Chemical Engineering Journal 243 (2014) 3142

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Chemical Engineering Journal

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Combined magnetic eld and adsorption process for treatment

of biologically treated palm oil mill efuent (POME)
Rae Rushdy Mohammed a, Mohammad Reza Ketabachi b, Gordon McKay c,
a
Department of Chemical Industries, Mosul Technical Institute, Al-Majmoaa Al-Thaqaya, Mosul, Iraq
b
Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham Malaysia Campus, 43500 Semenyih, Selangor, Malaysia
c
Department of Chemical and Biomolecular Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong Special Administrative Region

h i g h l i g h t s

 A novel method was introduced by integrating magnetic eld exposure with adsorption technique.
 Combined magnetic eld and adsorption process has a vital role in treating POME.
 Adsorption performance and adsorption rate could be enhanced by magnetic eld.
 Magnetization process accelerated the removal of colour, TSS and COD in adsorption process.
 The new method increased the percentage removal of colour, TSS and COD by 39%, 61% and 46% respectively.

a r t i c l e i n f o a b s t r a c t

Article history: The production of palm oil, however, results in the generation of large quantities of polluted wastewater
Received 23 September 2013 commonly referred as palm oil mill efuent (POME). There is an actual need to seek factors intensifying
Received in revised form 25 December 2013 the treatment processes of POME. The new methods which not required extension of existing plants or
Accepted 27 December 2013
building very expensive bioreactors are still searching. In recent years increasing attention has been
Available online 7 January 2014
directed to the possibility of improvement of waste water treatment by static magnetic eld. The aim
of our study was to determine the impact of constant magnetic eld as well as the integration of this
Keywords:
technique with the famous technique used for wastewater treatment which is adsorption by activated
Palm oil mill efuent (POME)
Biological treatment
carbon as a novel method for POME treatment. This new method has been found to be a useful method
Magnetic eld for removing colour, TSS and COD from biologically treated POME.
Activated carbon adsorption 2014 Published by Elsevier B.V.
Colour
TSS and COD

1. Introduction of water soluble components of palm fruits as well as suspended

Palm oil, the most important commodity, and its industry are a
signicant contributor to the Malaysian economy with over 4.9
million hectares of planted area with a production of 17 million
tones of palm oil. Malaysia is the largest exporter of palm oil and
exported to more than 100 countries with export earnings of RM
62 billion [1]. Extraction of palm oil involves a number of processes
that require large quantities of water. It usually requires an esti-
mated 1.5 m3 of water to process a ton of fresh fruit bunch, and
half of this amount becomes palm oil mill wastewater (POMW)
[2]. Due to the high production rates, a large quantity of polluted
wastewater, (POMW) is generated. Palm oil mill efuent consists
Corresponding author. Tel.: +852 2358 8412; fax: +852 2358 0054.
E-mail address: kemckayg@ust.hk (G. McKay).
materials like oil residues, short palm ber, cell walls, organelles,
a variety of lipids and carbohydrates ranging from cellulose to
simple sugars, Phenol and phenolic compounds, a range of nitrog-
enous compounds from proteins to amino acids, free organic acids
and assembly of minor organic and mineral constituents. Nutri-
ents contain in POME according to are nitrogen, phosphorus,
potassium, magnesium and calcium [3]. If the efuent is dis-
charged untreated, it can cause signicant environmental impact
due to its high biochemical oxygen demand (BOD), chemical oxy-
gen demand (COD), oil and grease, and total solids. Therefore, a
cost-effective treatment of POME to an acceptable level for dis-
charge continues to be a big challenge to the industry. In the last
decade, several treatment methods have been studied for POME
treatment such as: anaerobic digestion [46], Aerobic oxidation
based on an activated sludge process [7], aerobic and anaerobic
digestions [810], ultraltration Membrane separation [11],

