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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

Sorption of Iron from Phosphoric Acid Solution Using Polyacrylamide


Grafted Activated Carbon

A.A.El-Zahhar, S.E.A. Sharaf El-Deen, R.R.Sheha


Nuclear Chemistry Department, Hot Labs. Center, Atomic Energy Authority, Cairo, Egypt.

Received: 1/1/2013 Accepted: 12/3/2013

ABSTRACT
Polyacrylamide grafted activated carbon (PAAm-Ac) was prepared from
chemically activated carbon of rice husk and rice straw onto polyacrylamide. The
prepared composite adsorbent was used for removal of iron from wet-phosphoric
acid solution through batch- and column experiments. Different parameters
affecting the adsorption process such as pH, contact time, metal ion concentration,
adsorbent dose and anion concentration were investigated. The adsorption
isotherms were studied to evaluate the maximum sorption capacity of adsorbent.
The results showed that the adsorption is highly pH-dependent and reach 95% at
initial concentration of 50mg/l at pH 4.8. The equilibrium adsorption follows
Langmuir isotherm well with maximum Fe(III) uptake capacity of 6.15mg/g.

Key words: Iron/ Wet phosphoric acid/ Sorption/ Polyacrylamide activated


Carbon composite

INTRODUCTION
Phosphoric acid was produced by two processes. The thermal process produces pure acid with
huge energy consumption, while the wet-process involves chemical reaction of phosphate rock with
mineral acid. The wet-process is economically applied for production of phosphoric acid in many
countries(1-3). The mineral acid used in phosphate rock dissolution also dissolves different impurities.
Consequently the wet-process phosphoric acid (WPA) must be purified before use in several industries
such as (food additives, fertilizers and detergents)(4). Different techniques were studied for purification
of WPA as; precipitation, adsorption, ion exchange and solvent extraction(5, 6). Solvent extraction is the
widely used procedure for WPA purification either through separation of phosphate or separation of
impurities. Column techniques were also studied for selective extraction of WPA(7). Purification of
WPA from heavy metals was studied through precipitation as sulfides(8). Also other cationic impurities
were removed from WPA by precipitation, as; Fe, Al, Mg, and Ca. Precipitation of metal cations in
phosphoric acid were induced by increasing the pH. One of the most important impurities is iron. The
content of iron as (Fe2O3) in fertilizer grade phosphoric acid (50% P2O5) must be not more than 1.5%
Fe2O3(9). While higher iron content negatively affects the solubility of fertilizer P2O5 in water(10). The
Egyptian phosphate ores when leached with H2SO4 or recycled H3PO4, the produced phosphoric acid
(50% P2O5) contains 4% or 2.7% Fe2O3, respectively. Decreasing the iron content in wet phosphoric
acid was studied using different precipitating reagents as sodium silicate, silicon dioxide, potassium
sulfate, calcium sulfate and potassium amyl xanthate(10) and also using different chelating compounds
as amino tri-mthylene phosphonic acid(11). Another study, Soliman et al. (2009) proved the removal of
iron from crude phosphoric acid using organosilicon compound(12). The purification of wet process
phosphoric acid by decreasing iron and uranium was studied using white silica sand(13).

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

In the present work PAAm-Ac -composite adsorbent material was prepared by supporting
activated carbon of rice husk and rice straw onto polyacrylamide polymer. The prepared adsorbent
was characterized and used for iron adsorption from phosphoric acid solutions of different
concentrations. The parameters affecting the sorption process were studied and optimized.

EXPERIMENTAL
Materials:
All chemicals used in this study were of analytical grade and were used without further
purification. Polyacrylamide (PAAm) with average molecular weight over 5000000, ferric nitrate and
N,N'-Methylenebis-acrylamide (NMBA) were purchased from Merck, Hydrochloric acid and sodium
hydroxide solutions were used to adjust the pH of the aqueous solutions.

