Ijciet 06 09_002

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International Journal of Civil Engineering and Technology (IJCIET)
Volume 6, Issue 9, Sep 2015, pp. 08-19, Article ID: IJCIET_06_09_002
Available online at
http://www.iaeme.com/IJCIET/issues.asp?JTypeIJCIET&VType=6&IType=9
ISSN Print: 0976-6308 and ISSN Online: 0976-6316
© IAEME Publication
___________________________________________________________________________
COLUMN STUDY OF THE ADSORPTION OF
PHOSPHATE BY USING DRINKING WATER
TREATMENT SLUDGE AND RED MUD
Prof. Dr. Alaa Hussein Al-Fatlawi
College of Engineering / Babylon University/Iraq
Mena Muwafaq Neamah
College of Engineering / Babylon University/Iraq
ABSTRACT
The present study investigates the efficiency of phosphate removal from
wastewater by the Drinking Water Treatment Sludge (DWTS), and Red Mud
(RM) sorbent. Wastewater was taken from the effluent channel of Almuamirah
wastewater treatment plantin at Al-Hilla city/Iraq. Drinking Water Treatment
Sludge (DWTS), was taken from the sedimentation tanks of Al-Tayara drinking
water treatment plant, in the same city.
Column experiment was carried out to study the adsorption isotherm of
phosphorus at 25±1⁰C and solution of different pH and adsorbent dosages.
The effects of (DWTS) dose, bed height (H), contact time (T), agitation speed
(S), hydrogen ion concentration (pH), (DWTS –RM) ratio, were studied.
All continuous experiments were conducted at constant conditions, bed
depths 25 cm, initial phosphate concentration 4 mg/L, flow rate 5 mL/min,
particle size (1mm) for (DWTS), and (0.425mm) for (RM) and solution pH of
4.
The results show that the use of (RM) reduces the operating time by about
21% compared to the use of (DWTS).Increasing (RM) ratio increasing the
removal efficiency and decreasing the equilibrium time in about 57% and 38%
for 50% and 33% (RM) ratio respectively.
At the highest phosphate concentration of 4 mg/l, the (DWTS) bed was
exhausted in the shortest time of less than 9 hours leading to the earliest
breakthrough. Percent of phosphate removal decreased with the increase in
initial concentration. Both the breakthrough and exhaustion time increased
with increasing the bed height.
The results show that a significant increase in the operating time is
achieved by adding different ratios of (RM) to (DWTS). Adding 33%, and 50
% (RM) weight ratios to the (DWTS) bed decreases the operating time by
about 18%, and 30% respectively.

Column Study of The Adsorption of Phosphate by Using Drinking Water Treatment Sludge
and Red Mud
Key words: Column Study, Adsorption, Drinking Water Treatment Sludge
(DWTS), and Red Mud (RM), phosphate.
Cite this Article: Prof. Dr. Alaa Hussein Al-Fatlawi and Mena Muwafaq
Neamah. Investigating Column Study of The Adsorption of Phosphate by
Using Drinking Water Treatment Sludge and Red Mud. International Journal
of Civil Engineering and Technology, 6(9), 2015, pp. 08-19.
http://www.iaeme.com/IJCIET/issues.asp?JTypeIJCIET&VType=6&IType=9
1. INTRODUCTION
Phosphorus (P) is an essential nutrient for the growth of organisms in most
ecosystems, but superfluous phosphorus can also cause eutrophication and hence
deteriorate water quality. Phosphorus is released into aquatic environments in many
ways, of which the most significant are human industrial, agricultural, and mining
activities. Although phosphorus removal is required before discharging wastewater
into bodies of water, phosphorus pollution is nevertheless increasing. Therefore, there
is currently an urgent demand for improved phosphorus removal methods which can
be applied before wastewater discharge. In wastewater treatment, enhanced biological
phosphorus removal (EBPR) is becoming an increasingly popular alternative to
chemical precipitation (CP) because of its lower costs and reduced sludge production.
Much water treatment sludge is produced in the production of service water and
drinking water. It is impossible to prevent the production of water treatment sludge.
The water treatment sludge is liquid and solid and is regarded as a waste.
Consequently, the water treatment sludge must be handled in accordance with
regulations in forces. The quantity of the water treatment sludge is rather high. The
water treatment sludge is placed mostly in landfills. In some countries, for instance in
the Netherlands, about 25 per cent of the produced water treatment sludge is re-used,
(Miroslav, 2008).
It is still an issue to choose a disposal or liquidation method for the water
treatment sludge that would be reasonable in terms of technology and economy.
According to environment protection regulations it is required to minimise the
quantity of wastes produced. If possible, the wastes should be re-used or processed as
secondary raw materials as much as possible. If this is not possible, the solid wastes
should be put back in the environment where the space occupied should be as little as
possible and minimum costs should be incurred, (Moldan et al., 1990).
Phosphorus removal from wastewater has been widely investigated and several
techniques have been developed including adsorption methods, physical processes
(settling, filtration), chemical precipitation (with aluminum, iron and calcium salts),
and biological processes that rely on biomass growth (bacteria, algae, plants) or
intracellular bacterial polyphosphates accumulation (de-Bashan et al., 2004).
Recently, the removal of phosphate from aqueous solutions via adsorption has
attracted much attention. The key problem for many phosphorus adsorption methods,
however, is finding an efficient adsorbent. Several low-cost or easily available clays,
waste materials and by-products.