1385-8947/$ - see front matter 2014 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.cej.2013.12.084
32 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142
up-ow anaerobic sludge xed lm (UASFF) reactor [12], chemical
coagulation and occulation [13,14], Solvent extraction [15], Elec-
trocoagulation [16], Electrootation [17], Adsorption [18], and
Hydrolysis [19].
The current treatment system, which is based mainly on biolog-
ical treatments of anaerobic and aerobic systems, is quite inefcient
and this unfortunately leads to the environmental pollution issues
[19].
Liquid-phase adsorption processes have been proven to be
highly efcient for removal of colours, COD, suspended solids,
and organic and inorganic pollutants from industrial processes.
Activated carbon is the most effective and widely used adsorbent
for wastewater treatment [18].
More frequently the technological systems are introduced with
physical factors. For instance, positive results can be obtained
when treating wastewater with a periodical eld of external oscil-
lations, e.g. an acoustic, temperature eld with dened parameters,
as well as ultrasounds or UV radiation [20].
One of the most important physical factors is the magnetic
eld. Since several decades, researchers have found that magne-
tism is a unique property that independently helps in water puri-
cation by inuencing the physical and chemical properties of
contaminants in water [21]. For a long time now, in numerous re-
search centers investigations have been made in order to discover
the mechanism of changes occurring in solutions under an impact
of this physical factor. However, the optimal conditions for mag-
netic activation of liquids are sought, and attempts made to deter-
mine the favourable technological effects of such treatment.
Among different physical and chemical methods of water and
wastewater treatments; magnetic methods attract a special atten-
tion due to their ecological purity, safety, simplicity and less oper-
ating costs. Until now, there has been no unequivocal explanation
about the modications mechanisms in the magnetically-treated
wastewater.
Magnetic eld-exposed methods have gradually drawn atten-
tion to improving the adsorption and separation. Some research-
ers described the impacts of magnetic exposure on nonmagnetic
colloidal particles in aqueous solutions and the comparison of
physiochemical properties before and after magnetic exposure
[22]. Magnetic exposure on the water changed water properties
and the interface between water and solid surface by magnetic-
eld-induced adsorption and desorption [23]. There are only few
studies that use magnetic eld for wastewater treatment pro-
cesses, and in most of them, magnetic eld is used only for sepa-
ration of solids or attached microorganisms from efuent.
However, there is an important observation here, which is the in-
creased biological activity with the magnetic eld application
[24]. Yulan et al. [25], found that using magnetic eld enhanced
the biological treatment of wastewater. ebkowska et al. [26], de-
duced that the static magnetic eld had a positive effect on form-
aldehyde biodegradation in wastewater by activated sludge. Duan
et al. [27], demonstrated that the adsorption ability, including
adsorption amount and adsorption rate of Pb(II) using modied
chitosan could be enhanced with a suitable magnetic eld. How-
ever, until recently, there is some lack of knowledge about mag-
netic effects on adsorption and the mechanism of magnetic
exposure on adsorption characteristics. Till now the effect of mag-
netic eld exposure and the enhancement of magnetic eld to
adsorption process for the treatment of palm oil mill efuent have
not been investigated.
Static magnetization is convenient, simple, of little cost, and may
be an alternative by itself or to improve the adsorption. This paper
aims to provide basic experimental ndings of magnetic and mag-
netic assisted adsorption and to guide the application of the mag-
netic chemistry on adsorption process and palm oil mill efuent
treatment.
2. Experimental
2.1. Materials
Biologically treated POME samples were collected from a palm
oil mill in DengkilMalaysia. Sample was stored in a cold room at
4 C prior to use. Biologically treated POME was analysed for col-
our, total suspended solids (TSS), chemical oxygen demand (COD)
and pH, the results are shown in Table 1. The table also lists the
POME standard discharge limit of Environmental Quality Act
(EQA) 1974, Department of Environment (DOE), Malaysia [28]. It
can be observed from Table 1 that the biologically treated POME
exceeded the standard discharge limit. Commercial activated car-
bon with a mesh size of 30 was supplied by GlobeChem (Malaysia).
Distilled water was used for any dilution.
2.2. Methods
In this study, a separate and combined process concept of acti-
vated carbon adsorption, and magnetic eld were applied for the
treatment of biologically treated POME. It was proposed that the
substantial removal of colour, TSS, and COD from wastewater by
adsorption to activated carbon enhanced by magnetic eld would
signicantly facilitate the POME treatment process.
According to the studies of Oshitani et al. [29] and Zhang et al.
[30], solutions can be magnetized within a strong eld such as the
magnetic apparatus we used generated. The magnetic eld of the
apparatus was adjustable and permanent, and the magnetic ux
density was high, up to 0.5 T.
Optimum conditions were examined for each process sepa-
rately. Then these processes were carried out consecutively. At
the last stage a combination of the two processes was examined
simultaneously.
2.2.1. Adsorption experiments
To select the optimal adsorption condition without magnetic
eld, we varied the adsorbent (commercial activated carbon) dos-
age from 5 g/100 ml to 25 g/100 ml, and the range of contact time
from 0.5 to 6 h. A batch adsorption studies were conducted by add-
ing different amounts (5, 10, 15, 20 and 25 g) of activated carbon,
into a 250 ml asks each containing 100 ml of biologically treated
POME. The conical asks were then covered with glass stoppers
and placed on a shaker at shaking speed of (150 rpm) and at con-
stant temperature of (25 C) for a certain period of (30, 60, 120
180, 240, 300 and 360 min). The samples were then withdrawn
at appropriate time intervals using glass pipette, the sample then
ltered and the ltrate was used to determine the residual concen-
trations of colour, TSS and COD.
The amounts of colour, TSS and COD adsorbed at time t, qt (mg/g)
and at equilibrium, qe (mg/g) were calculated using Eqs. (1) and (2):
C o  C t V
qt 1
m
C o  C e V
qt 2
m
Table 1
Properties of biologically treated POME and the regulatory discharge limits.
Property Values Standard discharge limits [28] Units
pH 8.4 59
Colour 9900 PtCo/l
TSS 1800 400 mg/l
COD 4700 mg/l
BOD5 1350 100 mg/l
 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142 33

performed by placing the samples between magnets for 15 and

180 min at 25 C. The intensity of the magnetic eld is 200 mT.
Each experiment was conducted in triplicate. The average values
were reported. The experimental diagram is depicted in Fig. 1.

