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Study of Adsorption Phenomena by Using Almond Husk for Removal of Aqueous Dyes

M. Bhanuprakash1*and S. L. Belagali1

DOI:http://dx.doi.org/10.12944/CWE.12.1.10

在空气和土壤中,水污染as an important one. Deterioration of water resources by the addition of various pollutants leads to the major threat to water quality and use of water for domestic purpose which leads to unaesthetic. For the plants, animals and human beings dyes are considered as most hazardous among various water pollutants. The present paper describes the adsorption behaviour of adsorbent almond husk with respect to dyes of Crystal violet, Bromocresol green, Pararosaniline and Victoria blue was investigated. The batch method was used and parameters like pH, adsorbent dosage, contact time and initial and final concentration of dyes were studied. Adsorbent used to be effective, with total removal of all dyes of 90%, with higher percentage removal from bromocresol green 97.5%, Crystal violet 96.9%, Pararosaniline 95.6% and Victoria blue 95%. Almond husk was an effective adsorbent with maximum percentage removal of 97.5% bromocresol green. Adsorbent was analysed by the instrument of scanning electron microscopy and Fourier infrared spectroscopy. In the present study almond husk almond husk was studied as a very good adsorbent for the removal of dyes from the aqueous media. Isotherm model of Langmuir, Freundlich and Dubinin-Radushkevich were considered to be favourable.


Almond husk; Adsorbent; Batch mode; Dose; Adsorption

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Bhanuprakash M, Belagali S. L. Study of Adsorption Phenomena by Using Almond Husk for Removal of Aqueous Dyes. Curr World Environ 2017;12(1). DOI:http://dx.doi.org/10.12944/CWE.12.1.10

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Bhanuprakash M, Belagali S. L. Study of Adsorption Phenomena by Using Almond Husk for Removal of Aqueous Dyes. Curr World Environ 2017;12(1). . Curr World Environ 2017;12(1). Available from://www.a-i-l-s-a.com/?p=16796


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Received: 2017-01-11
Accepted: 2017-02-24

Introduction

Waste water from industries represents a challenge to biological and conventional physicochemical treatment methods considering for both effluent composition and volume of discharged.1Among various industries, textile industries waste water discharge is a major environmental problem throughout the world, because it contains various synthetic dyes which lead to environmental pollution.2It has been considered that using of more than 10,000 (worldwide) commercial dyes by textile and manufacturing industries, consumption of dyes 1000 tons/year. During dyeing process 10 to 15% of these dyes is discharged as effluents in to the waste streams.3Industries like paper, leather tanning, cosmetic, food, woollen and carpet also contributes the pollution load.4Most of the dyes released by textile industries have complex aromatic structure, resistant to light and harmful to the aquatic environment, biological activity and another degradative process.5Some of the dyes are carcinogenic which leads to skin irritating, allergic dermatitis, dysfunction of kidney, liver, brain and central nervous system.6,7Decolorization of textile waste water is the worldwide problem. Many treatment methods have been applied for the removal of textile dyes from wastewaters which include adsorption, nano-filtration, electro kinetic coagulation, ozonisation and precipitation, advanced chemical oxidation, electrochemical oxidation, supported liquid membrane, liquid-liquid extraction and biological process ,8coagulation,9Ozonisation and membrane separation,10anaerobic decolourisation,11Oxidation,12flocculation13and adsorption.14Adsorption has evolved as one of the most effective physical processes for removal of dyes. The number of adsorbents likeFicus racemosaplant barks,15Water hyacinth,16Silica gel,17Hazelnut shells,18Sugarcane bagasse,19Coralwood tree legume pod,20Aspergillustamarii,21Rice Husk,22agriculture residue based adsorbent,23Various adsorbent,24Biomass ,25Composite adsorbent,26Low cost adsorbents,27Potatohusk.28的literature survey reveals that almond husk has not been used as an adsorbent for the synthetic dyes such as Crystal violet, Victoria blue, bromocresol green and pararosaniline. So, we considered this material for further observation.

