Journal of Water Process Engineering 19 (2017) 267–276

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Journal of Water Process Engineering

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Selective removal of uranium from wastewater using sludge collected from MARK
refinery wastewater treatment: Equilibrium, thermodynamic and kinetics
studies
Ahmed M. Solimana,d,⁎, Ahmed A. Muradb, Ehab S. El Sheikhd, Ali M. Massadc, Ismail M. Alid
a
Chemistry Department, College of Science, United Arab Emirate University, United Arab Emirates
b
Geology Department, College of Science, United Arab Emirate University, United Arab Emirates
c
Chemistry Department, Faculty of Science and Technology, Umdorman Islamic University, Sudan
d
Nuclear Fuel Technology Department, Hot Laboratory Center, Atomic Energy Authority, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: Adsorption of uranium as uranyl ion UO22+ was investigated on the surface of pretreated refinery wastewater
Uranyl ion sludge. The sludge was chemically activated using different acids (HCl, HNO3, H2SO4, H3PO4), and its uranium
Adsorption uptake capacity from aqueous solution was checked after each activation process. The highest uptake capacity
Wastewater was obtained for sludge treated by phosphoric acid followed by washing with Na3PO4 (0.2 M). The effect of pH,
Kinetics
point of zero charge pH pzc, uranyl ion concentration and adsorbent dose on adsorption processes were studied.
Activation energy
The adsorption is high in the pH range of 3.5–7.2 with optimum value at pH 5.3. The point of zero charge was
found to be at pH 3.95. The adsorption capacity increases with increasing uranyl ion concentration but decreases
with increasing sludge dose. The equilibrium studies showed that the adsorption fits Langmuir adsorption iso-
therm. Also, the kinetic studies showed that the adsorption is pseudo-second order with activation energy
31.15 kJ/mol, indicating that the process is chemical in nature. The activated sludge showed high selectivity for
UO22+ among Zr(IV), Fe(III), Cr(III), Gd(II), Sr(II), Co(II), Ca(II), Cs(I) and Na(I) ions.

1. Introduction
Recognition of the faith of emitted radioactive waste from a variety
of industries such as nuclear and medical practices remains a highly
challenging task globally [1]. Uranium represents a vital component of
the nuclear fuel cycle and because of its increasing demand in the nu-
clear industry, the efforts are being made to recover of uranium from
expected high-level effluents [2]. Moreover, uranium-bearing effluents
may contaminate surface and groundwater and thus become a source of
health hazard. The toxic nature of uranium causes many health pro-
blems as liver and kidney damage [3].
Several techniques are available for removal of U(VI) from aqueous
solution: including solvent extraction, chemical precipitation [4],
membrane filtration processes [5], reverse osmosis [6] and ion ex-
change and adsorption, which are effective and economic methods.
Adsorption technology is one of the effective methods to remove heavy
metals from aqueous solutions. Low-cost adsorbents from industrial
waste by-products and agricultural wastes are the most potential water
treatment methods [7,8]. Industrial waste: waste slurry, iron (III) hy-
droxide, blast – furnace slag and red mud from aluminum industry were
used for removal of heavy metals from wastewater [9–12]. Electro-
coagulation processes for waste water treatment generate large quan-
tity of sludge. This sludge is mainly composed from alumina when
aluminum metal is used as anode.
In the present investigation, inexpensive and accessible sludge
composed of mainly aluminum oxide with minor metals was used in the
experimental design with details of the material composition reported
by Ahmed et al. [13]. The major objective is to explore the adsorption
and selectivity of the activated refinery wastewater sludge for removal
of uranium from aqueous solutions. The activation of the collected and
treated sludge was accomplished through treatment with different acids
(HCl, HNO3, H2SO4 and H3PO4).
The selectivity of the activated sludge for UO22+ was explored in
the presence of different competing ions (Zr4+, Cr3+, Gd2+, Sr2+,
Co2+, Cs+ and Na+) which expected to be in the nuclear effluent
especially from nuclear power plants or polluted groundwater sites. The
effects of different factors as uranyl ion concentrations, adsorption
doses, pH, point of zero charge and temperature on the adsorption
process were studied. Additionally, the equilibrium isotherm, kinetics
and thermodynamics of adsorption processes are further evaluated by