Sorbent preparation:
The starting material, chemically activated carbon (CAC) was firstly prepared following the
method: 20 gm sample of rice straw and rice husk (1:1) was soaked in 70% H3PO4 and heated on a hot
plate at 80oC with stirring, then left in the furnace at 80oC till complete dryness. After drying, the
sample was left in the tube furnace at 500oC for two hours. The sample was washed with bidistilled
water till being neutral, and then dried at 110oC for 24 h.

Polymeric composite sorbent containing chemically activated carbon was prepared according to
the following procedure: 1g NMBA and 3g PAAm (in 50.0ml distilled water) were introduced into a
250ml flask, equipped with stirrer, thermometer and nitrogen gas aeration. The mixture was
vigorously stirred till complete dissolution of NMBA, and then appropriate amount of CAC was
dispersed in the mixture. After being purged with nitrogen gas for 30min. (for removal of dissolved
oxygen), the mixture was stirred for 2 hours. This solution was stirred vigorously till obtaining
complete homogeneity. Finally, the mixture was irradiated at ambient temperature in gamma radiation
cell (MC-20 Russian) with dose of 30kGy at fixed dose rate of 3.5 kGy h -1. After irradiation, the
composites were washed in acetone for removal of unreacted monomers, cut into small pieces, dried,
ground and stored for further use. The content ratio of CAC in prepared composite was 50% of total
weight.
Material Characterization:

Polyacrylamide grafted activated carbon (PAAm-Ac) was characterized by scanning electron


microscopy (Jeol Analytical SEM) (JSM-6510 LA, Japan), fourier transform infrared (FTIR) spectra
were recorded with (Nicolet spectrometer from Meslo, USA).The specific surface area was determined
from the standard N2 adsorption isotherms at 77K using an automatic adsorption instrument (Nova
3200 series, USA). Fe(III) concentrations were measured using Solaar-II MS atomic absorption
spectrometer (AAS) from (Thermo Fisher Scientific Inc. Cambridge, UK).
Sorption experiments
The removal of iron from phosphoric acid solution was studied using PAAm-Ac with respect to
time, sorbent concentration, iron concentration and acid concentration. Where a constant volume of
the acid solution was mixed with the appropriate amount of solid composite adsorbent and left with
shaking to appropriate time. After shaking the acid solution was separated from the solid adsorbent
and the concentration of iron was measured using atomic absorption spectroscopy (AAS). The
removal percentage was calculated as:

(1)

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

The distribution coefficient Kd was calculated using the equation:

(2)

Where, Co and Ce are the initial and equilibrium iron concentration in acid solution (mg/l),
respectively, V is the volume of the solution (ml) and m is the weight of adsorbent (g). The V/m ratio
is kept constant at 100 for all the experimental work.

Batch sorption experiment:


The prepared composite adsorbent was applied for removal of iron from crude wet process
phosphoric acid through batch experiment. In this experiment an appropriate weight of adsorbent was
mixed with appropriate volume of phosphoric acid solution containing 50mg/l Fe(III) for 24 hour at
room temperature. The concentration of iron was measured before and after experiment using atomic
absorption spectrometry.

Column experiment:
The fixed bed column experiment was performed using a glass column of 1 cm diameter and
25cm in length. 2g of (PAAm-Ac) was wet backed into the column with the aid of distilled water and
adjusted at pH 7. Iron containing acid solution was passed through the column with different flow rate.
The effluent acid solution was collected in fractions (2ml) for measuring iron concentration using
AAS. The break through percentage was calculated as:

(3)

Where, Co and C are the iron concentration in the influent and effluent acid solution (mg/l),
respectively. The break through capacity was studied as a function of flow rate, iron concentration in
influent solution, bed volume and acid concentration.