Prof. Dr. Alaa Hussein Al-Fatlawi and Mena Muwafaq Neamah
2. MATERIAL AND METHODS
2.1 Adsorbate
Phosphate was selected as a representative of a contaminant because the it is the main
nutrient for the growth of aquatic microorganisms like algae but the excess content of
phosphorus in receiving waters leads to extensive algae growth (eutrophication).
The samples was collected from the effluent channel of Almuamirah wastewater
treatment plant in Al-Hilla city, Iraq. These samples were immediately transported to
the laboratory for processing. The total amount of plant nutrients and other pollutants
present in a sewage plant effluent is subjected to seasonal, daily, and hourly variation.
Table 1 summarizes the composition and variability of the effluent under study. The
wastewater sample was used as stock solution to provide the specific value of
phosphate concentration. Where necessary, pH adjustment was made on each sample
by addition of 0.1 M HNO3 and NaOH solutions using a HACH-pH meter.
Table 1 Physico-chemical analysis of secondary wastewater effluent sample, (Almuamirah
wastewater treatment plant, 2014)
parameters Quantitative composition
E.C, µs/cm 3.5
T.D.S, mg/L 1288
Salinity, mg/L 2.18
Total hardness, as CaCo3, mg/L 1200
pH 7.9
Mg, mg/L 232.8
Ca, mg/L 160.3
So4, mg/L 769.4
Cl, mg/L 289.9
Po4, mg/L 2.7
No3, mg/L 0.46
T.S.S, mg/L 40
BOD5, mg/L 32
COD, mg/L 54
DO, mg/L 2.3
Fecal coliform, mpn/100 ml 120000
Total coliform, mpn/100 ml 128000
2.2 Adsorbent
Two types of adsorbent were used in the present study for adsorption of phosphate
from secondary effluents of wastewater treatment plant they are:
1. Drinking Water Treatment Sludge (DWTS),
2. Red Mud (RM).
2.2.1. Drinking Water Treatment Sludge (DWTS)
The composition and properties of the water treatment sludge depends typically on the
quality of treated water as well as on types and doses of chemicals used during the