Materials and Methods

Preparation of adsorbent for study

From bakery and sweet shops, almond husk was collected. It was washed with water, dried in sunlight followed by hot air oven at 1000c. The adsorbent was made into small pieces by hand and then it was crushed into powdered by mixer grinder at 5 to 10min. It was sieved by 2mm mesh to get uniform particle size for adsorption. The adsorbent was treated by 2N NaOH and 2N HCl followed by washed from distilling water to maintain pH neutral condition.

Preparation of dye solutions

100 ppm of (Crystal violet, Victoria blue, Bromocresol green and Pararosaniline) different dye solutions were prepared by dissolving 10mg of dye in 100ml of distilling water and was diluted to required concentrations. For all dye preparation procedure was same. We used simple possible equipment one can have in the lab for the analysis of the dye and the adsorbent sample that is UV-visible spectrophotometer and pH instruments were used. Scanning electron microscopy and Fourier transform infrared spectroscopy instruments was used for the surface analysis to confirm adsorption.

Experimental section

Batch Experiment

的100ml stock solution was taken to conduct batch mode experiments for dye adsorption. The parameter of pH, adsorbent dose, concentration of adsorbate and contact time was studied. For the process of adsorption of the dye solution adsorbent was kept aside for adsorption to take place.

10ppm/L dye solutions were taken in five number of 25ml beakers for that adsorbent of 0.25g to 1.25g was added and adsorption was studied.

25毫升样品与不同浓度的染料solution (2, 4, 6, 8 and 10 ppm) were taken in five beakers with a constant dose of 0.25g adsorbent added to each and allowed the process to go at room temperature.

25ml samples of (2 to 10ppm) of dye solutions taken in five beakers and adsorbent of varying doses of 0.25g to 1.25g put in an increasing manner. The solution was placed aside for adsorption. For the effect of contact time, a 25ml sample of 10ppm dye solution was studied by adding a 0.25g dose of adsorbent.

Adsorption isotherms

为了确定的吸附势广告sorbent, the study of sorption isotherm was essential in selecting an adsorbent for the removal of the dyes. The adsorption process was studied with the Freundlich and Langmuir isotherms (Adamson, 1960).29

Formula

where, qeis the amount of dye adsorbed per unit mass of adsorbent at equilibrium (in mg/g), K and n are respectively the measures of sorption capacity and intensity of adsorption, Ceis the equilibrium concentration of dyes (in mg/L) and Qoand b are the Langmuir constants indicating the sorption capacity (in mg/g) and energy of adsorption (in gm/L) respectively from the slope and intercept.

Kinetics of the Adsorption

的adsorption kinetics were found to be of the first order. The following equation proposed by Kannan and Vanamudi (1991)30was employed for adsorption data:

Formula

where, Coand Ctare concentrations of dyes at zero time and at time t (min). The values of log (Co/Ct) were found to be linearly correlated with the contact time for all the above dyes.Further, the essential characteristics of the Langmuir isotherm can be described in terms of a dimensionless constant, namely a separation factor or equilibrium parameter, RLwhich was defined by Weber and Chakravorti (1974) [31] in the equation: RL= l/(labia), where, b is the Langmuir constant and ci是染料的初始浓度(ppm)。的value of the parameter, RLindicates the nature of the isotherm as given below. A standard RLvalue which indicates the nature of the developed Model shows in the table 1.

Table 1: Nature of the isotherm and their range

RLvalue

Nature of isotherm

RL> 1

0 < RL< 1

RL=1

RL= 0

Unfavorable

Linear

Favorable

Irreversible

的Dubinin-Radhuskevich isotherm model is another empirical model which initially formulated for the adsorption process following a pore filling mechanism (Dubinin 1960).32It is generally applied to express the adsorption process occurred onto both homogeneous and heterogeneous. The non-linear expression of dubinin-radushkevich isotherm model can be illustrated as

Formula
Where qe= amount of adsorbate in the adsorbent at equilibrium (mg/g); qm= theoretical isotherm saturation capacity mg/g; β = Dubinin-Radhuskevich isotherm constant (mol2/kg2) and Ɛ = Dubinin-Radhuskevich isotherm constant.