RESULTS AND DISCUSSION


Characterization of the prepared composite adsorbent
Fourier Transform Infrared (FTIR):
The FTIR spectrum of activated carbon and polymeric composite are shown in Figure 1. The
spectrum of Ac contains peaks at 3448, 2369, 1567, 1186, 1038 and 498 cm-1 (Figure 1a). The broad
band centered at 3448cm-1 can be assigned to O-H stretching of carboxylic acid functional group and
the band at 2369cm-1 is assigned to carbon-oxygen bonds, perhaps due to ketone(14). The band at about
1567cm-1 is ascribed to highly conjugated C=O stretching of the carboxylic group. The sharp beak at
1186 cm-1 corresponds to C-O stretching and O-H bending of phenol, alcohol and carboxylic groups.
Also, the beak for Si-O-Si bond at 1038-1100cm-1 is appeared(15, 16) and the band at 498 cm-1 is an
indication of the presence of free SiO2. The IR spectrum of PAm-Ac composite (Figure 1b) was
changed drastically compared to the characteristic bands of Ac, disappeared and new bands due to the
polymerization of activated carbon using the acrylamide and the adsorbed acrylamide is appeared. In
the spectrum of Pam-Ac, more bands were observed in the NH- stretching region of the Pam-Ac
composite, evidently due to the presence of the amide groups in the composite. Hence the absorption
bands observed in the region 3189-3500 cm-1 are assigned to N-H symmetric and asymmetric
stretching modes in the NH2 group(17,18). The bands around 3600 and 2950 cm-1 corresponds to O-H
stretching of hydroxyl group(18) and C-H stretching band of the acrylamide methyl group(17),
respectively. The band occurring at 1737 cm-1 is expected to be the C=O stretching vibration of the

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

acrylamide and the bands observed at 1617cm-1 and 1592cm-1 are assigned to C=C stretching band and
NH2 deformation modes, respectively. The C-N stretching band was observed at 1277 cm-1. The bands
observed at 648 and 759 cm-1 are also doubly assigned to NH2 wagging and CH3 wagging,
respectively(19).

Morphological characterization:
Morphological characterization studies were performed done with SEM, which indicate the
morphology of the composite. Scanning electron micrographs of AC and PAAm-Ac composite are
shown in Figure 2. The image in figure (2a) of AC illustrate that the particles are more agglomerated
and there are a lot of pores between the particles. But in figure (2b), the image clarify that the
composite have homogeneous rods and this may be due to the polymerization process on activated
carbon surface.
(a) AC (a) AC

(b) PAm-AC (b) PAm-AC

Fig. (1): FTIR spectra of (a) AC and Fig. (2): SEM image of (a) AC and
(b) PAm- AC. (b) PAm- AC.

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

ADSORPTION STUDIES

(1) Effect of pH :
The speciation of iron in aqueous solutions depends greatly on the pH, which consequently
affect the adsorption reaction. With respect to Fe(III), it goes precipitated at pH greater than 4.5 (20, 21).
The removal of Fe(III) from phosphoric acid solution (1 molar) of varied pH using polyacrylamide-
chemically activated carbon composite adsorbent (PAAm-Ac) was studied, and the obtained results
are given in Fig. 3. It was found that the removal of Fe(III) ion from wet process phosphoric acid
solutions increased with pH. The results in the figure show that with respect to pH, firstly the
adsorption increased with pH (1-4), followed by nearly steady uptake to pH 10. At low pH the protons
competes with Fe(III) which results in lower uptake of iron ions, and the active sites go de-protonated
with increasing pH, consequently the removal increased with pH. Therefore, at these pH values, the
adsorption and precipitation are the effective mechanisms to remove the Fe(III) ions in aqueous
solution. The iron cations in aqueous solution convert to different hydrolysis products (20).

(2) Effect of contact time:


The required contact time for sorption to be completed is important to give insight about the
kinetics of the sorption process. Also it gives information on the minimum time required for
considerable adsorption to occur, and also the possible diffusion control mechanism between metal
ions (adsorbate). The required time for equilibrium could give information about the movement of
Fe(III) ions from the bulk solution towards the adsorbent surface. The adsorption of Fe(III) ions from
wet process phosphoric onto PAAm-Ac was studied at different time periods, with keeping other
parameters constant (ion concentration, adsorbent concentration and pH). The effect of contact time on
sorption of Fe(III) ions onto PAAm-Ac is shown in Fig. 4. Initially, a rapid raise of removal was
obtained, which could be due to the availability of adsorbent active groups. Generally the adsorption
kinetics depends on: (i) the adsorbent surface area, (ii) the nature and concentration of the surface
active groups present on the adsorbent, which could react with Fe(III) ions. The removal of Fe(III)
reached its maximum value after 120min. Science, after that time, there is no significant increase in
removal of Fe(III) from wet phosphoric acid. This is due to the decreased or lesser number of active
sites.
6
200 150
100
140
5
130
kd 80
U% 120
4
Qe(mg/g)