and Red Mud
water treatment. Depending on the quality of the treated water, the water treatment
sludge contains suspensions of inorganic and organic substances.
The (DWTS) used in this study was taken from the sedimentation tanks of Al-
Tayara drinking water treatment plant, in Al-Hilla city, Iraq. This sludge was dried at
atmospheric temperature for 5 days, and then sieved on 2 mm mesh to achieve
satisfactory uniformity. The sludge had a particle size distribution ranged from 150
μm to 10 mm (Fig. 1) with an effective grain size, d10, of 250 μm, a median grain size,
d50, of 460 μm and a uniformity coefficient, Cu= d60/d10, of 2.24.
Figure 1 Gradation curve for (DWTS) used in the present study.
The geometric mean diameter (1.19) is given by where d1 is the
diameter of lower sieve on which the particles are retained and d2 is the diameter of
the upper sieve through which the particles pass (Alexander and Zayas, 1989). Table
2 presents the physical and chemical characteristics of this (DWTS).
Table 2 Physical and chemical characteristics of DWTS
Element Quantitative composition
T.O.C, mg/L 4.29
E.C, µs/cm 620
T.D.S, mg/L 312
Salinity, mg/L 0.2
pH 8.1
L.O.I, mg/L 15.76
Fe2O3, mg/L 3.6
CaO, mg/L 15.32
SO3, mg/L 0.63
MgO, mg/L 3.66
Al2O3, mg/L 11.56
R2O3, mg/L 15.16
SiO2, mg/L 45
2.2.2. Red Mud (RM)
The Red Mud (RM) used in this study was supplied by the Iraqi commercial markets.
It is a solid waste produced in the process of alumina production from bauxite
following the Bayer process. Red mud, as the name suggests, is brick—red in colour
and slimy, having an average particle size of <10μm. A few particles greater than
0
20
40
60
80
100
120
0.1 1 10
%ofcumulativepassing
Partical size (diameter , mm)

20μm are also available [Liu et al., 2011].The mesh size of red mud used in the study
was of 1mm. This size was obtained by sieving analysis using the American Sieve
Standards in the building of Materials Engineering laboratory at the University of
Babylon. Its composition, property and phase vary with the type of the bauxite and the
alumina production process, and also change over time. The chemical composition of
the red mud is given in Table 3.
As a pre-treatment, (RM) was crushed and sieved to get granular (RM)with
particle size of 0.425 mm to be used in present experiments as shown in Fig. 2.The
granular (RM) was firstly washed with distilled water and then dried in an electric
oven at 120⁰C, overnight. This time was usually enough to remove any undesired
moisture within the particles. It was then placed in desiccators for cooling.
Figure 2 Gradation curve for (RM) used in the present study.
Table 3 The main chemical constituents of (RM), (Ping and Dong, 2012)
Chemical constituent Quantitative composition, %
Fe2O3 26.41
Al2O3 18.94
SiO2 8.52
CaO 21.84
Na2O 4.75
TiO2 7.40
K2O 0.068
Sc2O3 0.76
V2O5 0.34
Nb2O5 0.008
TREO 0.012
Loss 9.71
0
20
40
60
80
100
120
0.1 1 10
%ofcumulativepassing
Partical size (diameter , mm)

and Red Mud
3. PREPARATION OF SAMPLES WITH DIFFERENT (DWTS)
AND (RM) RATIOS
Two different (DWTS) and (RM) weight and ratios of (DWTS) to (RM) were used
starting with 0%, 33% and then 50%. The added (DWTS) was with a size of 1mm
while the size of (RM) was of 0.425mm. Each sample was mixed by shaking using a
shaker for 1 hour. The 0% ratio was first prepared and used in the experiments. When
an increase in the operating time was achieved, the addition ratio was raised to 50%.
4. EXPERIMENTAL PROCEDURES
The reactor setup (Fig. 3) used in the present study is constructed of pyrex glass tube
of (100 cm) height, and (7.5 cm) internal diameter. The column was made in a
methacrylate cylinder, thus allowing for visual examination of the progress of the
wetting front and detection of preferential flow channels along the column walls. The
column dimensions were defined to minimize the occurrence of channeling by
making the column diameter at least 30 times the maximum particle size found in the
material used. The column dimensions also met the minimum length-to-diameter
requirement (Relyea, 1982). This means the column length (100 cm) must be four
times greater than its diameter (7.5 cm). Attached to the lower part of the column was
a plastic funnel, inside which a perforated fiberglass plate was installed to support the
column’s methacrylate structure. The plate was covered by a mesh to act as a filter
and to retain the porous medium. The entire device was mounted on top of a metal
structure that allowed its height above the surface and the verticality of the column to
be regulated (Fig. 3). The column was packed with (DWTS) and (RM) in different
ratios as filter. Fluid entered the column, previously saturated with the wastewater.
Contaminant up gradient wastewater (Table 1) was used to flow through the layer of
packed materials. A constant-head reservoir of 50 liter volume polyethylene container
was used to deliver influent wastewater at a flow rate of 5 mL/min. The sample was
collected as a function of time at the bottom of the column through a 30 liter
polyethylene container to collect the effluent solution. Two valves were used to
control the desired flow rate through the adsorption column. The first sample,
corresponding to time 0, was taken when water started to flow from the lower part of
the column. Samples were filtered through 0.45µm cellulose acetate filters.
Figure 3 Experimental set-up of column test used in the present study.
Monitoring of phosphate concentrations in the effluent was conducted for a period
of 120 hr. Samples were taken regularly (after different periods) from the effluent.
The water samples were immediately introduced in glass vials and then analyzed by
AAS.

