Iraqi Journal of Chemical and Petroleum Engineering 

 Vol.14 No.3 (September 2013) 55- 62 

ISSN: 1997-4884 

 

 

 

 

Removal of Phenolic Compounds from Aqueous Solution by Using 

Agricultural Waste (Al-Khriet) 

 
Hayder A.K. Al-jandeel 

Chemical Engineering Department, College of Engineering, University of Baghdad 
 

Abstract 

   Adsorption techniques are widely used to remove organics pollutants from waste 

water particularly, when using low cost adsorbent available in Iraq. Al-Khriet powder 

which was found in legs of Typha Domingensis is used as bio sorbent for removing 

phenolic compounds from aqueous solution. The influence of adsorbent dosage and 

contact time on removal percentage and adsorb ate amount of phenol and 4- nitro 

phenol onto Al-Khriet were studied. The highest adsorption capacity was for 4-

nitrophenol 91.5% than for phenol 82% with 50 mg/L concentration, 0.5 gm. dosage 

of adsorbent and pH 6 under a batch condition. The experimental data were tested 

using different isotherm models. The results show that Freundlich model resulted in 

the best fit also the kinetic study make it clear that the adsorption process proceeded 

according to the pseudo second order model. 
 

Key Words: Al-Khriet, Agricultural waste adsorbent, Bio sorption, phenolic 

compound, isotherm kinetic model  
 

Introduction 

   Phenols and their derivatives are 

known to be highly toxic for human 

beings and the aquatic life [1]. They 

result from different industrial 

processes such as, synthetic rubber, 

petrochemical industry, plastics, 

coking, paper, phenolic resin 

industries, and oil refineries [2, 3]. The 

use of water contained phenol can 

result in retardation of the central 

nervous system (CNS), impairment of 

the liver, kidney and irritation of the 

eyes, skin and mucous membrane [4]. 

It had been concluded from earlier 

studies that the skin is a route of 

entrance of phenol [5]. A 32 years old 

man died soon after spilling strong 

solution of phenol above his shoulder 

and other part of his body. Chronic 

phenol poisoning is diagnosed by the 

disfunction of different body system 

such as the nervous system. The 

human eyes is very sensitive to the 

chemical especially the phenol causing 

swelling and burns as well as the 

cornea may become white or even 

loosen sensation. Loss of vision has 

happened in some case [6]. According 

to the world health organization 

(WHO), the recommended 

concentration of phenolic compound in 

drink water is 1 mg/L [7] and that is 

why it is strongly recommended to 

remove phenolic compounds from 

wastewater. For this reason different 

environment friendly process had been 

used. Several physicochemical and 

biological treatment techniques such as 

chemical oxidation [8], ultrasonic 

Iraqi Journal of Chemical and 

Petroleum Engineering 

 

University of Baghdad 

College of Engineering 



Removal of Phenolic Compounds from Aqueous Solution by Using Agricultural Waste (Al-Khriet) 

 

 

56                                  IJCPE Vol.14 No.3 (September 2013)           -Available online at: www.iasj.net 
 

degradation [9], photo catalytic 

degradation using son photo chemical 

[10], enzymatic polymerization [11], 

ion exchange by resin [2] and 

adsorption [12] but the most efficient 

process and economically feasible 

technology for removal phenol in 

adsorption, especially when using 

locally available adsorbent. Many 

research have studied the feasibility of 

inexpensive adsorbents such as Al-

Khriet, (a powder which has been 

found in the legs of Typa 

Domingensis) agricultural waste and it 

is easily available in the waste could be 

an alternative for cheaper raw 

materials that are used to treat waste 

water. According to the literature there 

is no present study on the biosorptive 

removal of phenolic compound from 

aqueous solution using Al-Khriet. , 

they were selected for this research 

because they represent commonly 

encountrated phenolic pollutants in 

waste water treatment. The aim of this 

study is to look closely into the 

adsorption of Al-Khriet for removing 

phenol and 4-nitrophenol from 

aqueous solution. The effect of various 

factors, such as time of contact, bio 

sorbent dosage and initial adsorbent 

concentration on the adsorption 

process is investigated under batch 

experiments. Kinetic and equilibrium 

models were used to fit experimental 

data. 
 

