Equilibrium and Kinetic Modelling on Reactive Blue 171 Dye from Aqueous Solutions using Cyperus pangorei

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Abstract: In the present study, Cyperus pangorei biomasses were used as a low-cost adsorbent for the anionic dye (Reactive Blue 171) adsorption in a batch process at 30C. Equilibrium sorption isotherms and kinetics studies were established. The equilibrium data were analyzed using Langmuir and Freundlich isotherm models. The adsorption isotherm data were fitted well to the Langmuir isotherm when compared to Freundlich isotherm and the monolayer adsorption capacity was found .The kinetic data obtained at different initial concentrations were analyzed using pseudo-first order and pseudo-second order kinetics. The kinetic data was found to be fitted very well with pseudo-second order kinetics. The results revealed that the dead biomass of Cyperus pangorei, being waste, have the potential to be used as a low-cost adsorbent for the removal of Reactive Blue 171 from aqueous solutions.

Introduction
Many industries like textiles, paper, plastics, leather, food, cosmetics, etc., use dyes or pigments to color their final product. Such widespread use of dyes and pigments often poses problems in the form of colored waste water that require pre-treatment for color prior to disposal into water bodies [1]. Two major sources of dye pollution are the textile and dyestuff manufacturing industries. Effluents of these industries are highly colored and very difficult to treat [2]. Discharge of dye wastewaters into water bodies can adversely affect aquatic environment by reducing light penetration and photosynthesis, and being hazardous and toxic to aquatic life [3]. Conventional methods for treating dye wastewater, e.g. coagulation/flocculation, chemical oxidation, activated sludge process, are having economic disadvantage. Adsorption is an attractive and effective method for dye removal

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from wastewater, especially if the adsorbent is cheap and widely available. Many lowcost adsorbents have been investigated on dye removal, such as fly ash [4], bottom ash [5], clay, zeolite [6], calcine alunite [7], peanut hull, and brown seaweed [8, 9]. In the present study Cyperus pangorei was used as sorbent for the removal of a Reactive blue 171 dye. Batch studies were carried out with the effect of initial sorbent dosage, pH and dye concentration. Equilibrium and kinetic data were processed to understand the sorption mechanism of dye molecule onto Cyperus pangorei.

Materials and Methods

Adsorbate The Navy blue (Reactive Blue 171) dye used was purchased from Jagson Colorchem Limited; Ahmedabad, India. Absorbance values were recorded at wavelength of maximum absorbance (max) corresponding to the dye and the dye solution was initially calibrated for concentration. The concentration of Reactive Blue 171 in aqueous solution was determined using UV spectrophotometer at max of 590nm.

Reactive blue 171 Biosorbent The Cyperus pangorei plant was collected from Trichy. It was washed thoroughly with distilled water to remove the surface adhered particles and water-soluble materials. Then it was sliced, spread on trays and oven dried at 60 oC for 48 hours. The dried slices were grounded and sieved with different mesh screens. These adsorbents of 80 mesh size were used for the experiment. No other chemical of physical treatments were used prior to adsorption experiments. Batch Studies Batch experiments were adopted in the present study in order to obtain the optimum operating conditions for the adsorption of reactive blue 171 from aqueous solution. Biosorption experiments were carried out in a rotary shaker at 180 rpm at room temperature. The dye solution was prepared to get a required concentration of 50 mg/L at

30oC. Weighed amount of dried biomass was introduced in to the dye solutions. Samples were withdrawn at different time interval and centrifuged at 12,000 rpm for 10 min and the absorbance of the supernatant was determined at maximum wavelength of max at 590 nm. The amount of adsorption at equilibrium, qeq (mg/g), was calculated by: qeq = (Co-Ce)V/W (1) where C0 and Ceq (mg/L) are the liquid-phase concentrations of dye at initial and equilibrium, respectively. V (L) is the volume of the solution and W (g) is the mass of dry sorbent used. Study of Biosorbent Dosage Different quantities of dried Cyperus pangorei biomass varying from 0.1 g to 0.5 g in 100 ml of each dye solution at a concentration of 50 mg/L were shaken at 30C in a rotary shaker operating at 180 rpm. Then the mixtures were centrifuged at 12000 rpm for 10 min, and the supernatant was analysed using UV spectrophotometer at wavelength of 590 nm. Study of pH Each dye solution at concentration of 50 mg/L with 0.1 g of Cyperus pangorei was shaken at 30C over a range of pH values from 1 to 6 on rotary shaker operating at 180 rpm. The dye solution pH was adjusted to obtain required initial pH values by HCl and NaOH. . The samples were withdrawn at pre determined time intervals and centrifuged at 12000 rpm for 10 min and the absorbance values were determined using UV spectrophotometer. Study of Initial Dye Concentration The influence of initial dye concentration varying from 50 to 120 mg/L on equilibrium uptake capacity of Reactive Blue171 on the biomasses of Cyperus pangorei was studied with the optimum biosorbent dosage and pH. 100 mL of required concentration of dye solution with the optimum pH and dosage of biosorbent was maintained and agitated in a temperature controlled shaker. Samples were withdrawn, centrifuged and the uptake capacity was determined using UV spectrophotometer.

