The Effect of Temperature on the Adsorption of 4-Nitrophenol onto Palm Shell based Activated Carbon

Norzilah Abdul Halif, Wan Mohd Ashri Wan Daud, Iskandar Mohd Noor, Che Rosmani Che Hassan.
Dept. of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia Email: nahwanz@yahoo.com

ABSTRACT: A series of experiments was conducted to study the adsorption of 4-NP onto Palm Shell based Activated Carbon (PSAC) and the results obtained were compared to two commercial products, one is Coal based Activated Carbon (CBAC) and another is Coconut Shell based Activated Carbon (CSAC). The experiments were carried out in batch mode with the temperatures of the operation were varied from 25 to 40C and the 4-NP concentrations were varied from 500 to 2000 mg/L. The Langmuir and Freundlich isotherms were found to represent the measured adsorption data well

( R 2 > 0.90) . The results show that in all

cases, increasing the temperature from 25 to 40C, the affinity decreases and CSAC has the lowest (26.13%), followed by CBAC (46.13%) and then PSAC (50.30%). Similar trends also found in the adsorption intensity, where CSAC was the lowest (11.12%), followed by PSAC (21.66%) and CBAC the highest (27.94%). The findings of this investigation suggest that PSAC can be used as an effective adsorbent for the removal of 4-NP from wastewater. Keywords: Adsorption, 4-nitrophenol, palm shell based activated carbon, Freundlich isotherm, Langmuir isotherm.

(1)

INTRODUCTION

The presence of phenol and phenolic compounds in water and wastewater has been of great public concern and it is one of the most frequent contaminants at hazardous-waste sites. Nitrophenols are usually formed due to the photo degradation of pesticides and these phenols have considerable solubility in water. There are very toxic to flora and fauna and therefore, pose serious environmental problems. In order to reduce this problem, various regulatory agencies have set a limit on the concentration of phenolic compounds in industrials effluent before it can be safely discharged to water bodies and in Malaysia, the concentration should not exceed 10 g/L [1]. Adsorption has been found to be superior and preferred choice than other techniques for water re-use because of low initial cost, simplicity of design, ease of operation and insensitivity to toxic substances. Activated carbons of high porosity, high surface are frequently used in industry for purification and environmental remediation. It can be produced from a number of precursors such as coal, wood and agricultural wastes. Recognizing the economic drawback of activated carbon, such as high cost, many investigators have studied the feasibility of using cheap, yet commercially available materials as potential adsorbents such as the low rank coal [2], ash [3], and clay [4]. Another viable option is by converting agriculture waste to activated carbon. Palm shell is an agricultural waste from palm oil industry and in South East Asia there is an

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abundance of this material and currently it has no significant technical application. In Malaysia alone approximately 10 million tones of palm shell was generated annually and it creates large disposal problem. Several studies concluded that a good quality activated carbon could be produced from palm shell [5,6]. Currently, there is no meaningful study has been conducted on the possibility of using PSAC in liquid phase applications such as water treatment. Several studies have been carried out to determine the equilibrium relationship on adsorption of phenol on activated carbon using isotherm model such as Freundlich and Langmuir [7,8]. There are many factors that affect the adsorption capacity such as particle size [9], initial concentration [10], pH [11], and temperature [12]. Studies on adsorption equilibrium behavior with temperature variation from 10 to 80C have been carried out [13,14]. In this study 4-NP is used as the model adsorbate, since it has been recommended as representative of aqueous organic pollutants [2]. The aim of this work is to study the suitability of PSAC to remove 4-NP from aqueous solutions and the effects of temperature (25, 30, 35, and 40C) on the equilibrium isotherm. The results obtained will be compared to the results obtained using two commercial activated carbons, CSAC and CBAC.

(2) 2.1 2.1.1

EXPERIMENTAL Materials Adsorbate diluted

4-NP with purity greater than 99.5% supplied by Scharlau Chemie S.A. was with distilled water to prepare a desired concentration of simulated wastewater. 2.1.2 Adsorbents

The palm shell based activated carbon was supplied by local company, while commercial coal and coconut shell based activated carbons were obtained from a multinational company. 2.2 2.2.1 Analyses Nitrogen Adsorption/Desorption Isothems

The sample porosity is determined using nitrogen adsorption/desorption isotherm at 77 K were determined volumetrically using a Micromeritics ASAP 2010 Porosimeter. Before the experiment began, the adsorbents were degassed ( 10 mmHg ) at 393 K. The surface areas of the samples were measured based on Brunauer-Emmet-Teller (BET) method and the tplot method was applied to calculate the micropore volume. 2.3 2.3.1 Experimental Procedures Preparation of Adsorbent
4

PSAC, CBAC and CSAC were grinded and sieved into a fixed particle size range (105-150 m). After that the samples were dried in oven at 110C overnight and then cooled down in a desiccator.