Material and Adsorbent Properties 

   Al-Khriet, a powder was collected 

from the marshes in the south of Iraq, 

first it was washed with dionized water 

several times to remove impurities and 

dried in air for two days before drying 

in oven at 100°Cover night finally Al-

Khriet powder was stored in dictator. 
 

Experimental Work 

   Different concentrations of phenol 

and 4-nitrophenol aqueous solution 

were prepared from stock of 500 mg/L 

by dissolving a proper amount of 

phenol and 4-nitrophenol in deionized 

water. The properties of phenol and 4-

nitrophenol are shown in Table 1.  

   Another reason for choosing these 

compounds is their difference in 

molecular structure; phenol is two 

dimensional, flat structures, while 4-

nitrophenol is three dimensional.  
 

Table 1, Physical properties of adsorbents [13] 

Adsorb ate Phenol 4-nitrophenol 

Molecular 

weight (g/mol.) 
94.1 139.1 

Water solubility 

(g/ LH2O) 
93 17 

Molecular 

dimensions, (A
0
) 

5.76*4.17 6.84*4.17 

 

Adsorption was performed in a batch 

mode. The equilibrium isotherm was 

determined by mixing 0.5 gm of Al-

Khriet with 25 ml of phenol and 4-

nitrophenol solution with different 

initial concentration (50-200) mg/L in 

conical flask. The flask was shaken in 

shaker at room temperature of 25°C for 

3 hrs. Such a time is indeed to reach 

equilibrium according to series of 

experiments. The suspension of Al-

Khriet was then filtered and the 

residual phenol concentration was 

measured by uv-visible (Shimadzu uv-

160A) spectrophotometer.  The latter 

was calibrated at a wavelength of 270 

nm, 320 nm for phenol and 4-

nitrophenol respectively using a 

number of aqueous solutions of phenol 

and 4-nitrophenol at known 

concentration in order to calculate the 

calibration curve. 

   The adsorbed amount at equilibrium, 

e
q (mg/g) and removal percentage of 

phenol and 4-nitrophenol onto Al-

Khriet were calculated according to the 

following equation [14]. 
 

 
w

VCC
q

e

e

)(
0


                           … (1) 

 

100*%
0

0

C

CC
R

e


                      … (2) 



Hayder A.K. Al-jandeel 

 

-Available online at: www.iasj.net               IJCPE Vol.14 No.3 (September 2013)                              57 
 

Where R is the removal percentage, 

0
C  and 

e
C  are the initial and 

equilibrium concentrations of adsorb 

ate (mg/L) respectively, V is the 

volume of solution (L), w is the weight 

of adsorbent used (gm.). 
 

   The adsorption kinetics was analyzed 

by adding 0.5gm of Al-Khriet to 25 ml 

of 50 mg/L of phenol and 4-

nitrophenol solutions. The sample was 

shaken and examined at different time 

intervals. The effect of adsorbent 

dosage and the initial concentration of 

feed solution were also studied by 

using different amount of adsorbent 

(0.2-1) gm for the 50 mg/L solution of 

phenol and 4-nitrophenol. 
 

Results and Discussion  

Effect of Contact Time 

   As shown in Fig.1 the percent 

removal of phenol and 4-nitrophenol 

by adsorption onto Al-Khriet increases 

with contact time until attain 

equilibrium of about 3 hr. Removal 

percent equal to 91.5% and 82% for 4-

nitrophenol and phenol respectively at 

pH 6 and of 50 ppm ions concentration 

for each adsorb ate and 0.5 gm. of 

adsorbents. The result indicates that the 

rate of sorption of 4-nitrophenol and 

phenol on Al-Khriet were fast because 

of a largest amount of two compounds 

attached to the adsorbent within 1 hr of 

adsorption. The similar results have 

been reported by Khorsravi R. et al 

[15].    
 

