5418 A0) (θ = 30) for the ground powder of SWY
found to be 1.4722 nm.
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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 ºC 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
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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
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Langmuir isotherm best represents the equilibrium adsorption of BB 41 onto SWY. The
isotherm constants and the correlation coefficient, R 2 with the experimental data is given in Table
2 and 3.
3.8. Kinetics of biosorption
The experimental kinetic data were applied to two kinetic models, namely pseudo-
first 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 CAPTIONS
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
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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
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Table 1
Main physical properties of Spent Waste Yeast (SWY)
Sample SBET (m2/g)
BET Surface area
Vt (cm3/g)
Total pore volume
Wav (Ao)
Average pore width
SWY 0.6025 0.002171 144.68
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Table 2 Langmuir constants for the biosorption of BB 41onto SWY
Dye Qm (mg/g) K L (L/mg) R 2L
BB 41 68.49 0.184 0.9896
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Table 3 Freundlich constants for biosorption of BB 41onto SWY
Dye K F (mg/g) n R 2F
BB 41 4.24 4.860 0.9856
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Table 4 Pseudo First order kinetic parameters for the biosorption of BB 41onto SWY
C0
(mg/L)
Pseudo-first order
qs
(mg/g)
k f
(min-1)R 2f
50 3.66 0.0135 0.9544
100 3.33 0.0126 0.9828
150 2.47 0.0122 0.8447
Table 5 Pseudo Second order kinetic parameters for the biosorption of BB 41 onto SWY
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C0
(mg/L)
Pseudo-second order
qs
(mg/g)
k s x 10-3
(g/mg/min)R 2s
50 22.93 0.757 0.974
100 30.39 1.723 0.9918
150 34.84 4.446 0.9993
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Figure 1 Chemical structure of BB 41
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(a) (b)
Figure 2 SEM images of SWY (a) 500 x (b) 1000 x
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Figure 3 FT-IR spectra of SWY
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Figure 4 Effect of pH for the biosorption of BB 41onto SWY
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Figure 5 Effect of temperature for the biosorption of BB 41 onto SWY
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Figure 6 Effect of biosorbent dosage for the biosorption of BB 41 onto SWY
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Figure 7 Effect of contact time for the biosorption of BB 41 onto SWY
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Figure 8 Effect of initial dye concentration for the biosorption of BB 41 onto SWY
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Figure 9 Pseudo-first order kinetic model for the biosorption of BB 41on SWY