2.3. Adsorption isotherm models

To investigate the magnetic eld enhanced adsorption mecha-

nism, commercial activated carbon was used as adsorbent with
200 mT magnetic eld in biologically treated POME with different
initial concentrations of colour, TSS and COD. The acquired data
from adsorption isotherm experiments were analysed using the
Langmuir equation [31] (Eq. (4)) and the Freundlich equation
[32] (Eq. (5)) utilizing correlation method.
Q 0 bC e
qe 4
1 bC e
Fig. 1. Graphical representation of adsorption with magnetic eld experimental
apparatus. qe K F C 1=n
e 5
where Q0 is the maximum amount of sorbate per unit weight of cell
The percentage of removal (%R) of each parameter and the to form a complete monolayer on the surface bound at high Ce (mg/g),
amount that adsorbed by the adsorbents were calculated by the and b is a constant representing the afnity of the binding sites. Q0
following equations: stands for a practical limiting adsorption capacity when the surface
is fully covered with sorbate molecules and assists in the compari-
C o  C t
%R  100 3 son of adsorption performance, particularly in cases where the
Co
sorbents do not reach their full saturation. Values of Q0 (mg/g), b
where Co, Ct and Ce (mg/L) are the liquid-phase concentrations at (L/mg), and KF, and 1/n were calculated from the linear plot of
initial, time t and equilibrium, respectively. V (L) is the volume of Ce/qe vs. Ce, the intercept of linear regression, and the plot of log
the solution and M (g) the mass of activated carbon adsorbent used. qe vs. log Ce, respectively.
Each experiment was conducted in triplicate and the average values
were reported. 2.4. Adsorption kinetic models

2.2.2. Magnetic eld experiments
The effective of magnetic eld on POME treatment as colour,
TSS and COD removal was investigated at different magnetic eld
intensity ranged from 5 mT (weak magnetic eld) to 500 mT
(strong magnetic eld), and different periods of exposure time
from (15 to 180 min).
A separate set of experiments have been done using magnetic
eld exposure followed by adsorption at the optimum conditions
stemmed from the above experiments. Combined adsorption
enhanced by magnetic eld experiments were performed in well-
tight polyethylene 50 ml bottles at 25 C. Samples of activated
carbon, 20 g/100 ml dry weight, were suspended in the biologically
treated POME. The magnetic treatment of the solution was
The study of adsorption dynamics with magnetic treatment de-
scribes the solute uptake rate and evidently this rate controls the
residence time of adsorbate uptake at the solidsolution interface.
The kinetics of colour, TSS and COD adsorption on the activated
carbons were analysed using pseudo rst-order [33], pseudo sec-
ond-order [34], intraparticle diffusion [35,36] and Elovich [37,38]
kinetic models, Table 2.
2.5. Error analysis
In the isotherm and kinetic studies, the optimization procedure
requires an error function to be dened in order to be able to eval-
uate the t of the model to the experimental data. In this study,

Table 2
List of Kinetic models used.

Model name Model equation Parameters

Pseudo rst order qe = the amount of solute adsorbed (mg/g) at equilibrium
qt = the amount solute adsorbed at time t (mg/g)
Lnqe  qt Lnqe  K 1 t 6 k1 = the rate constant of the adsorption process (min1)

Pseudo second order K2 = the rate constant of pseudo second-order adsorption (g mg1 min1)
 
t 1 1
t 7
qt K 2 q2e qe

Intraparticle diffusion Kp = Intraparticle diffusion rate constant (mg g1 min1/2)

qt K p t1=2 8

Elovich a and b are model constants (mg g1)

qt abLnt 9
34 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142

linear coefcients of determination and a nonlinear Chi-square

test, as described in the literature [39], were used.
Coefcient of determination, which represents the percentage
of variability in the dependent variable (the variance about the
mean) is employed to analyse the tting degree of isotherm and ki-
netic models with the experimental data. Its value may vary from 0
to 1. The nonlinear chi-square test is a statistical tool necessary for
the best t of an adsorption system, obtained by judging the sum
squares differences between the experimental and the calculated
data, with each squared difference is divided by its corresponding
value (calculated from the models). The equivalent mathematical
statement is:

X
N
qe;exp  qe:;calc 2
v2 10
i1
qe;calc

If data from the model are similar to the experimental data, v2

will be a small number; if they are different, v2 will be a large
number. Therefore, it is necessary to also analyse the data set using
the Chi-square test to conrm the best-t isotherm or kinetic for
the sorption system.