110
60
U%

100
kd(ml/g)

100
U%

3
90 40
80

70 20 2
Qe(mg/g)
60 U%

50 0 1
0 20 40 60 80 100 120 1000 1500 2000 2500 3000
0 40
0 2 4 6 8 10 Time (min)
pH

Fig. (3): Effect of pH on the sorption of Fig. (4): Effect of contact time on the
Fe(III) ions from wet-process sorption of Fe(III) ions from
phosphoric acid solution (1M) wet-process phosphoric acid
using PAAm -Ac.; sorbent dose solution using PAAm-Ac.;
20g/l, time 24h, [Fe(III)] 50mg/l. [Fe(III)] 50mg/l, pH 4, dose 20g/l.

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

(3) Effect of adsorbent doses:


Different weights of the prepared composite adsorbent were used for iron removal at 25◦C
within dose range of 5 to 50g/L while the other parameters were kept constant. Wet process
phosphoric acid containing 50ppm Fe(III) was used to optimize the required amount of adsorbent
under prescribed conditions for maximum uptake. Fig. 5 shows that the adsorption of Fe(III) increases
by increasing adsorbent doses, this could be due to the higher dose of adsorbent in the solution, the
greater availability of exchangeable sites for the ions, i.e. more active sites are available for binding of
Fe(III) ions. A significant increase in iron removal was observed within the dose range from 5 to
20g/l. It is clear in the figure that the maximum removal for Fe(III) of 95% is observed with the
dosage of 20g/l. Further increase in adsorbent dose beyond this range did not produce significant
increase in iron adsorbed amount. A possible explanation is clusters formation by adsorbent particles
resulting in decreased surface area and surface active sites on the adsorbent(22, 23).

(4) Effect of initial metal ion concentration:


Batch experiments were conducted to study the effect of varying initial iron concentration on the
removal percentage and distribution coefficient of Fe(III) from wet phosphoric acid solution by
(PAAm-Ac) composite adsorbent with keeping other parameters constant. The experiments were done
using 20g/l adsorbent with different iron concentration within range 2 - 90mg/l. In figure 6, the
concentration of iron was represented against both the amount of
removal (qe) and the distribution coefficient. It could obviously deduced that at the same adsorbent
doses, there is an increase in qe and distribution coefficient with increasing initial Fe(III)
concentrations. This finding could be due to at lower initial metal concentrations, sufficient adsorption
sites were available for the sorption of metals ions. However, at higher concentrations the adsorption
sites available metal ions adsorption was relatively low when compared to available adsorption sites.
In other words, the distribution coefficient, Kd values increase with increasing the initial metal
concentration up to 50mg/l. At higher concentration, the Kd values highly decreased with
concentration. These results indicate that energetically less favorable sites became involved with
increasing metal ions concentration and attributable to competition which cause blocking to available
adsorption sites on adsorbent(24).
10 5000

100 4500

4000
8 Qt(mg/g)
kd(g/ml) 3500
90

3000
6
Qt(mg/g)
R% of Fe(III)

kd(g/ml)

80 2500

2000
4
70 1500

1000

60 2 500

0
10 20 30 40 50 60 70 80 90 100
50
0 10 20 30 40 50 [Fe] (mg/l)
Adsorbent dose g/L

Fig. (5): Effect of adsorbent dose on the Fig. (6): Effect of ion concentration on the
sorption of Fe(III) ions from wet- sorption of iron onto PAAm- Ac.;
process phosphoric acid solution pH 4, dose 20 g/l, time 24h
(1M) using PAAm-Ac.; pH 4,
time 24h, [Fe(III)] 50 mg/l.