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2.3.2.

Determination of Equilibrium Time

For each kinetics experiment, 0.2 g of activated carbon was contacted with 100 ml of 4-NP solution of 500 mg/l in 250 ml Ermenlayer flasks and was shaken at room temperature at 200 rotations per minute (rpm) for several durations (5, 10, 15, 20, 25, 30, 35, 40 h). The contents of each flask were then filtered and the concentrations were measured using a spectrophotometer. These experiments were conducted to establish an equilibrium time to be used as contact time in the subsequent isotherm experiments. 2.3.3 Equilibrium studies

A typical experiment began by changing 0.2 g of activated carbon into a 250 ml Ermenlayer flask containing 100 ml of 4-NP solution having concentrations 500, 800, 1000, 1500, 1800 and 2000 mg/l for a contact time of 35h. The experiment was repeated at different temperatures of 30, 35, and 40C. Then, suspensions were filtered through Whatman No. 542 filter paper and the residual adsorbate concentrations were determined spectrophotometrically. The isotherms were then analysed using Freundlich and Langmuir models. The Freundlich equation model can be expressed as:

Qe = K f Ce

(2)

Where K F and n are empirical constants dependent on several environment factors such as such temperature. In a linear form;

ln Qe = ln K f + 1 ln Ce n

(3)

The Langmuir model is based on a monolayer of the adsorbate adsorbed onto the carbon surface and the model can be expressed as follows:

Qe =
Where;

X m K LCe 1 + KCe

(4)

Qe = amount of solute adsorbed on the adsorbent (mg of adsorbate per g of adsorbent) Ce = concentration of adsobate in solution (mg/l) X m =maximum adsorption capacity corresponding to complete monolayer coverage (mg of
solute adsorbed per g of adsorbent) K L = Langmuir constant related to energy of adsorption Eq. (3) can be rearranged in a linear form;

Ce 1 C = + e Qe X m K L X m

(5)

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Where;

C o = Initial concentration of adsorbate in solution (mg/l) K L = Langmuir constant related to energy of adsorption
(3) 3.1 RESULTS AND DISCUSSION Pore Structure Analysis Table 1: Structural parameters of CSAC, CBAC and PSAC.

Adsorbent

BET
(m
2

t-plot

g)

Vmic ( cm 3 g )
0.294300 0.339851 0.258907

CSAC PSAC CBAC

869.0395 867.9529 748.6172

As shown in Table 1 CSAC has the highest BET surface area followed by PSAC and CBAC. It should be noted that BET surface area is apparent surface area and do not represent the true surface area. The values were provided to indicate a measure of comparative variation in surface area as a function of type of activated carbons. 3.2 4-nitrophenol Analysis

The analysis was done using a Hitachi UV Spectrophotometer and a good linearity is obtained between the absorbency versus 4-nitrophenol concentrations at maximum absorbency wavelength of 317.0 nm. 3.3 Equilibrium Time

The amount of 4-NP adsorbed increases with time before it gradually attains equilibrium in 35 hr. The removal curves are smooth and continuous, indicating the formation of monolayer coverage onto surface of the activated carbon. Previous studies shows that time to achieve equilibrium were varied from 24 hr [15] to 4 days [13]. 3.4 Equilibrium Studies

The adsorption isotherm reveals the distribution of adsorbate molecule in liquid and solid phase when the adsorption process has reached an equilibrium stage. The results indicate CSAC has the highest adsorptive capacity and CBAC has the lowest. It is interesting to note that although PSAC has the highest micropore volume, it has lower 4-NP adsorption capacity as compared to CSAC. This could be due to the fact that not all the micropores available are assessable to 4-NP molecules. In this case, BET surface area could be more reflective to indicate 4-NP adsorption. The isotherms were analyzed using the Langmuir and Freundlich models and the results are shown in Table 2 together with the regression coefficient, r . At all temperatures, the samples give a better fit in the Freundlich and Langmuir model.
2

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3.4.1

Freundlich Isotherm

The Freundlich model has found wide acceptance because of its accuracy and broad applicability. The results of Freundlich analysis are summarized in Table 2. Of particular interest are the values of the constant n and KF. Similar values for the constant mean similar adsorptive properties for the carbons. This intensity of adsorption process, n indicates a favorable adsorption when 1<n<10, and it is more favorable as 1/n <1. From Table 2, in general CBAC has marginally the higher value of n, followed by PSAC then CSAC. Thus, it indicates that CSAC has slightly stronger force that fixes the adsorbate, 4-NP onto its surface as compared to PSAC and CBAC. KF is relative to the adsorption capacity and at low temperature of 25 and 30C, CBAC has marginally higher value of KF, followed by CSAC then PSAC. However, at higher temperature, the difference in the KF values is significant. 3.4.2 Langmuir Isotherm