⁎
Corresponding author.
E-mail address: a.soliman@uaeu.ac.ae (A.M. Soliman).

http://dx.doi.org/10.1016/j.jwpe.2017.08.007
Received 8 May 2017; Received in revised form 19 July 2017; Accepted 6 August 2017
Available online 31 August 2017
2214-7144/ © 2017 Elsevier Ltd. All rights reserved.
A.M. Soliman et al.
batch experiments.
2. Experimental studies
2.1. Sludge collection and activation
The aluminum sludge generated from refinery of wastewater by
electrochemical coagulation was used for purification of wastewater
polluted with organic pollutants [13]. Previous study showed that this
sludge is chemically stable and insoluble in moderate acidic and basic
media as well as high thermal stability [13]. The sludge used in this
investigation was collected and treated according to the earlier reported
procedure [13]. The chemical composition of the sludge contains 92%
alumina (Al2O3) with traces of iron, chromium, silicon and sulfur and
its chemical formula is: Al15 (Cu0.4Ca0.3Fe1.4)(SiO4)0.3Cl (SO4)0.3(OH)45.
xH2O. In this work, the sludge was activated by soaking 5 g sludge in
250 ml solution of 0.2 M HNO3, H2SO4, HCl and H3PO4 separately for
24 h, followed by washing with deionized water. The modified sludge
was oven dried at 80 °C for 4 h before using for adsorption tests. Further
treatment of the sludge was made with 0.2 M Na3PO4 solution for ad-
sorption experiments. Samples from each activation method were col-
lected and tested for uranium adsorption. Scanning electron microscope
(SEM) supplied with Electron Dispersive X-ray spectroscopy (EDXS)
model (Joel, JSM 840-A, Japan) was used for elemental analysis of
sludge before and after the uranium adsorption experiments.
The Brnauer-Emmett-Teller surface area and micropore volume of
sludge were determined under nitrogen gas at −196 °C by using a
physisorption analyzer Micrometrics Tri-Star II plus (Tri-Star II 3020).
2.2. Adsorption parameters
The effect of adsorbent dose on adsorption capacity was carried out
using different quantities (0.1-0.5 g) of adsorbent which were equili-
brated with a fixed quantity (50 ml) and concentration of uranyl ion at
pH 4.0 (UO22+) and room temperature. The concentration of residual
uranium species at equilibrium was calculated. The effect of different
uranyl ion concentrations (20–260 ppm) on the adsorption capacity
was studied by equilibration with fixed quantity of sludge at pH 4.0 and
room temperature.
The point of zero charge, (the net charge on the surface of sludge at
specific pH values), was determined by the method of shift in pH [14].
0.2 g of sludge was equilibrated with 50 ml of 0.1 M KNO3 solution in
the pH range of pH (2.0–10.0) for 24 h. Initial pH values were adjusted
by adding appropriate amounts of 0.1 M KOH or HNO3 solution,
keeping the ionic strength constant. The final pH was measured after
24 h under agitation at room temperature. The initial and final pH
values were measured using pH meter Orion model 150A+ pH meter.
The point of zero charge was determined as the pH value at which a
plateau is obtained on the graph pH final = f (pH initial). Finally, the
effect of pH on uranyl ion adsorption was achieved using of 50 mg
sludge that containing 50 ml uranyl solution (40 mg/L) under shaking
condition at 25 °C. The experiments were carried out in the pH range of
2.0–10.0 for 280 min contact time shaking at 120 rev/min. The pH was
adjusted by adding few drops of dilute 0.1 M HNO3 or 0.1 M NaOH.
2.3. Batch experiments
Uranium stock solution (1000 mg/L) was prepared by dissolving
2.013 g of uranyl nitrate hexahydrate UO2 (NO3)2·6H2O (FLUKA) in 1L
deionized H2O.
The adsorption equilibrium experiments were carried out by adding
a fixed amount of sludge 50 mg to 50 ml of uranyl ion of different initial
concentration in plastic vials. All adsorption experiments were carried
out twice and the mean value was taken.
The sample was agitated for 180 min at 25 °C in water bath shaker
model (HACK SWB 20) at 120 rev/min and the adsorbent is separated
268
Journal of Water Process Engineering 19 (2017) 267–276
by using centrifuge BECKMAN model, TJ-6 at 5000 rpm. The con-