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

(5) Effect of chloride, nitrate and sulphate concentration:


The adsorption of iron from wet-phosphoric acid solution onto PAAm-Ac was studied in
presence of different concentrations of chloride, nitrate and sulphate and the results are presented in
figure 7. The uptake percentage of iron(III) from wet-phosphoric acid solution onto PAAm-Ac
slightly decreases with increasing the concentrations of these anions. This observation could be due to
the formation of soluble anionic complexes at higher concentrations of chloride, nitrate and sulphate is
responsible for this inhibition effect(25). The observed decrease in the adsorption rate indicates that the
anion complexes have lower affinity than free metal ions towards PAAm-Ac. This observation could
also reflect the propensity of iron(III) to complex preferentially with anion rather than getting
adsorbed onto the composite PAAm-Ac surface(26).

(6) Effect of phosphate concentration:


The effect of phosphate on the adsorption of Fe(III) onto PAAm-Ac was studied from
phosphoric acid solution containing different phosphate concentrations. The results in figure 8 show
that the sorption of Fe(III) increased with increasing the phosphate concentration. This observation
could be explained on the bases of the effect of phosphate on iron speciation (27-29). Phosphate has
effect on the electron transfer between Fe(II)-Fe(III) which could enhance the
Sorption process(30). Also the phosphate concentration enhances the cation sorption (31-33).

70
100

90 60

80
50
70
U% of Fe
U% of Fe(III)

60 40

50
30
40 Chloride ion
Nitrate ion
Sulphate ion 20
30

20
10
0.0 0.5 1.0 1.5 2.0
10
0.0 0.1 0.2 0.3 0.4 0.5 [H3PO4], (mol/l)
Anion concentration mol/L

Fig. (7): Effect of anion concentration on Fig. (8): Effect of phosphate concentra-
the sorption of Fe(III) from wet- tion on the sorption of Fe(III)
phosphoric solutions using PAAm- onto acid PAAm- Ac.; dose 20 g/l,
Ac.; dose 20 g/l, pH 4, time 24h, time 24h, [Fe(III)] 50 mg/l.
[Fe(III)] 50 mg/l.

(7) Adsorption isotherm:


Adsorption isotherm was assayed by studying the adsorption of Fe(III) of wide concentration
range upon the polymeric composite adsorbent. The amount adsorbed of iron onto adsorbent (mg/g)
was represented against the equilibrium concentration of iron (Fig. 9).

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

Qe(mg/g)
4

0
0 5 10 15 20 25 30
Ce(mmol/L)

Fig. (9): Adsorption isotherm of iron onto PAAm-Ac, pH 4, dose 20g/l.

Langmuir isotherm model (34) is based on the assumption that maximum adsorption corresponds
to a saturated monolayer of adsorbate molecules on the adsorbent surface that the energy of adsorption
is constant and that there is no transmigration of adsorbate in the plane of the surface. Adsorption
isotherm was obtained by shaking the adsorbent of fixed doses and the adsorbate solution of varied
concentration for 24 h, in order to reach equilibrium.

The Langmuir isotherm represents the equilibrium distribution of metal ions between the solid
and liquid phases. The following equation can be used to describe adsorption isotherm according to
Langmuir:
) (4)

where, Ce is the equilibrium concentration (mg/l), Qe is the amount adsorbed at equilibrium time
(mg/g), Q◦ is the maximum metal ions uptake per unit mass of adsorbent (mg/g), which is related to
adsorption capacity and b is Langmuir constant (l/mol) which is exponentially proportional to the heat
of adsorption and related to the adsorption intensity. Thus, a plot of 1/Qe vs. 1/Ce should be linear if
Langmuir adsorption was applicable; consequently the Langmuir constants could be calculated. Fig. 9
shows the equilibrium adsorption isotherm of Fe(III) from wet phosphoric acid solution using PAAm-
Ac as an adsorbent. The isotherm rises sharply in the initial stages for low Ce and Qe values. This
indicates that there are plenty of radial accessible sites. Eventually a plateau is reached, indicating that
the adsorbent is saturated at this level. The decreases in the curvature of the isotherm are tending to a
monolayer adsorption. Considerably increasing the Ce values for a small increase in Qe, is possibly due
to less active sites being available at the end of the adsorption process and/or the difficulty of the edge
molecules in penetrating the adsorbent, Fe(III) ions partially covering the surface sites. In order to
optimize the design of a sorption system to remove Fe(III) from commercial wet process phosphoric
acid, it is important to establish the most appropriate correlation for the equilibrium curve. The linear
Langmuir plot according to Eq. (4) is shown in Fig. 10. The Langmuir parameters were calculated and
recorded in Table (1).