The value of Langmuir adsorption isotherm for PSAC is given in Table 2 and this indicates the monolayer coverage of 4-NP molecules onto the outer surface of the adsorbent. The values of Langmuir constant, Xm and KL were determined from the slopes and intercepts of the plots respectively. The adsorption of 4-NP onto activated carbon is directly related to the available surface area of the adsorbent. Normally, large surface areas signify high adsorption of organic compounds. Hence, surface area can be considered as an important attribute in selectivity of an adsorbent. Other factors that influence the adsorption are the physical and chemical properties of the substrate, such as molecular dimension [3]. The forces of attraction between carbon and a molecule are greater when the size of the molecule is closer to the size of the pores of the carbon. 4-NP has molecular dimension of 0.813 nm while most of activated carbon tested here has pore diameter of 2-4 nm, with CSAC has the highest, followed by PSAC and CBAC. This could be partly contributed to the higher adsorption of 4-NP in CSAC. 3.5 Effect of Temperature

The temperature has significant effects on the adsorption process. Increasing the temperature is known to increase the rate of diffusion of the adsorbate molecules across the external boundary layer and in the internal pores of the adsorbent particle, owing to the decrease in the viscosity of the solution. However, changing the temperature will change the equilibrium capacity of the adsorbent for a particular adsorbate. In this part, a series of experiments were conducted at 25, 30, 35, and 40C to study the effect of temperature on the adsorption isotherm. 3.5.1 Freundlich Isotherm

Table 2 depicts the values of parameter KF and n at different temperatures. The results show that both parameters decrease with the increase in temperature. For PSAC, the decrease in KF is 21.66, 27.94% for CBAC and 11.12% for CSAC. The value of n represents the force, which fixes the 4-NP molecule onto the adsorbent. From Table 2, it is clear that for all the adsorbents the strength of the forces for each of adsorbent was decreased with the increase in temperature. The decrease could be attributed to the higher kinetics energy possessed by the adsorbed molecules at higher temperature to escape from the surface.

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3.5.2

Langmuir Isotherm

The adsorption affinity of the three carbons for 4-NP can be assessed by comparing the apparent dissociation constant, KL, which is the measure of the stability of the complex formed between 4-NP and the functional groups on the carbon surface under specified.

Table 2: Langmuir and Freundlich isotherms parameters T (C) Adsorbent Langmuir Freundlich n 5.9137 5.1652 4.9140 5.4612 5.0813 4.6511 4.8924 4.6773 4.5025 4.5737 4.3917 4.3048

Xm
25 CBAC PSAC CSAC CBAC PSAC CSAC CBAC PSAC CSAC CBAC PSAC CSAC
( mg / g ) 476.190 476.190 555.556 500.000 476.190 526.316 500.000 500.000 526.316 526.316 526.316 526.316

KL
(l/mg) 0.01939 0.01825 0.01780 0.01365 0.01852 0.01585 0.01052 0.01729 0.01554 0.01041 0.00907 0.01314

KF
(l/g) 146.0282 122.5967 125.9015 129.7358 119.1639 113.3862 114.4113 115.2035 112.3142 105.2249 96.0434 111.8994

30

35

40

0.9879 0.9985 0.9978 0.9883 0.9963 0.9970 0.9902 0.9941 0.9948 0.9782 0.9841 0.9937

0.9250 0.9764 0.8702 0.9896 0.9714 0.9699 0.9928 0.9410 0.9895 0.9794 0.8514 0.9922

experimental conditions. A small KL value indicates that the carbon has a low affinity for 4-NP and vice versa. When the KL value is high, more surfaces are covered with adsorbate molecule due to stronger affinity of adsorbate molecule towards the surface. Similarly, when the heat of adsorption increases, the amount adsorbed increases due to the higher energy barrier that adsorbed molecules have to overcome to be released back to the liquid phase and more bonds are formed. In relation to temperature, increasing the temperature will decrease the amount adsorbed, Xm at a given pressure due to greater energy acquired by the adsorbed molecule to escape from the surface. From Table 2, the decrease in KL for each of adsorbents with the increase of temperature from 25 to 40C are 50.30% for PSAC, 46.31% for CBAC and 26.18% for CSAC, which means that CSAC has a highest affinity and PSAC in the lowest. (4) CONCLUSIONS

PSAC is relatively a good adsorbent for 4-NP adsorption. The result obtained show that it is slightly inferior as compared to CSAC and slightly better than CBAC. In all cases, when temperature is decreased from 25 to 40C, the adsorption affinity decreases and the decreased was lowest for CSAC (26.13%), followed by CBAC (46.13%) and then PSAC (50.30%). Similar trends were also found in the adsorption intensity, with CSAC has the lowest reduction (11.12%), PSAC (21.66%) and CBAC the highest (27.94%).

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