2.6. Analytical procedure

Colour, TSS and COD detection were carried out with standard
methods. HACH Spectrophotometer DR2800 was used according
to the procedure 8025 PlatinumCobalt standard method. Method
No. 8006 was used to determine COD concentration of the sample
carried in COD vials (HR 201500 mg/L) by APHA potassium
dichromate method using HACH spectrophotometer DR2800 and
DRB 200 reactor. TSS was determined in conformity with the stan-
dard method No. 8000 using HACH spectrophotometer DR2800.
The magnetic eld intensity was measured by a magnetic eld
meter (microteslometer) (CLASS TOUCHSTONE-10). The eld
homogeneity was measured in different horizontal sections in
the zone of the exposed reactor. In accordance with the readings
the experimental set-up provides a homogeneous eld in 25 ml
of the reactor volume placed between the poles. The homogeneous
eld of the reactor volume has a maximum deviation from the
average value of 10.

3. Results and discussion

3.1. Adsorption only

To select the optimal adsorption condition without magnetic

eld, we varied the dosage of activated carbon from 5 g/100 ml
to 25 g/100 ml. It was found that as the dosage of adsorbent was
increased, the percentage of colour, TSS and COD removal also in-
creased, as shown in Fig. 2.
It could be noticed from the gure that the best results were ob-
tained on 20 g of adsorbent for colour, TSS and COD. The removal
efciencies, at equilibrium, increased from 28.35%, 29.02% and
65.9% to 68.05%, 93.71% and 100% by increasing the dosage from
5 to 20 g/100 ml for colour, TSS and COD respectively. This can
be attributed to increased adsorbent surface area and availability
of more adsorption sites with more functional groups resulting
from the increase adsorbent dosage. These ndings are agreed with
Igew et al. [40], who investigated the use of boiler y ash for the
reduction of biochemical oxygen demand (BOD), (TSS) and colour
from (POME). However, the amount adsorbed per unit mass of
the adsorbent decreased considerably (Fig. 3). The decrease in unit
adsorption with increasing dose of adsorbent is basically due to
adsorption sites remaining unsaturated during the adsorption
[41]. Suspended and dissolved particles in water inuence colour.
The dark brown colour of palm oil mill efuent consisted of many
Fig. 2. Effect of contact time on percentage removal of (a) colour, (b) TSS and (c)
COD for different amount of adsorbent dosage for adsorption process only.
organic compounds such as anthrocyanin and carotene pigment
that was extracted from fresh fruit bunches in the sterilization pro-
cess. Moreover, it included polyphenol compounds, tannin, polyal-
cohol and melanoidin [42]. From the previous facts, it is obvious
that colour removal is strongly dependent on the removal of total
suspended solids and other soluble organic compounds.
The inuence of contact time on percentage removal of studied
parameters is also shown in Fig. 2. By increasing contact time, the
residual adsorbate concentrations have a longer residence time for
adsorption on the activated carbon surface area. Initially there is
strong adsorption and then reaches to equilibrium after around
 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142 35

Fig. 3. Effect of adsorbent dosage on the quantity adsorbed of colour, TSS and COD
on activated carbon.

300 min. At equilibrium, the surface of the activated carbon was

covered with adsorbate molecules; therefore a longer mixing time
does not increase the percentage removal from POME.

3.2. Magnetic eld

The present study attempts to determine the impact of the

magnetic treatment on biologically treated POME. The effective-
ness of the technological systems consisting of different-strength
magnetic elds generated by a lab-scale device of static magnets
was applied. The parameters whose concentration clearly varied
were colour, TSS and COD. These parameters values were system-
atically decreasing in the examined POME, along with the time of
the experiment duration (Fig. 4).
It is thought that modications to the properties of solutions
exposed to stagnant magnetic eld resulted from changes in the
molecular structure of liquids, polarization and arrangement of
particles, and nally from changes of the electric potential
[4345]. Most of the technological effects of magnetic water can
be attributed to a decrease in surface tension of the water and
decreased wetability of the solid phase due to a larger contact
angle of the solid/liquid phase boundary. The practical result of
these phenomena is accelerated occulation and improved settling
of suspended solids [46].
The study found that magnetic treatment reduced colour, TSS
and COD effectively, a maximum degradation of 16.13% of colour
when magnetic intensity was 200 mT; for TSS, a maximum degra-
dation of 34.34% was obtained, while 44.29% COD removal were
achieved for the same magnetic eld intensity.
The reason for the reduction may have been degradation at the
Fig. 4. Effect of different magnetic eld intensity and contact time on the
contribution of atmospheric oxygen. A conrmed effect of water
percentage removal of (a) colour, (b) TSS and (c) COD.
and wastewater magnetic preparation is the modication of the
contained gases concentration. Magnetized solutions are charac-
teristic among others of the diminished surface tension and in con- effectively reduced the concentration of organic matter contained
tact with the atmosphere adsorb the paramagnetic particles of in the analysed liquids. The process of water molecule disintegra-
oxygen; eventually their concentration in water solutions tion with the formation of free radicals takes place when sufcient
increases. High concentrations of the molecular oxygen in the ana- energy has been provided [43].
lysed wastewater may have accelerated the processes of organic The precise mechanism for COD removal by magnetization was
matter degradation, especially since the compounds resistant to still obscures [48]. Based on theories of energy changes in mass
degradation were absent in that case [32,33]. reaction as well as the kinetics of magnetic eld [4952], the
Another phenomenon which occur under the impact of mag- magnetizing mechanism for COD removal may be interpreted as:
netic eld is the intensication of free radicals formation. For these The organic molecules in wastewater would absorb the energy
reasons, this physical factor is thought to be the element responsi- when the wastewater exposed to magnetic eld. Some energy
ble for generating hydroxyl radicals OH [47]. High reactivity and enhanced molecules were then induced to an excited state, which
high oxidation potential of those chemical compounds may have was unstable relative to the ground state; this increased the rate of
36 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142