The favorable nature of adsorption can be expressed in terms of a dimensionless separation


factor (RL) of equilibrium parameter, which is defined as(35, 36):

(5)

Where, b is the Langmuir constant and Co is the initial concentration of the adsorbate in
solution(35). RL was less than one indicating favorable adsorption. The Langmuir constant values (Qo)
can be used to estimate the specific surface area, S, of sorbent (36) using the following equation

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

(6)

where S is the specific surface area, (m2/g) of adsorbent; Qo is monolayer sorption capacity, gram
metal per gram adsorbent; N is Avogadro number, 6.02×1023; A is the cross-sectional area of metal
ions, M is molecular weight of metal. The cross-sectional areas of Fe(III) has been determined to be
0.949Å2 . The maximum specific surface area of polymeric composite adsorbent towards Fe(III)
binding is 35.157m2/g. The increased adsorbent surface area tends to increase the adsorbent removal
efficiency (37). The results indicate that PAAm-Ac could be potentially adsorb Fe(III).

Table (1): Langmuir constants for adsorption of Fe(III) onto PAAm-Ac.


Langmuir model Freundlich model
Qo B R2 Kf N R
6.15 0.0383 0.992 0.285 1.01 0.984

The Freundlich model was chosen to estimate the adsorption intensity of the metal ions on the
sorbent surface. The Freundlich equation is presented as fellow(38):

(7)

Where Kf (mg/g) and n are Freundlich constants incorporating all factors affecting the
adsorption process such as, adsorption capacity and intensity of adsorption. These constants are
determined from the intercept and slope of linear plot of log Qe versus log Ce, respectively (Fig.11).
The constants are listed in Table 1. Although the correlation coefficients are greater than 95%, they do
not correlate the data as well the Langmuir isotherm, which has consistently higher correlation
coefficient.
1.0

2.5
0.8

2.0 0.6
log(Q mg/g)

0.4
1/Qe (g/mg)

1.5
e

0.2

1.0
0.0

0.5 B
-0.2 B
Linear Fit of Data1_B
Linear Fit of Data1_B

0.0 -0.4
0.0 0.1 0.2 0.3 0.4 0.5 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
1/Ce(L/mmole) log Ce mmol/L

Fig. (10): Langmuir plot for adsorption Fig. (11): Freundlish plot for adsorption
of Fe(III) onto PAAm-Ac. of Fe(III) onto PAAm-Ac.

(8) Sorption-desorption regeneration study:

The prepared PAAm-Ac was applied for removal of iron from crude wet process phosphoric
acid using batch experiment. In this concern, 1g of the composite adsorbent was mixed with 25ml crud
acid in which iron concentration is 50mg/l and left for 24 hour with continuous shacking at room
temperature. The iron concentration before and after experiment was measured using AAS, and the
removal percentage was calculated and recorded. The results indicate that the removal percentage
reaches to 95%. The loaded composite was regenerated using 0.5M HCl, where the adsorbent was
shacked with 20ml solution of 0.5M HCl. The regenerated adsorbent was used in repeated sorption
desorption regeneration cycles up to four cycles without sign-ificant decrease in sorption capacity and
the results are presented in Table (2).

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

Table (2): The removal percentage and sorption capacity of Fe(III) onto PAAm-Ac in repeated
sorption desorption regeneration cycles.
Cycle no. Removal % Sorption capacity (mg/g)
1 75 1.60
2 70 1.43
3 64 1.31
4 60 1.30

The treated wet phosphoric acid (containing about 25-30 ppm) was oriented towards another sorption
cycle, which could produce phosphoric without iron.