 
Fig.1 Effect of time on removal efficiency 

using Al-Khriet as adsorbent 

The Effect of Adsorbent Dosage  

   The adsorption of phenol and 4-

nitrophenol on Al-Khriet was carried 

out by various adsorbent dosages. The 

relationship between adsorbent dosage 

and percent of removal is presented in 

Fig.2. It can be perceived the percent 

of removal increased with increasing 

of Al-Khriet dosage while the loading 

capacity 
e

q (mg/g) decreased, this is 

due to increase surface area, more 

adsorption sites are available. The 

optimum weight of adsorbents was 

found (0.5) gm. for Al-Khriet.  

  

Fig.2 Effect of adsorbent dosage on percent 

removal for phenol and 4-nitrophenol by Al-

Khriet, contact time 3 hr. initial concentration 

for both ions 50 ppm 

 

   It is appears from this figure that the 

removal percent of 4-nitrophenol is 

higher than phenol that is due to its 

lower water solubility and larger 

molecular weight of 4-nitrophenol 

when compared to phenol according to 

Table 1. In general, the adsorptive 

capacity was related to the electron- 

with drawing or electron- donating 

functional groups, water solubility of 

the compound and the molecular 

structure of the adsorb ate. The less 

soluble compounds are easier to be 

adsorbed [2].   
 

Effect of Phenol and 4-nitrophenol 

Concentration  

   The effect of phenol and 4-
nitorphenol concentration on percent of 

removal was studied. The 

0

20

40

60

80

100

0 50 100 150 200 250

tim e(m in)

R
%

4-Nitrophenol

phenol

60

70

80

90

100

0.2 0.5 0.75 1

Adsorbent dosage (gm)

R
e
m

o
v
a
l 

p
e
r
c
e
n

t

0

1

2

3

4

5

L
o

a
d

in
g

 c
a
p

a
c
it

y
 q

e

4-Nitrophenol

Phenol

4-Nitrophenol

Phenol



Removal of Phenolic Compounds from Aqueous Solution by Using Agricultural Waste (Al-Khriet) 

 

 

58                                  IJCPE Vol.14 No.3 (September 2013)           -Available online at: www.iasj.net 
 

concentration was varied from (50-

200) ppm on 0.5 gm. of Al-Khriet at 

room temperature. The result in Fig. 3 

shows that the percent removal 

decreased as the concentration of 

phenol and 4-nitorphenol increased, 

indicating the less favorable sites and 

available for adsorb ate with increasing 

concentration. Removal percent equal 

to 85 % and 74% for 4-nitrophenol and 

phenol respectively at 200 ppm 

concentration, using 0.5gm of Al-

Khriet and pH of 6. The pH value were 

6 before and after mixing with 

adsorbent. 0.1M of NaOH and HCl 

were used for pH adjustment to fix the 

pH value in all experiments. 

 

 
Fig.3 Removal of phenol and 4- nitro phenol 

using different concentration of ions 

 

Kinetic Studies 

   Different kinetic models including 

the pseudo first order model (PFOM) 

and pseudo second order model 

(PSOM) were examined for the 

experimental data to estimate the 

adsorption kinetics. The PFOM and 

PSOM may be represented by the 

following equations respectively [16]. 

 

tkqqq
ete 1

ln)ln(                    … (3) 

 

eet
q

t

qkq

t


2

2

1
                        … (4) 

 

   Where
e

q ,
t

q  is the amount of 

adsorbed at equilibrium (mg.g
-1

),
1

k  

and 
2

k   is the rate constant for PFOM 

and PSOM respectively. The slope and 

intercept of plots )ln(
te

qq   versus 

time were used to determine the 
1

k  

while the slope and intercept of plot of  

t
q

t
 versus t were used to calculate

2
k . 