chemical reactions for the degradation of organic substances in the

magnetizing process [53]. Reference data would suggest that mag-
netic eld supports reduction of the surface tension and thus en-
ables introduction of numerous oxygen particles to the
wastewater mass. This phenomenon should inuence positively
the biodegradation process and limit the concentration of organic
substances in the wastewater and the COD value in the efuent
[54].
It is also found that the adsorbed layer is thickened by the mag-
netic exposure [29]. The efcient coagulation induced by the mag-
netic eld may also have positively inuenced the bonding and
removal of sorbates, also the suspended particles carry a surface
charge, and this charge is affected by the imposed magnetic elds.
It has been proven that the physical factor modies the electro-
kinetic potential [45] and inuences the coagulation process [55].
One may conclude that the coagulation process in solutions can
be initiated by magnetic waves having the effect on a liquid with-
out the application of any supporting chemical agents [20]. It has
been also evidenced that it is possible to initiate the coagulation
process in water solutions without chemical substance application,
but only with the use of magnetic eld forces. Studies of the mag-
netic treatment inuence on the physico-chemical properties of
municipal sewage have revealed that the settlement time of sew
age prepared with magnetic eld decreased considerably in com-
parison to the settlement time of non-prepared sewage. Addition-
ally, a tendency was detected to coagulate ne particles of sludge
in the magnetically prepared sewage, which eventually accelerates
sedimentation and increases dewatering susceptibility [54].
These results suggest that magnetic effects play an important
role in the conformational change of the water molecules around
an ion or on a solid surface.

3.3. Magnetic eld followed by adsorption

After the pretreatment of wastewater by magnetization, the re-

moval of colour, TSS and COD in subsequent adsorption process
was performed and the results were shown in Fig. 5. Results de-
duced that the primary exposure to magnetic eld highly affect
the adsorption process through the high rates of percentage re-
moval of sorbates.
It is clear that the percentage removals of all sorbates are higher
than that obtained from adsorption only experiments; moreover
equilibrium state had been reached faster. This consolidates that
the main role of magnetization was to improve the physical and
chemical characteristics of the POME so as to enhance the capaci-
ties of subsequent adsorption process and the adsorption behav-
iour of the activated carbon. Oshitani et al. [29] demonstrated
that the magnetic effect remains for at least 3 days but disappears
completely at 6 days. It is quite mysterious that the magnetic ef-
fects are memorized in the samples for such a long period after
the magnetic exposure, but the same kind of memory effect is
Fig. 5. Effect of magnetic eld followed by adsorption on the percentage removal of
found in all other researches experiments although the duration
(a) colour, (b) TSS and (c) COD for different intervals of time and different magnetic
time is different [56,57]. So it is hypothesized that the magnetic eld intensity.
exposure forms a quasi-stable structure of water molecules, and
the effect remains until the structure is destroyed by external dis-
turbances [58]. molecules; because of some components in the activated carbon
were magnetic sensitive, which would enhance the adsorption un-
3.4. Combined magnetic eld and adsorption der magnetic eld exposure.
After the treatment of biologically treated POME by combined
Under magnetic eld exposure, the properties of adsorbate and magnetization and adsorption process the results were shown in
adsorbent would change, e.g. magnetized water [29], and the sur- Fig. 6. This Figure presents the effects of magnetic eld intensity
face morphology of the adsorbents may become less homogeneous and contact time on colour, TSS and COD removal efciency.
under magnetic exposure [59] which would increase the surface Fig. 6 shows that the percentage removal was rst increased by
area of activated carbon particles to enhance the adsorption of sor- increasing the magnetic eld strength and reached a maximum at
bates. On the other hand, the exposure to the magnetic eld could 200 mT then decreased with the further increases. At higher mag-
inuence more the activated carbon particles than the sorbate netic eld strength more free radicals are formed and these free
 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142
radicals may combine with each other forming hydrogen peroxide
which could consider less reactive compared to the free radicals
and hence the suitable magnetic effect on degradation could not
be achieved [20]. In general the application of such combination
of magnetic eld and adsorption may greatly affect the content
of organic compounds in POME, and resulted in increasing the
capacity of adsorbent.
Fig. 7 represents a condensed comparison between the different
types of treatment processes. Positive integration of adsorption
and constant magnetic eld are conrmed by the results of the
treatment of biologically treated POME. Adsorption process
Fig. 6. Effect of magnetic eld intensity combined with adsorption on percentage
removal of (a) colour, (b) TSS and (c) COD on activated carbon for different contact
time.
37
improved by constant magnetic eld resulted in limitation of the
amount of used adsorbent at the same effectiveness of pollutants
removal from POME. The process was fast and the impact of con-
stant magnetic eld was shown after shorter time of exposure to
POME. The experiment revealed that there is a possibility of appli-
cation of lower doses of adsorbent at the same effectiveness of
POME treatment when constant magnetic eld was introduced.
Fig. 7a showed the effect of magnetization followed by adsorp-
tion on removal of colour gradually approached to its maximum
(69.78%) and the maximum was obtained at 4 h, whereas the un-
magnetized wastewater obtained its maximum at 6 h. However,
Fig. 7. Comparison of efciency for different treatment processes as percentage of
removal of (a) colour, (b) TSS and (c) COD for different contact time.
38 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142