centration of uranyl ion at equilibrium and at t = 0 was measured by
using Cary 50 Conc. VARIAN spectrophotometer at λmax 384 nm after
complexation with 8-hydroxy quinolone.
The uranyl samples were mixed with 1.5% 8- hydroxy quinolone in
ethanol at pH 5 then the adsorption spectra were measured to de-
termine the amount of uranyl ion [15]. Calibration curve was con-
structed and used for determination of the concentration of the uranyl
ion of samples after equilibrium. The quantity adsorbed at equilibrium
Qe (mg/g) was calculated as:
Co − Ce
Qe = V
m (1)
where Co and Ce in mg/l are the initial and equilibrium uranyl ion
concentration respectively.
V (liter) is the volume of uranyl ion solution and m is the mass of the
dried sludge in gram. The percentage removal was also calculated as:
C0 − Cf
%Removal = × 100
C0 (2)
where Co and Cf in mg/l are the initial and final uranyl ion con-
centration respectively.
For kinetic studies, 50 mg of sludge was contacted with 50 ml of
uranyl solution at concentration ranged from 10 to 260 mg/L, then
shaking (120rev/min) at 25 °C. Periodically, solution was analysed for
uranium content. These experiments were carried out at different
temperatures using thermostatic shaker (HAAK SW20). The amount of
adsorbed uranyl ion at different times was calculated by Eq. (1).
Batch adsorption experiments were carried out to explore selectivity
of the prepared sludge for uranyl ion. A specific quantity of sludge was
equilibrated with multi-ions. The selectivity of the activated sludge was
tested by competition adsorption experiments of uranyl ion in a mixture
of Zr4+, Cr3+, Gd2+, Sr2+, Co2+, Cs+ and Na+ which were expected to
be present in wastewater and groundwater. The concentration was
0.5 mmol for each metal ion and the mixture solution pH was 4. The
metal ions concentration was measured before and after adsorption
experiments using ICP-OES (Varian model 710).
Uranium selectivity (Su) was used to describe the efficiency and
degree of selectivity of the prepared activated sludge for sorption of
uranium. The selectivity was calculated by the equation given as [16].
Qeu
Su = *100
Qet (3)
Where Qeu is the amount of uranium sorbed, and Qet is the amount of all
sorbed metals in (mmol g−1).
Batch and column reusability tests were carried out in triplicate for
reproducibility of the data. The obtained experimental data were within
the average error limit of 3%.
2.4. Column adsorption study of UO2++
Sorption and desorption study were carried out to check the reu-
sability of the spent sludge. A steal cylindrical tube of 0.5 cm inner
diameter and a height of 25 cm was used as an adsorbent column. The
column was packed with the adsorbent between cotton wool and sup-
ported by inert glass beads (Anti-bumping granules BDH). The UO2++
solution at 80 mg/L was passed through the column with help of
peristaltic pump at an optimum flow rate of 0.25 ml/min. The solutions
coming out from the column were taken out periodically and analysed
for UO2++. Till its concentration was found to be equal to the inlet feed
so the breakthrough and the exhaustion points can be determined.
Desorption study of UO2++ was carried out with 1 M HNO3. Then the
column was washed with deionised water and used for another ad-
sorption desorption cycle.
A.M. Soliman et al.
3. Results and discussion
3.1. Activation of the sludge
Determination of UO2++ uptake capacity before and after sludge
acids activation was indicated in Fig. 1. The results indicate that higher
uptake capacity in all treated sludge by acids compared to untreated
one. Furthermore, the highest uptake capacity was obtained in case of
activation with phosphoric acid that followed by washing with sodium
phosphate solution. Since, the sludge is mainly composed of aluminum
oxide (Al2O3), its surface contains basic and acidic sites at the oxygen
and aluminum atoms (Al+++), respectively. Consequently, cations and
anions could be adsorbed on the surface of the sludge. The high ur-
anium adsorption capacity of the sludge treated with phosphoric acid
followed with phosphate could be explained due to high affinity of
