ion of Basic Dye Using Industrial Waste Spent Brewery Yeast

8/3/2019 ion of Basic Dye Using Industrial Waste Spent Brewery Yeast

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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.

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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.



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



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.



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



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. 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



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 SBET (m2/g)

BET Surface area

Vt (cm3/g)

Total pore volume

Wav (Ao)

Average pore width

SWY 0.6025 0.002171 144.68



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



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



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



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



Figure 1 Chemical structure of BB 41



(a) (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

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