Formula
β can be denoted as isotherm constant mean while the parameterƐcan be calculated as

Formula
Where R,T and Ce代表气体常数(8.314 J /摩尔K),呈献te temperature (K) and adsorbate equilibrium concentration (mg/l).

Results and Discussion

的rate of adsorption of an adsorbent for an adsorption varies with different conditions i.e adsorbate concentration, adsorbent dose, pH and contact time, etc. In the present study, the effect of adsorption on different condition was carried out to determine the adsorption rate.

Effect of pH on the rate of adsorption

的table 2. shows the time taken for the adsorption of different dyes at acidic and neutral media.

Table 2: Adsorption of dyes with different pH

Dyes used

Adsorption time at different pH

Acidic (hrs)

Neutral (hrs.)

Basic (hrs.)

Crystal violet

LA

5

LA

Bromocresol green

7

LA

LA

Pararosaniline

6

LA

LA

Victoria blue

5

LA

LA

Note: LA-less adsorption

From the data:Adsorption was carried out in neutral media for Crystal violet, whereas Bromo cresol green, pararosaniline and victoria blue were in the acidic media.

Effect of adsorbent dose

0.25g to 1.25g of the adsorbent dose was added to five numbers of 25ml samples of 1% dye for adsorption study. Adsorption was increased by increasing of dose for all dye solution (Fig. 1).

Fig-1: Graph showing the effect of dose for all dyes.


Figure1: Super-elastic effect
Click here to View figure

Effect of concentration

25ml samples of (2-5%) concentration of dye solution taken in five beakers at room temperature for that constant dose 0.25g added separately was studied for adsorption, which indicates that the concentration of the dye solution increases, the adsorption of the adsorbent decreases. (Fig. 2). Adsorption rate was decreased due to increase in concentration for all dye solution.

Fig-2: Graph showing effect of concentration for all dyes


Figure 2: Graph showing effect of concentration for all dyes
Click here to View figure

Effect of Dose v/s Concentration

的varying adsorbent dose of (0.25g to 1.25g) was added in series to five numbers of 25ml samples of (2 to 5%) dye solution and it was kept for adsorption to take place. From the result which indicates, concentration of the dye solution and dose are correlated with each other (Fig.3)

Fig-3: Graph(A) showing the effect of Dose v/s Concentrations for Victoria blue and Crystal violet dye, Graph(B) showing effect of DoseVrs Concentration for Bromocresol green and Pararosaniline


Figure 3: Graph(A) showing the effect of Dose v/s Concentrations for Victoria blue and Crystal violet dye, Graph(B) showing effect of DoseVrs Concentration for Bromocresol green and Pararosaniline
Click here to View figure


Effect of contact time

25ml of 10ppm dye solution added with 0.25g of adsorbent was investigated. From the result of all the dyes as the contact period increases adsorption increases. The contact time of all dye solution was within 12hrs.

Fig-4: Graph showing the effect of contact time for all dyes.


Figure 4: Graph showing the effect of contact time for all dyes.
Click here to View figure

Scanning Electron Microscopic Image

的scanning electron microscope graph was taken at 50µm resolution. In the fig.a unadsorbed material shows voids and holes like structure with the irregular, rough surface area which are considered as active sites, for the adsorption of dyes.