PO43− to bond on Al3+ sites than other anions (SO42−, NO3− and Cl−)
[17–20]. According to the literature, uranium has strong affinity for
bonding with phosphate anions [21,22].
However the presence of phosphorous on the surface from EDX
analysis Fig. 2(a and b) confirm the fixation of the phosphate anions on
the surface of the sludge which adsorbed from solution during the
treatment process in the form of PO4−−−. The morphology of sludge
(Fig. 2a) changed after loading with metal ions (Fig. 2b), where irre-
gular agglomerations in a porous sponge like network with irregular
shapes can be observed in SEM images after loading with UO2++. This
explains the high capacity of the sludge treated samples for adsorbing
uranium more than the sludge treated by other reagents. The adsorp-
tion of uranium at the sludge surface is shown schematically in Fig. 3.
Moreover, specific surface area and porosity were measured. Fig. 1S
shows adsorption–desorption isotherm at 77 K. Based on the interna-
tional union of Pure and Applied Chemistry classification, the N2 ad-
sorption – desorption isotherm of the sludge belongs to the type IV
isotherm with a hysteresis loop in the range 0.5–1.0 P/P0 [23]. This
observation indicates the mesoporous structure of the sludge. Fig. 2S
shows the pore size distribution of the sludge. The BET surface area,
average pore diameter and average pore volume of the sludge are cal-
culated to be 170 m2/g, 9.7 nm and 0.41 cm3/g respectively.
3.2. Selective sorption of uranium
The results of adsorption capacity of different metal ions (Zr4+,
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Journal of Water Process Engineering 19 (2017) 267–276
Fig. 1. Adsorption capacity of sludge without activation and
with activation.
Fe3+, Cr3+, Gd2+, Sr2+, Co2+, Cs+ and Na+) by competition adsorp-
tion experiments is showed in Fig. 4. Efficient removal of uranium re-
quires high selectivity for uranium ion among the competing ions in
aqueous solution. The adsorption capacity was found to be 28 mg/g for
uranium among 8-coexisting metal ions whereas 2.5, 1.5, 3.6, 1.3, 4.1,
1.1, 0.09 and 2.2 mg/gm for Fe(III), Co(II), Zr(IV), Gd(II), Cr(II), Ca(II),
Cs(I) and Na(I), respectively. Uranium showed highest adsorption ca-
pacity among all the cations. This feature could be explained by the
high affinity of uranyl ion (UO22+) to adsorbed phosphate group on the
sludge surface [21,22].
3.3. Adsorption experiments
3.3.1. Batch experiments
Since, the adsorption process is affected by the adsorbent dose,
adsorbate concentration, pH of the solution and point of zero charge, it
was essential to discuss these factors before carrying out kinetic, ther-
modynamic and equilibrium studies.
3.3.1.1. Effect of adsorbent dose. The effect of adsorbent dose on the
adsorption capacity of sludge and percentage removal of uranyl ion
from solution is shown in Fig. 5, which clearly demonstrates that the
adsorption capacity, decreases with increasing amount of sludge. This
feature may be due to overlapping or aggregation of adsorption sites
resulting in a decrease in total adsorbent surface area available to
uranium ions and an increase in the diffusion path length. However,
increasing adsorption dose has dramatic positive impact on the
percentage removal and comparable results were obtained with
activated carbon and chitosan for adsorption of heavy metals and
dyes [24].
3.3.1.2. Effect of uranyl ion concentration. The effect of uranyl ion
concentration on adsorption capacity of the sludge and percentage
removal of uranyl ion from solution was reported. Fig. 6 indicates that
adsorption capacity increased with increasing initial uranyl ion
concentration, but the removal percentage of uranyl ion is apparently
decreased. The adsorption capacity increase with increasing UO2++
concentration is attributed to the availability of more number of uranyl
ions in solution for adsorption [25]. Furthermore, higher initial
adsorbate concentration provided higher driving force to overcome
all mass transfere resistances resulting in high adsorption of UO2++.
A.M. Soliman et al. Journal of Water Process Engineering 19 (2017) 267–276