Results and Discussion

Effect of Biosorbent Dosage It has been found from Fig. 1 that the equilibrium dye uptake capacity was found to be decreased with increase in biosorbent dosage. The decrease in equilibrium uptake capacity may due to the solute transfer rate on to adsorbent surface. The equilibrium dye uptake capacity is the amount of dye compounds adsorbed on to unit weight of the adsorbent [10]. In case of Reactive Blue 171 the dye uptake was 15.78 mg/g at the dosage of 0.1gm. The optimum sorbent dosage was concluded to be 0.1 gm and the equilibrium time was found to be 270 minutes.

Fig. 1: Effect of sorbent dosage on the Reactive blue 171 dye using Cyperus pangorei (Co: 50 mg/L, Temperature: 30C, Agitation rate: 180 rpm) Effect of pH The initial pH value of the solution is an important factor which must be considered during sorption studies [11]. The effect of pH on the amount of dye removal was analyzed over the pH range from 1 to 6. Dye solution of 50 mg/L was distributed in seven 250 ml conical flasks. Then the optimum amount of biomass (0.1 g/100 ml) was added to each flask. It was found from the Fig. 2 that equilibrium dye uptake capacity was found to be more at pH of 3. It may be due to the electrostatic attraction between the positively charged biomass surfaces to the negatively charged dye anions [12].

Fig. 2: Effect of pH on the Reactive blue 171 dye using (Co: 50 mg/L, Temperature: 30C, Agitation rate: 180 rpm) Effect of Initial Dye Concentration The dye solutions were prepared with different concentrations (50, 70, 90,120 mg/L) and the solution pH was adjusted to the optimal value of 3 by addition of HCl or NaOH. The higher initial dye concentration increases the number of collision between dye compounds anions and sorbent, which enhances the sorption process [13]. It was found that the higher initial dye concentrations enhanced the adsorption process at temperature of 30C. At 30C, dye uptake capacity of the biosorbent was found to be increased from

24.56 mg/g to 40.34 mg/g with increase in the initial dye concentration from 50 mg/L to 120 mg/L (Fig. 3).

Fig. 3 Effect of Initial Dye Concentration on the dye uptake capacity of Reactive blue 171 dye using Cyperus pangorei (pH 3, Temperature: 30C, Agitation rate: 180 rpm) Biosorption Kinetics In order to investigate the biosorption of Reactive Blue 171 on the surface of Cyperus pangorei biomass, different kinetic models are used to examine the controlling mechanism of adsorption process. The proposed kinetic models are based on literature for sorption processes and adsorption capacity of adsorbent. In this study, pseudo-first order kinetic model and pseudo-second order kinetic model are used to find the best fitted model for the experimental data. Pseudo-First Order Kinetic Model This model assumes that the rate of change of solute uptake with time is directly proportional to difference in saturation concentration and the amount of solid uptake with time. In most cases the biosorption reaction preceded by diffusion through a boundary, the kinetics follows the pseudo-first order rate equation. The rate law for a pseudo firstorder reaction becomes
log (q eq q ) =log q eq k 1, ad 2.303 t

(3)

A linear fit of log (qeq q) versus t shows the applicability of this kinetic model. From the slope and intercept, the pseudo-first order rate constant (k1,ad) and qeq values were determined and shown in the Table 1. From the Table 1 it is observed that the experimental data point does not fit a straight line, it may be concluded that the kinetics of Reactive Blue 171 adsorption on Cyperus pangorei is not following the pseudo first order kinetic model.

Table 1: The pseudo-first and second order rate constants, calculated and experimental qeq values for the biosorption of Reactive Blue 171 using C. pangorei

Pseudo-first order Initial dye concentrat ion (mg /L) qeq,exp (mg /g) k2,ad (g /mg/min) X 10-3

Pseudo-second order

k1,ad (per min)

qeq,cal (mg /g)

R2

qeq,cal (mg /g)

R2

50 70 90 120

24.75 30.26 34.52 40.25

0.001 0.124 0.120 0.013

16.67 19.6 21.86 28.6

0.874 0.951 0.949 0.974

2.0 1.3 1.2 0.9

26.31 32.15 37.59 43.29

0.994 0.990 0.992 0.989

Pseudo-Second Order Kinetic Model Biosorption process with chemisorptions being the rate-control follows pseudo-second order model. The sorption kinetics may be represented by pseudo-second order model as
t 1 1 = + t 2 q q eq k 2, ad q eq