 

The PFOM and PSOM plots are shown 

in Fig. 4 and Fig. 5 respectively. A 

comparison of kinetics model is 

included in Table 2, based on their 

correlation coefficient (R
2
). The 

adsorption of phenolic compounds 

onto Al-Khriet is suitable for PSOM, 

based on higher correlation 

coefficients.  

 

 
Fig.4 PFOM plots for phenol and 4-

nitrophenol 
 

 
Fig.5 PSOM plots for phenol and 4-

nitrophenol 

0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200 250

ppm

R
% 4-Nitophenol

Phenol

-4.5

-4

-3.5

-3

-2.5

-2

-1.5

-1

-0.5

0

0 50 100 150 200

tim e

ln
(
q

e
-
q

t)

4-Nitrophenol

Phenol

0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200

tim e(m in)

t
/q

t 4-Nitrophenol

Phenol



Hayder A.K. Al-jandeel 

 

-Available online at: www.iasj.net               IJCPE Vol.14 No.3 (September 2013)                              59 
 

Table 2, The rate constant and correlation 

coefficient for pseudo first and second order 

for the kinetic models 

Kinetic 

model 
Parameters Nitrophenol Phenol 

PFOM k1(min
-1

) 0.022 0.016 

 eq  (mg/g) 0.733 0.613 

 R1
2
 0.926 0.94 

PSOM 
k2 (mg.g

-1
. 

min
-1

) 
0.055 0.048 

 eq  (mg/g) 2.37 2.14 

 R1
2
 0.999 0.998 

 

Equilibrium Isotherms 

   Langmuir (LM), Freundlich (FU) 

and Dubinin-Rodushkevich (D-RU) 

were chosen in this study to assess the 

relationship between the equilibrium 

concentration and the amount of 

phenol and 4-nitrophenol adsorbed on 

Al-Khriet. The LM assumes that the 

adsorption occurs at specific 

homogenous sites within the adsorbent 

and has found successful application in 

many studies of monolayer adsorption. 

The LM equation is given by the 

following equation [17].  

 

maxmax

1

q

C

Kqq

C
e

Le

e
                   … (5) 

 

Where 
e

q is the solid phase adsorbate 

concentration in equilibrium (mg/g), 

max
q the maximum adsorption capacity 

corresponding to complete monolayer 

coverage (mg/g), 
e

C the concentration 

of adsorb ate at equilibrium (mg/L) and 

L
K is the Langmuir constant L/mg. 

The  
L

K and 
max

q can be evaluated 

from the slopes and intercept of linear 

plots 
ee

qC / versus 
e

C as shown in Fig. 

6, the parameter of these model were 

tabulated in Table (3).  

Fig.6, Adsorption isotherm of phenol and 4-

nitrophenol at pH (6) by using Langmuir 

 

Table 3, Parameter of isotherms for phenol and 

4-nitrophenol and correlation coefficient for 

Langmuir isotherm R
2
 

Kinetic 

model 
Parameters 

4-

nitrophenol 
phenol 

Langmuir max
q

(mg/g) 
15.24 16.6 

 L
K  

L/mg 
0.0.039 0.015 

 R
2
 0.979 0.99 

 

Freundlich model is present by 

following equation [18]. 

 

efe
C

n
Kq ln

1
lnln                     … (6) 

 

   Freundlich describes the adsorption 

on an energetically heterogeneous 

surface on which the adsorbed 

molecules are interactive. This 

isotherm dose not predict any 

saturation of the sorbent by sorbate, 

indicating multilayer sorption where 

f
K is the Freundlich constant 

(mole/gm.) and n stands for the 

adsorption intensity. The value of   
f

K  

and 1/n were calculated from slope and 

intercept of the plot between 
e

qln and 

e
Cln as shown in Fig. 7. The value of 

f
K  and n were tabulated in Table (4).  