Fig. 2. SEM and EDX spectra for sludge, before (a) and after (b) loading uranyl ion.

Fig. 3. Schematic representation of adsorbed uranyl ion adsorbed on the sludge surface. Fig. 5. The effect of adsorbent dose on the adsorption capacity of sludge and percentage
removal of uranyl ion.

Fig. 4. Competitive sorption capacities of coexisting ions on activated sludge Co Fig. 6. The effect of uranyl ion concentration on the adsorption capacity of the sludge and
.0005 mol/L for all cations at pH 4, T 25 °C, V = 50 ml and m = 50 mg. percentage removal of uranyl ion.

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A.M. Soliman et al.
The same phenomenon was observed with similar studies for Cr(VI) and
methylene blue dye [26–28].
Also, this behavior indicates the formation of monolayer coverage of
uranyl molecules at the outer interface of the sludge [29].
3.3.1.3. Point of zero charge. The pH of zero charge where the net
charge on the surface of sludge is zero was found to be at pH 3.95 Fig. 7.
The surface of the sludge is positive at pH below this point and negative
at pH above this point. The same method for determination of pHzpc
was applied before [30]
3.3.1.4. Effect of pH. The pH of the solution is important for any
adsorption process. Nevertheless, the pH of the solution has effects on
both uranium ion species present in solution and the surface of sludge.
The effect of pH on the adsorption capacity of sludge is shown in Fig. 8.
From Eh-pH species distribution diagram Fig. 9, it is clearly shown that
adsorption capacity is very low below pH 4, and then sharply increased
between pH 4.0 and 7.0. Finally, the adsorption capacity decreased
above pH 7.3. The effect of pH depends on the surface charge on sludge
and the predominant uranium species. However the sludge material
contains almost 92% aluminum oxide, the surface of this oxide is
hydroxylated. This surface hydroxyl (−OH) group may ionize as
Bronsted acidic or basic sites depending on the pH of solution as
shown in chemical reactions (i) and (ii). Consequently, the surface of
the sludge may be positive, neutral, or negative. It is positive below pH
3.95, neutral at pH 4, and negative above pH 4.
]AlOH + H+ → ]AlOH2+ ˂pH 4.0
Fig. 8. The effect of pH on the adsorption capacity of the sludge.
Journal of Water Process Engineering 19 (2017) 267–276
Fig. 7. Point of Zero Charge of the sludge.
]AlOH → ]AlO− + H+ ˃pH 4.0 (ii)
Fig. 8. shows the effect of pH on the adsorption capacity of the
sludge. Adsorption capacity started to increase near pH 4 reaching
maximum at pH 5.3 then decreases above pH 7. This low adsorption
capacity below pH 4 is attributed to the repulsion between positively
charged surface and UO22+ which is the predominant species at this
pH. According to Fig. 9, the adsorption capacity increases in the pH
range of pH 4.0–7. This attributed to the strong attraction between
neutral surface and negative surface of sludge and UO2(OH)+, (UO2)3
(OH)5+, (UO2)2 (OH)2++ species which are prominent at this pH
(Fig. 9).
The dramatic decrease in the adsorption capacity above pH 7.4 may
be attributed to the repulsion between negatively charged surface of
sludge and negatively charged species UO2(OH)3− and UO2(OH)42−,
which are predominant at this pH. Similar results have been reported
for removal of uranium (VI) from aqueous solution onto natural se-
piolite [31–33].
3.4. Equilibrium studies
The equilibrium adsorption isotherm is important for any adsorp-
tion process. It gives description about the nature of the surface of the
adsorbent and its affinity for adsorbent species. In the present study
Langmuir and Freundlich adsorption isotherms are applied for equili-
brium adsorption of uranyl ion on the activated sludge. The Langmuir
model assumes monolayer adsorption. All sites are identical and en-
(i) ergetically equivalent and the adsorbent are structurally homogeneous
[34,35].
At equilibrium, the sorption takes place at specific sites within the
adsorbent where each site retains one molecule of the given compound.
The adsorbent has a finite capacity for the adsorbate at equilibrium; a
saturation point is reached where no further adsorption can occur.
The following reaction is considered:
Free site + solute = surface complex
The linear form of Langmuir isotherm usually written as:
Ce C 1
= e + Qm
Qe Qm Ki (4)
−1
Where (Ce), the liquid-phase equilibrium concentration (mg L ), (Qe),
is the adsorbed amount at equilibrium (mg g−1) and (Qm) is theoretical
maximum monolayer adsorbent capacity (mg/g), (Ki) is Langmuir’s
constant. qm and Ki are related to adsorption efficiency and energy of
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Fig. 9. Eh-pH species distribution diagram.