(4)

Fig. 4 shows that the plot of t/qt versus t is a straight line with slope of 1/qeq and intercepts 1/k2,ad q2eq. Using the value of qeq calculated from the slope, the value of k2,ad is determined from the intercept. The calculated value of K2,ad, qeq and their corresponding regression coefficient (R2) values are presented in Table 1. If second order kinetics is applicable, the plot of (t/q) against t of Eq. (4) should give a linear relationship and there is no need to know any of the parameters beforehand. In contrast to the other model, it predicts the behavior over the whole biosorption range and is in agreement with a biosorption mechanism being the rate-controlling step [13, 14]. The value of regression coefficient is nearly unity for 50 and 70 and 90 mg/L of Reactive Blue 171 which confirms that, the sorption kinetics follows a pseudo-second order process. Thus, it may be concluded that the biosorption of reactive blue 171 by Cyperus pangorei can be better explained by pseudo-second order kinetic model than pseudo-first order kinetic model.

Fig. 4 Pseudo-second order kinetic model for the adsorption of Reactive Blue 171 Dye on Cyperus pangorei Biosorption Equilibrium Biosorption properties and equilibrium parameters are the adsorption isotherms. It describes how the dye interacts with biosorbent, and comprehensive understanding of the nature of interaction. Isotherms help to provide information about the optimum use of adsorbent. So, in order to optimize the design of an adsorption system to remove dye from solutions, it is essential to establish the most appropriate correlation for the equilibrium curve. There are several isotherm equations available for analyzing experimental sorption equilibrium parameters. However, the most common types of isotherms are the Langmuir and Freundlich models. Langmuir Isotherm The Langmuir isotherm theory assumes monolayer coverage of adsorbate over a homogenous adsorbent surface [15]. A basic assumption is that sorption takes place at specific homogeneous sites within the adsorbent. Once a dye molecule occupies a site, no further adsorption can take place at that site. The Langmuir isotherm is [15]:
Q b Ceq qeq = 1 +b Ceq

(5)

Where qeq (mg/g), Q (mg/g), Ceq (mg/L) and b (L/mg) are the Langmuir isotherm constants. The Langmuir isotherm model has been successfully applied to many adsorption processes. The equilibrium data were fitted very well to Langmuir isotherm and the constants together with the R2 value are listed in Table 2. Fig. 5 shows the experimental equilibrium data fitted with of Langmuir isotherm.

Fig. 5 Langmuir adsorption isotherm for Reactive Blue 171 using Cyperus pangorei biomass. Freundlich Isotherm Model The Freundlich isotherm [16] is an empirical equation assuming that the adsorption process takes place on heterogeneous surfaces and adsorption capacity is related to the concentration of reactive blue 171 dye at equilibrium: 1/ n qeq = K F Ceq (6) where KF and n are the Freundlich constants of the system. KF and n indicate adsorption capacity and adsorption intensity, respectively. The best fit of equilibrium model was determined based on the correlation coefficient R2. Table 2: Langmuir and Freundlich Model Langmuir model Q0 b R2 KF Freundlich model n R2

58.139

0.028

0.9926

2.2248

2.33

0.9233

Conclusion From the present investigation, it was observed that C. pangorei waste biomass could be used as a potential low cost biosorbent to treat the textile effluent. As this material is readily available, no regeneration is necessary and spent biosorbent could be used as fuel. Biosorbent dosage, pH and initial dye concentration were found to affect the biosorption capacity of the C. pangorei. Maximum equilibrium uptake capacity was obtained at initial biosorbent dosage value of 0.1 g per 100 mL and pH of 3. Equilibrium uptake capacity was found to be more at initial dye concentration of 120 mg/L when compared to all other initial dye concentration studied in the present investigation.

From the kinetic study, it was observed that the kinetic data fitted very well with the pseudo-second order rate equation when compared to pseudo-first order rate equation. The Langmuir and Freundlich isotherm equations were used for mathematical description of the biosorption of Reactive Blue 171 dye onto the C. pangorei and it was found that the biosorption equilibrium data fitted well to the Langmuir isotherm model. Nomenclature b [L/mg] Ceq [mg /L] k1,ad [per min] k2,ad [g /mg /min] Qo [mg /g] Q [mg /g] qeq [mg / g] qeq,cal [mg /g] qeq,ex [mg/ g] constant related to the affinity of the binding sites unbiosorbed dye concentration in solution at equilibrium rate constant for pseudo-first order biosorption rate constant of the pseudo-second order biosorption maximum amount of dye biosorbed per unit weight of biomass amount of dye biosorbed on the biosorbent at time t equilibrium dye uptake capacity calculated equilibrium dye uptake capacity experimental equilibrium dye uptake capacity

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