R
2
 = 0.99

R
2
 = 0.9787

0

1

2

3

4

5

6

7

8

0 10 20 30 40 50 60

Ce

C
e
/
q

e

4-Nitrophenol

Phenol



Removal of Phenolic Compounds from Aqueous Solution by Using Agricultural Waste (Al-Khriet) 

 

 

60                                  IJCPE Vol.14 No.3 (September 2013)           -Available online at: www.iasj.net 
 

 
Fig.7 Adsorption isotherm of phenol and 4-

nitrophenol at pH (6) by using Freundlich 

 

Table 4, parameter of isotherms for phenol and 

4-nitrophenol and correlation coefficient for 

Freundlich isotherm R2
 

Kinetic 

model 
Parameters 

4-

nitrophenol 
phenol 

Freundlich 
n

f
mg

L

g

mg
K

1

)(

 

0.886 0.414 

 n 1.50 1.36 

 R
2
 0.998 0.999 

 

   The Dubinin-Rodushkevich model is 

an empirical equation employed to 

determine if the adsorption occurred by 

a physical or chemical process. The 

Dubinin-Rodushkevich[19] equation is 

more general than Langmuir because it 

does not assume a homogenous surface 

or a constant sorption potential. The 

linear form of this model is represented 

by  

 
2

lnln Bqq
me
                          … (7) 

 

B (
22

.


Kjmol ) is the constant related to 

sorption energy while   is the polanyi 
sorption potential.  
 

)
1

1ln(
e

C
RT                         … (8) 

 

R is the gas constant 8.314 J.mol
-1

K
-1

, 

T is the temperature in Kelvin. The 

value of B, 
m

q  were calculated from 

the slopes and intercept of the plots 

e
qln versus 

2
  as shown in Fig. 8 and 

9 [19], the parameter of these models 

were tabulated in Table (5). 

 

 
Fig.8 Adsorption isotherm of 4-nitrophenol  at 

pH (6) by using Dubinin-Rodushkevich 

 

 

Fig.9 Adsorption isotherm of phenol at pH (6) 

by using Dubinin-Rodushkevich 

 

Table (5) parameter of isotherms for phenol 

and 4-nitrophenol and correlation coefficient 

for Dubinin-Rodushkevich isotherm R
2
 

Kinetic model Parameters 
4-

nitrophenol 
phenol 

Dubinin-

Rodushkevich B*
4

10  0.04 3 

 
m

q
m

q

 7 147.7 

 R
2
 0.886 0.998 

 

The experimental data yielded 

excellent fit within the following 

isotherm 

FU>LM> D-RU 

Based on its 
2

R  value as it gave the 

maximum 
2

R  value among the 

conceded model.  

R
2
 = 0.9982

R
2
 = 0.9991

0

0.5

1

1.5

2

2.5

0 1 2 3 4 5

ln(Ce)

ln
(
q

e
)

4-Nitrophenol

Phenol

0

0.5

1

1.5

2

2.5

0 50000 100000 150000 200000 250000 300000

ln
(
q

e
)

4-Nitrophenol

0

0.5

1

1.5

2

2.5

0 5000 10000 15000

ln
(q

e
)

Phenol



Hayder A.K. Al-jandeel 

 

-Available online at: www.iasj.net               IJCPE Vol.14 No.3 (September 2013)                              61 
 

Conclusion 

   Al-Khriet can be used for first time 
as effective, locally available 

adsorbents for the removal of phenol 

and nitrophenol from waste water. The 

adsorption of phenol and nitrophenol 

on Al-Khriet is dependent on contact 

time, initial concentration and 

adsorbent dosage. It was observed that 

the removal process increase with 

contact time and attain equilibrium 

about 180 minute. In the study of 

kinetics of adsorption, the pseudo- 

second order mode provides better 

correlation than pseudo first order 

model. Also Freundlich model was 

found to fit the present experimental 

data with high correlation factor. 

Finally Al-Khriet under consideration 

is not only economical, but also an 

agriculture waste and locally available 

which would be useful for economical 

treatment of waste water containing 

phenol compounds.  

                     

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Removal of Phenolic Compounds from Aqueous Solution by Using Agricultural Waste (Al-Khriet) 

 

 

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