The filling material in the column was assumed to be homogeneous and
incompressible, and constant over time for water-filled porosity. The volumetric water
discharge through the column cross section was constant over time and set as the
experimental values. The pollutant inlet concentration was set constant. All tubing
and fitting for the influent and effluent lines should be composed of an inert material.
Information from the column study can be used along with the site characterization
and modeling to help in designs the field-scale (DWTS).
5. RESULTS AND DISCUSSIONS
The adsorption experiments were carried out in columns that were equipped with a
stopper for controlling the column flow rate. This experiment is useful in
understanding and predicting the behavior of the process. The sample solution was
passed through the adsorption column with a known amount of (DWTS) at a flow rate
of 5mL/min by gravity. The flow rate was kept constant by controlling the stopper
valve. The concentration of phosphate residual in the sorption medium was
determined using fully automated PC-controlled true double-beam AAS with fast
sequential operation (Varian AA50 FS, Australia) for fast multielement flame AA
determinations with features 4 lamp positions and automatic lamp selection.
The results of phosphate adsorption onto different adsorption fixed beds using a
continuous system were presented in the form of breakthrough curves which showed
the loading behaviors of phosphate to be adsorbed from the solution expressed in
terms of relative concentration defined as the ratio of the outlet phosphate
concentration to the inlet phosphate concentration as a function of time (Ce/C₀ vs.
time).
5.2. Breakthrough Curves of the Different Adsorbents
Two continuous flow adsorption experiments were conducted to study the adsorption
behavior of fixed beds of (DWTS), and (RM). All the experiments were conducted at
constant conditions, bed depths 25 cm, initial phosphate concentration 4 mg/L, flow
rate 5 mL/min, particle size (1mm) for (DWTS), and (0.425mm) for (RM) and
solution pH of 4. The breakthrough curves of the experiments are presented in Fig. 4
in terms of Ce/C₀ versus time in minutes.
Figure 4 Experimental breakthrough curves for adsorption of phosphate onto DWTS and RM
at C₀=4 mg/L, pH=4, Temp. = 25 ⁰C, H= 25 cm.
0
0.2
0.4
0.6
0.8
1
1.2
0 1000 2000 3000 4000
Ce/C₀
Time, min.
DWTS
RM

and Red Mud
Fig. 4 shows that the two adsorbents used in present study are efficient in the
removal of phosphate. The use of (RM) reduces the operating time by about 21%
compared to the use of (DWTS). It is obvious from this figure that the breakthrough
curves for the two adsorbents used are of S shape.
5.2. Effect of Initial phosphate Concentration
The effect of changing of phosphate concentration from 2.7 mg/l to 4 mg/l with
constant bed height of (DWTS) of 25 cm, flow rate of 5 mL/min, and solution pH of 4
is shown by the breakthrough curves presented in Fig. 5. At the highest phosphate
concentration of 4 mg/l, the (DWTS) bed was exhausted in the shortest time of less
than 9 hours while its 50 hours for (RM).Leading to the earliest breakthrough. The
breakpoint time decreased with increasing the initial concentration as the binding sites
became more quickly saturated in the column. This indicated that an increase in the
concentration could modify the adsorption rate through the bed. A decrease in the
phosphate concentration gave an extended breakthrough curve indicating that a higher
volume of the solution could be treated. This was due to the fact that a lower
concentration gradient caused a slower transport due to a decrease in the diffusion
coefficient or mass transfer coefficient.
The effect of initial phosphate concentration onto (DWTS) and (RM) are shown
here (Fig. 5 and 6). It could be seen that the percent of phosphate removal decreased
with the increase in initial concentration. This means that the amount of these
phosphate sorbed per unit mass of sorbent increased with the increase in initial
concentration. This plateau represents saturation of the active sites available on the
(DWTS) samples for interaction with contaminants, indicating that less favorable sites
became involved in the process with increasing concentration.
Figure 5 Experimental breakthrough curves for adsorption of phosphorus onto DWTS at
different initial concentrations, pH=4, H=25 cm, Temp.=25 ⁰C.
0
0.2
0.4
0.6
0.8
1
0 1000 2000 3000 4000
Cₑ/C₀
Time, min.
C=2.7 mg/L
C=4 mg/L