by applying magnetic eld simultaneously with adsorption the col-

our removal efciency reaches its maximum (79.303%) after 3 h
only. Fig. 7b shows that, a better TSS removal was obtained during
adsorption with magnetic eld compared with adsorption without
magnetic eld. At magnetic eld strength of 200 mT and 120 min
contact time, the TSS removal is as high as 98.45% for the combined
process, but only 61.33% for adsorption without magnetic eld and
87.66% for magnetic eld followed by adsorption process. As it is
depicted in Fig. 7c, during adsorption combined with magnetic
elds at eld strength of 200 mT and 60 min contact time, the
COD removal efciency is as high as 98.99%, but only 67.87% for
adsorption process without magnetic eld, and 89.45% for mag-
netic eld followed by adsorption. This result indicated that the
magnetization process accelerated the removal of colour, TSS and
COD in adsorption process. At the same contact time, the pretreat-
ment of biologically treated POME by magnetization would en-
hance the capacity of adsorbent for removal of colour, TSS and
COD. This emphasizes that with the exerting of magnetic eld,
the adsorption capacity was improved. Therefore, applying magne-
tization technology is an important factor for further application of
magnetic eld assisted adsorption on POME treatment.
Based on the mentioned above, it could be concluded that the
use of magnetization in POME treatment would be benecial to
the removal of the colour, TSS and COD substances as well as the
cut of the costs in engineering applications.

3.5. Adsorption isotherms

Adsorption isotherms were employed to illustrate how the

adsorbate molecules distribute between the liquid phase and the
solid phase and are important for the design of the adsorption sys-
tem. In this work, the adsorption equilibrium data were modeled
to the Freundlich isotherm and Langmuir isotherm.
The linear models of Langmuir and Freundlich isotherms for the
data obtained from colour, TSS and COD adsorption on activated
carbon for adsorption process only and for magnetic eld enhanced
adsorption are shown in Fig. 8ac. Table 3 indicates the constants
of the aforementioned models for adsorption process without and
with magnetic eld respectively.
The plots, the R2 and Chi-squres values show that the Langmuir
model gave a very good t to the sorption process without mag-
netic eld for colour, TSS and COD. The values of the Langmuir con-
stants are shown in Table 3. The fact that the Langmuir isotherm
ts the experimental data well may be due to homogeneous distri-
bution of active sites on the activated carbon surface; since the
Langmuir equation assumes that the adsorbent surface is energet-
ically homogeneous [31]. A good t of this equation reects mono-
layer adsorption. The value of b (L/mg) parameter of the Langmuir
model is the constant representing the afnity of sorbate to sor-
bent. Higher b values mean more afnity of sorbate to sorbent
and so the higher the adsorption rate [20].
From Table 3 according to R2 and Chi-square values, it could be Fig. 8. Comparison between Langmuir and Freundlich model and experimental
seen that the Freundlich equation gave a very good t to the results for (a) colour, (b) TSS and (c) COD.
adsorption process combined with magnetic eld. With R2 value
of 0.9986 for TSS reduction, which is the highest, and Chi-square and steepness of the isotherm [61]. Thus, the higher the KF value,
value of 0.051557 which is the lowest, it means that the Freundlich the greater the adsorption intensity. Hence the higher value of KF
isotherm ts the adsorption of TSS more, followed by COD and for TSS adsorption followed by COD and then colour. Igew et al.
then colour. KF the characteristic coefcient of adsorbateadsor- [40], found that Freundlich isotherm gave a better t followed by
bent pair, a measure of the adsorption capacity of the adsorbent, Langmuir for the adsorption of BOD, TSS and colour from POME
given by the inuence of the different energies associated with on boiler y ash.
the heat of adsorption, n is an exponent. The constant (n) repre- The Freundlich isotherm does not exhibit a maximum number
sents a measure for surface sites energetic non-uniformity and of adsorption sites. It ts well data without physical meaning be-
the parameter (1/n) quanties the intensity of adsorption, in some cause Eq. (5) teaches that the adsorbed amount grows without
studies being called the intensity parameter [60]. The Freundlich restriction as the bulk concentration C increases. However, despite
exponents (1/n) are all less than one showing that signicant this formal drawback, this power-law relationship allows the
adsorption takes place. Also, KF and (1/n) determines the curvature surface heterogeneities to be taken into account, in away more
 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142 39

Table 3
Constants for Langmuir and Freundlich isotherm for adsorption of colour, TSS and COD on activated carbon without and with magnetic eld.