Column experiment:
In a column operation, the crude wet process phosphoric acid was percolated through a column
packed with PAAm-Ac held in a vertical position. The column of 1cm internal diameter and 50cm
length made of Pyrex glass was filled with 2g of dry adsorbent. The column was wet packed to avoid
gaps. The influent solution (containing 50mg/l iron) was allowed to pass through the bed at constant
flow rate of 1ml/min, in down flow manner with the help of a fine metering valve. The effluent
solution was collected at different time intervals. The breakthrough curve for PAAm-Ac column with
respect Fe(III) in wet-phosphoric acid solution are given in figure 12. The breakthrough adsorption
capacity of Fe(III) onto PAAm-Ac could be calculated using the equation:
(8)

Where Ci and Ce denote the influent and effluent (at breakthrough) of Fe(III) ions concentration (mg/l)
respectively, while bv is the breakthrough volume in liters and m is the mass of the adsorbent used (g).
After loading, the column was washed by 25ml of 0.5M HCl and desorption percentage is calculated
as:

(9)

The results of desorption cycles are given in figure 13. After desorption, the column was
washed with double distilled water and deionized water and consequently reloaded through allowing
the crude wet phosphoric acid to pass through the column with 1ml/min. The concentration of iron in
the effluent solution was measured using AAS. The column sorption –desorption –regeneration cycle
was repeated and the break through capacity was calculated and presented in table (3):

Table (3): Breakthrough capacity (B.T.C) of sorption – desorption – regeneration cycles.


Cycle No. B.T.C (mg/g) Desorption %
1 2.3 95
2 2.01 96
3 1.89 97
4 1.81 97

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Arab Journal of Nuclear Science and Applications, 46(4), (27-38) 2013

100 60

50
80

st
40
1 sorpn. cyc.
Break through %

60
nd
2 sorpn. cyc.

C/Co %
rd
3 sorpn. cyc. 30
th
4 sorpn. cyc.
40
20

st
1 Des. Cycle)
20
nd
10 2 Des. cycle)
rd
3 Des. cycle)
0 0
0 20 40 60 80 100 0 5 10 15 20 25 30 35 40 45 50
Effleunt vol. ml Volume (ml)
Fig( ) Break through behavior of PAm-Ac column for four repeated sorption cycles; Fe ion Fig( ) Desorption of Fe ions from PAm-Ac column after reapeted sorption
Fig. (12): Breakthrough behavior of Fig. (13): Desorption of Fe(III) from
concentration 50 mg/L, pH 2.3, resin weight 1g, column 1cm x25cm lenth , flow rate 1ml/min ) cycles using 0.5 HCl at flow rate 0.5 ml/min

PAAm-Ac column for four PAAm-Ac column using


Cycles. 0.5M HCl.
The results in the above table reflect that the PAAm-Ac polymeric composite could be applied
potentially for removal iron from wet process phosphoric acid. It could be regenerated and reused for
repeated sorption –desorption –regeneration cycles up to four cycles without significant change in the
break through capacity and without change its physical properties as well.

CONCLUSION
Based on the results obtained from the study of the removal of Fe(III) from wet phosphoric acid
by polyacrylamide- chemically activated carbon composite adsorbent (PAAm-Ac) using batch and
column techniques, it is observed that the maximum removal efficiency of Fe(III) ions occurs at initial
pH 4.5 and contact time of 120min. The sorption of Fe (III) ions increases as the dosage and initial
concentrations of adsorbent increases. The inhibitive effects of chloride, nitrate and sulphate were
observed. The isotherm study indicates that the Langmuir and Freundlich isotherms models can
adequately model sorption data. The dimensionless separation factor RL has shown that (PAAm-Ac)
can be used for removal of Fe (III) from wet phosphoric acid. It could be regenerated and reused for
repeated sorption desorption regeneration cycles up to four cycles without significant decrease in
sorption and breakthrough capacities. So, PAAm-Ac could be potentially adsorb Fe (III).

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