Figure 6 Experimental breakthrough curves for adsorption of phosphorus onto RM at
different initial concentrations, pH=4, H=25 cm, Temp.=25 ⁰C.
5.3. Effect of Adsorbent Bed Height
The eﬀect of bed height was investigated for phosphorus adsorption onto (DWTS);
the experimental breakthrough curves are presented in Fig. 7. This Fig. shows the
breakthrough curves obtained for phosphate adsorption on the (DWTS) for five
different bed heights of (5, 10, 15, 20, and 25 cm), at a constant flow rate of 5
mL/min, phosphate initial concentration of 4 mg/L, and solution pH of 4.It is clear
that the increase in bed depth increases the breakthrough time and the residence time
of the solute in the column.
Both the breakthrough and exhaustion time increased with increasing the bed
height. A higher phosphate uptake was also expected at a higher bed height due to the
increase in the specific surface of the (DWTS) which provides more fixation binding
sites for the phosphate to adsorb. The increase in the adsorbent mass in a higher bed
provided a greater service area which would lead to an increase in the volume of the
solution treated. (Gupta et al., 2001) reported in their works that when the bed height
is reduced, axial dispersion phenomena predominates in the mass transfer and reduces
the diffusion of the solute, and therefore, the solute has not enough time to diffuse
into the whole of the adsorbent mass.
The effect of bed depth on the adsorption capacity of (DWTS) was shown in
Fig.8, by plotting the capacity versus different bed depth. This Fig. shows that
increasing bed depth would increase the capacity because additional spaces will be
available for the wastewater molecules to be adsorbed on these unoccupied areas.
Furthermore, increasing bed depth will give a sufficient contact time for these
molecules to be adsorbed on the (DWTS) surface.
0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
Cₑ/C₀
Time, min.
C=2.7 mg/L
C=4 mg/L

and Red Mud
Figure 7 Experimental breakthrough curves for adsorption of phosphorus onto DWTS at
different bed thickness C₀=4 mg/L, pH=4, Temp.=25 ⁰C.
Figure 8 Effect of different bed depth on the adsorption capacity of DWTS (Q=5 mL/min,
C₀=4 mg/L, pH=4, Temp=25 ⁰C).
5.4. Effect of Different (DWTS) – (RM) Ratios
The effect of different (DWTS) – (RM) weight ratios were investigated for phosphate
adsorption onto (DWTS) by adding different weight ratios of (0.425mm particle size)
(RM) to the (DWTS) bed which was of (1 mm particle size). Three experiments were
conducted using different weight ratios of (DWTS) – (RM) (0%, 33%, and 50%). All
experiments were carried out at constant conditions, flow rate of 5 mL/min, initial
phosphate concentration of 4 mg/L, (DWTS) bed height of 25 cm, and solution pH of
4. The experimental breakthrough curves are presented in Fig. 9.
This Fig. shows that a significant decrease in the operating time is achieved by
adding different ratios of (RM) to (DWTS). Adding 33%, and 50 % (RM) weight
ratios to the (DWTS) bed decreases the operating time by about 18%, and 30%
respectively. In the packed bed of the (DWTS) column, the contact points between the
0
0.2
0.4
0.6
0.8
1
1.2
0 1000 2000 3000 4000
Cₑ/C₀
Time, min.
H=25 cm
H=20 cm
H=15 cm
H=10 cm
H=5 cm
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0 5 10 15 20 25 30
Adorptioncapacity,mg/g.
Bed depth, cm.