Langmuir model Freundlich model

2 2
Q0 (mg/g) b (L/mg) R v KF (mg/g)(L/mg)1/n 1/n R2 v2
Without magnetic eld
Colour 58.824 207.9  106 0.9938 0.091861 0.1869 0.5939 0.9811 0.426981
TSS 34.247 2.333  103 0.9913 0.217377 0.4219 0.5942 0.982 1.068192
COD 63.694 285.2  106 0.993 0.050708 0.0654 0.7652 0.9869 1.134951
With magnetic eld
Colour 87.719 156.5  106 0.9874 0.14199 0.1558 0.6643 0.9953 0.109748
TSS 42.735 2.573  103 0.9689 1.511188 0.9817 0.5001 0.9986 0.051557
COD 76.923 427.3  106 0.9209 2.419764 0.3099 0.6135 0.9982 0.235606

general than the Langmuir isotherm. Thus, the equation applies
very well to solids with heterogeneous surface properties and gen-
erally for heterogeneous solid surfaces [27].
Magnetic eld may affect activated carbon by enhancing the
high-adsorption of sorbent capacity for reactivity towards a wide
range of organic pollutants. This reactivity arises from the com-
plexity of its chemical surface groups compared to those of other
surfaces.
That difference in the adsorption caused by the use of magnetic
elds can likely be explained by the improvement in the orienta-
tion of the molecules of the adsorbate towards the activated car-
bon pores, facilitating the adsorptive process, and resulting in a
gain in the adsorption time [62].
3.6. Adsorption kinetics
In order to describe the adsorption kinetics for colour, TSS and
COD on activated carbon, pseudo rst-order, pseudo second-order,
intraparticle diffusion and Elovich model were applied to the
experimental data. The results of kinetic parameters are shown
in Table 4 for adsorption only process and for combined magnetic
eld and adsorption process. The conformity between experimen-
tal data and the model predicted values was expressed by the cor-
relation coefcients R2 (R2 values close or equal to 1) and nonlinear
Chi-square test. A relatively high R2 and low Chi-square values
indicate that the model successfully describe the adsorption kinet-
ics. The R2 value of pseudo second-order is higher compared to R2
values of other kinetic models tested. Moreover, the pseudo second
order model exhibited very low v2 values compared to other
kinetic models. Therefore, drawing conclusion from the non-linear
Chi-square analysis, the pseudo second order model was best t-
ting the kinetics.
The values for the equilibrium adsorption capacity as predicted
by the pseudo-second-order model coincided well with the exper-
imental uptake values (Fig. 9). These ndings revealed that the
pseudo second-order kinetic model provided a good correlation
for the adsorption of colour, TSS and COD onto activated carbon
compared to other kinetic model used. This suggests that the rate
controlling step of adsorption was largely attributable to chemical
sorption. The applicability of the pseudo-second order model
means the rat of adsorption was subject to a second order rate
law, with respect to the availability of adsorption sites on the
surface of adsorbent rather than adsorbate concentration in bulk
solution [63]. The pseudo-second-order rate constant, K2, for COD
was higher than for TSS and colour, demonstrating that the
adsorption rate of COD was higher than that of TSS and colour.
Compared to same process without magnetic eld, the adsorption
rates with the enhancement of magnetic eld were fast. Hence, a
practical advantage of using magnetic eld enhance adsorption
would be in its ability to remove more colour, TSS and COD from
biologically treated POME in a much shorter adsorption time.
Although the Elovich equation does not provide any mechanis-
tic evidence, it has proved suitable for highly heterogeneous sys-
tems [64] of which the adsorption of colour, TSS and COD onto
activated carbon is undoubtedly such a case.
Though the pseudo rst order model and the pseudo second
order model are widely applied to study kinetic adsorption it is
known that they are not suitable to explain the diffusion
mechanism occurring in the adsorption process, which is generally
the rate determining step [63]. Thus the intraparticle diffusion

Table 4
Parameters of the kinetic models for the adsorption of colour, TSS and COD on activated carbon without and with magnetic eld.