Fig 5  a) Unadsorbed adsorbent, b) Pararosaniline adsorbed  adsorbent, c) Crystal violet adsorbed adsorbent and d) Victoria  blue adsorbed adsorbent


Figure 5 a): Unadsorbed adsorbent, b) Pararosaniline adsorbed adsorbent, c) Crystal violet adsorbed adsorbent and d) Victoria blue adsorbed adsorbent
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While on careful observation the adsorption was not same for all the dyes. In fig.5 (b ) while treating with Pararosaniline dye, all voids are filled and it looked to be covering all the surface area. Similarly, in the case of Crystal violet dye fig.5(c), there is a layer of formation on the active surface layer. But not completed as in the case of Pararosaniline, this indicates that the adsorbent can be further used for adsorption of Crystal violet dye. While looking at the material adsorbed with Victoria blue dye fig.5 (d) the active voids can be seen in unadsorbed material, but during the adsorption in looks to be a layer formation on voids covering the whole surfaces. This looks to be saturated when considering the other two results. It seems that the material has uptake the highest possible amount of dye,that is further adsorption leads to the rupture of the layer and affect the adsorption process.

Fourier transforms infrared spectroscopy instrumental analysis is carried out to the adsorbent dyes of Crystal violet, Pararosaniline and Victoria blue. The FT-IR spectra show in fig 6.

Figure 6


Figure 6
Click here to View figure

的adsorption studies were also studied by the FT-IR spectral analysis the adsorbent also has some of the functional groups and also present in the dyes we can comprise both the unadsorbed and adsorbed adsorbent and can correlate the results. Because some of the interaction may be present in the functional groups of the dye and adsorbent. After adsorption, it can lead to the masking of some functional groups in the adsorbent, it may due to the chemical interactions between them. An adsorbent with crystal violet shows the absence of the peaks at 1424 cm-1which were present in the unadsorbed samples and the intensity of other peaks decreased. Pararosaniline adsorbed adsorbent shows the strong and wide peaks in at 3200-3300 which indicates the amine group which is present in the dye and also shows the absence of the peaks at 1424cm-1and also observe that increased Intensity of aromatic C-H stretching vibrations, because of the Victoria blue has plenty of aromatic C-H groups. From the above study, we can conclude that the distribution of functional groups differs in unadsorbed and adsorbed material, there we observe that disappearance of stretching frequency peak at 1424 cm-1(Nitro group) and increased intensity in the peaks of aromatic C-H and NH2groups. This change in functional group distribution in IR spectroscopy indicates the adsorption has taken place.

Adsorption Isotherm

Adsorption isotherm of Langmuir, Freundlich, and D-R isotherm is carried out on dyes of Bromocresol green, Crystal violet, Pararosaniline and Victoria blue. Looking at the results of adsorbent with different dyes, it is following the Fredlich Isotherm. It can be noted that the solpes with different dyes are above 2 and the interception of adsorbent with crystal violet dye is 3.03, indicating the effectiveness of adsorbent. The other isotherms are also displayed in the Table 3.

Table 3: Different adsorption isotherm studies

Adsorption Isotherm

Bromocresol green

Crystal violet

Pararosaniline

Victoria blue

Langmuir:

Slope(a)

Intercept (b)

Correlation Coefficient

1

0.06

1.08

0.14

0.002

0.152

1.3

1.19

1.04

1.15

0.533

0.993

Freundlich:

Slope(a)

Intercept (b)

Correlation Coefficient

2.72

1.51

0.2

2.3

3.03

0.35

2.0

1.53

1.0

1.64

1.16

0.53

Kinetics of adsorption:

102k/min.

Correlation Coefficient

7.67x10-03

0.2

9.7x10-03

0.35

0.010

1.0

0.022

0.53

D-R isotherm:

Slope (β)

Intercept (qm)

D-R value

0.015

0.045

5.88

2.23x10-07

5.9x10-06

4.74x10-07

0.72x104

0.21x104

8.33x10-3

0.86x109

0.5x108

2.41x10-10

Conclusion

Almond husk has shown excellent result as an adsorbent of dyes. To come to this conclusion adsorbent was exposed to various test with respect to concentration of dyes, pH, contact time and dosage of adsorbent was also analyzed. Based on these various isotherms were defined which showed that adsorbent has the ability to remove dyes from the aqueous system.

Acknowledgment

One of the Authors, Mr.Bhanuprakash M, is grateful to UGC Non-NET fellowship scheme, and thankful for the instrumentation facility to institute of excellence of the University of Mysore.

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