(DWTS) particles represent dead zones because they don’t contribute in the
adsorption process. So, adding a specific ratio of (RM) to the bed with a smaller
particle size fills the dead zones between the particles and increases the total specific
surface area of the bed leading an increase in the adsorption capacity and the
operating time.
Increasing the (RM) ratio to 50% caused the operating time to decrease as
compared to 33% ratio, but the bed was still achieving slightly higher operating time
and removal efficiency than the pure (0% ratio) (DWTS) bed. In fact, the (RM) has
higher adsorption capacity and higher porosity than (DWTS). Therefore; increasing
the (RM) ratio to 50% causes an increase in the available adsorption sites and the total
adsorption capacity of the bed, and this leads to a decrease in the operating time.
Figure.9 Experimental breakthrough curves for adsorption of phosphate onto different (RM)
ratios, (C₀ =4 mg/L, pH=4, H=25 cm, Temp=25 ⁰C).
6. CONCLUSIONS
The following Conclusions were obtain from this study:-
 (DWTS) seems suitable for use as filler for remediation of wastewater
contaminated by phosphate. The laboratory column experiment show the
possibility decrease of contaminants in treated wastewater.
 The use of (DWTS) as a reactive medium for the treatment of wastewater ensures
that significant rates of reduction of phosphate are achieved, particularly in cases
in which there is initially a high concentration.
 Results from the column study showed that higher initial concentration resulted
in shorter column saturation.
 (DWTS) is environment friendly, cost- effective, and locally available adsorbent
for the adsorption of phosphate ions from secondary wastewater effluents.
 The effect of different (DWTS) – (RM) weight ratios shows that a significant
decrease in the operating time is achieved by adding different ratios of (RM) to
(DWTS). Adding 33 %, and 50 % (RM) weight ratios to the (DWTS) bed
decreases the operating time by about 18%, and 30% respectively. Increasing the
(RM) ratio to 50% caused the operating time to decrease as compared to 33%
ratio.
 Increasing (RM) ratio increasing the removal efficiency and decreasing the
equilibrium time in about 57% and 38% for 50% and 33% (RM) ratio
respectively.
0
0.2
0.4
0.6
0.8
1
1.2
0 1000 2000 3000 4000
Cₑ/C₀
Time, min.
DWTS
33% RM
50% RM

and Red Mud
 One of the important aspects of the present study is represented by considering
the (DWTS) as reactive medium, i.e. not inert. The utilization of these conditions
is logic because the (DWTS) and (RM) may be worked together under the same
field conditions of the continuous flow.
REFERENCES
[1] Almuamirah wastewater treatment plant, 2014.
[2] Alexander, P.M., Zayas, I. Particle size and shape Effects on adsorption rate
parameters. Environ, Eng., 115(1), 1989, pp.41–55.
[3] De-Bashan, L.E., Bashan, Y., 2004, Recent advances in removing phosphorus
from wastewater and its future use as fertilizer (1997-2003). Water Research 38,
4222-4246.
[4] Gupta, V.K., Gupta, M., Sharma, S., 2001. Process development for the removal
of lead and chromium from aqueous solutions using red mud-an aluminum
industry waste, Water Res. 35(5), 1125–1134.
[5] Liu, W., Zhang, X., Jiang, W., 2011, Study on particle- size separation
pretreatment of Bayer red mud, Chin. J. Environ. Eng, 5, pp.921–924.
[6] Miroslav KYNCL, 2008, Opportunities For Water Treatment Sludge Re-Use.
Volume LIV, No.1, GeoScience Engineering, ISSN 1802-5420, pp. 11-22.
[7] Moldan, B., 1990, Životníprostředí Českérepubliky. 1.vydání. Praha: Academia,
228 s. ISBN 80-200-0229-8 (Environment of the Czech Republic).
[8] Relyea, J.F., 1982, Theoretical and experimental considerations for the use of the
column method for determining retardation factors, Radioactive Waste
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[9] Rodhan Abdullah Salih. Evaluation of the Drinking Water Quality and the
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[10] Kadhim Naief Kadhim Al-Taee, Thair Jabbar Mizhir Al-Fatlawi and Zainab
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