Adsorption without magnetic eld Adsorption with magnetic eld

Colour TSS COD Colour TSS COD
Pseudo rst order model
K1 8.09  103 6  103 1.62  103 8.4  103 7.4  103 8.7  103
R2 0.9893 0.9931 0.9684 0.8819 0.8989 0.7751
v2 0.4856 0.140671 2.370373 12.71623 0.028598 0.027146
Pseudo second order model
K2 1.918  104 6.944  104 4.713  104 3.016  104 3.19  102 3.203  102
R2 0.993 0.9847 0.9701 0.9716 1 1
v2 0.1765 0.028463 1.072847 0.839952 0.003224 0.001593
Intraparticle diffusion model
Kp 2.1022 0.4901 1.7207 3.2466 0.1336 0.1747
R2 0.9546 0.9719 0.8387 0.9112 0.8605 0.7879
v2 1.9326 0.266308 5.495229 2.220499 0.024304 0.02207
Elovich model
a 27.128 6.6302 16.368 24.765 6.2663 19.977
b 10.747 2.5673 7. 602 12.814 0.5436 0.7256
R2 0.994 0.9968 0.9407 0.9615 0.95 0.9061
v2 0.1978 0.054931 1.919106 1.011935 0.009204 0.009702
40 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142
Fig. 9. Comparison of different kinetic models with experimental data for the
adsorption of (a) colour, (b) TSS, and (c) COD on activated carbon combined with
magnetic eld.
model was introduced to give the explicit information about the
diffusion mechanism. According to this model, the plot of uptake,
qt, versus the square root of time, t1/2, should be linear if the
intraparticle diffusion is involved in the adsorption, and if these
lines pass through the origin, then intraparticle diffusion is the rate
controlling step, otherwise this indicates that two or more steps
occurred in the adsorption process [65]. The plots (shown in
Fig. 10) presented multilinearity, indicating that three steps took
place. As can be seen in Fig. 10, the rst sharper step was not
observed and completed before 15 min, which may be considered
Fig. 10. Intra-particle diffusion plots for the removal (a) colour, (b) TSS and (c) COD
onto activated carbon.
as the external surface adsorption. The second step described the
gradual adsorption from 10 to 65 min, where intraparticle diffu-
sion was rate-controlling. The third step was attributed to the nal
equilibrium stage, in which intraparticle diffusion started to slow
down due to the decrease of solute concentration in solution. The
R2 values of the intraparticle diffusion model were lower than that
of the pseudo-second-order kinetic model, but this model indi-
cated that the adsorption of colour, TSS and COD onto activated
carbon may be followed by an intraparticle diffusion model up
to 65 min. This implied that although intraparticle diffusion
was involved in the adsorption process, it was not the only
rate-controlling step [66].
 R.R. Mohammed et al. / Chemical Engineering Journal 243 (2014) 3142
It was previously reported [27] that magnetic treatment could
reduce the viscosity and surface tension of solutions, an effect
possibly concerned with resonance. When the magnetic eld and
the oscillation frequency of the molecules were in tune, resonance
could occur. This resonance would then impart energy to the sys-
tem for activation, changing the structure and nature of the mate-
rial in the magnetic eld. Magnetic treatment could thus promote
the adsorption of metal ions. However, the mechanism of magnetic
treatment remains to be claried in an in-depth study.
4. Conclusion
Based on the results presented above, the following conclusions
can be drawn for the combined magnetic eld and adsorption pro-
cess for treatment of biologically treated POME:
 From the adsorption only experiments it was found that the
removal efciencies increased from 28.35%, 29.02% and 65.9%
to 68.05%, 93.71% and 100% by increasing the dosage from 5
to 20 g/100 ml for colour, TSS and COD respectively. The best
results were obtained on 20 g of adsorbent and equilibrium
was reached at 5 h.
 The results of this study concluded that, the combined magnetic
eld and adsorption process has a vital role in treating biologi-
cally treated POME; the magnetic ux density increases the
removal efciency of colour, TSS and COD. The percentage of
colour removal was 79.303 compared to 57.111 without mag-
netic effect, so as TSS was 98.455 compared to 61.11, and COD
was 98.99 compared to 67.87, without magnetic eld at the
same contact time. This is one of the interesting ndings in this
eld of research. This encourages more research in this eld.
 The adsorption ability, including adsorption amount and
adsorption rate, could be enhanced with a suitable magnetic
eld. For example, upon treatment with eld strength of
200 mT, the adsorption equilibrium period for colour, TSS and
COD on activated carbon shortened from 300 min to 120 min.
In the future, the mechanism of magnetic treatment on ad-
sorption will have to be studied deeply.
Acknowledgements
This work has been carried out during sabbatical leave granted
to the author (Rae R. Mohammed) from Mosul Technical Institute,
so the author thanks Ministry of Higher Education/Iraq and Foun-
dation of Technical Education/Iraq, for their great support. We
would like to express the deepest appreciation to Mr. Shridharan
Parthasarathy for his great support throughout this work. This re-
search has been supported by the University of Nottingham/
Malaysia Campus and Hong Kong University of Science & Technol-
ogy as a research scholar fellowship.
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