adsorption and they can be calculated from the linear plot of Ce/Qe
versus Ce.
Freundlich isotherm is the most primitive known relationship for
multilayer adsorption. It is an empirical equation, which describes the
heterogeneous system. This model applies to adsorption on hetero-
geneous surfaces with interaction between adsorbed molecules [36].
The Freundlich isotherm is expressed by the following empirical
equation in the linear form:

1
lnQe = lnKF + ln Ce
n (5)

Where Qe = solid phase equilibrium concentration (mg g‐1),

Ce = liquid-phase equilibrium concentration (mg L−1) and (KF) and
(n)are Freundlich constants with n giving an indication of the facility
with which the adsorption process takes place. KF (mg g−1(L mg−1)1/n)
is the adsorption capacity of the adsorbent (i.e. the adsorption or dis-
tribution coefficient) and represents the quantity of uranyl ion adsorbed
onto the sludge per unit of equilibrium concentration [37,38].
The slope range of (1/n) between 0 and 1 is a measure of the ad-
sorption intensity or surface heterogeneity, this value becomes more
heterogeneous as it approaches to zero.
A value for 1/n below 1 indicates a normal Langmuir isotherm while
1/n above 1 is indicative of cooperative adsorption. Higher value of n
denotes that the system is more heterogeneous.
In the present study, the adsorption isotherm of uranyl ion on the
activated sludge was investigated in the range of uranyl ion con-
centration between 40 to 200 mg/L. The results of adsorption equili-
brium at pH 3.7 and 20 °C are shown in Fig. 10 which clearly indicates
that the adsorption was almost constant above 100 ppm uranyl ion
concentration. It is evident from this Figure that Langmuir model is best
fit to adsorption isotherm than that of Freundlich and so it may be
concluded that data fits better in Langmuir adsorption isotherm.
Langmuir and Freundlich adsorption isotherms were investigated
and the results are shown in (Fig. 11a and b) and their parameters are
shown in Table 1.
Fig. 10. Uranium adsorption isotherm on sludge activated by H3PO4 followed with
Na3PO4 at pH 3.7 and temperature 20 °C.
3.5. Kinetic studies
The rate of adsorption is essential for evaluation the efficiency of
any adsorption process. Accordingly, from the kinetic studies, the
model of the adsorption process and rate of adsorption could be iden-
tified. Many models could be applied for adsorption process of metal
ions to solid surface in aqueous solutions. The commonly used ones are
pseudo first order; pseudo second order and Elovich model [39–42]. In
this study the pseudo first order and second order were applied.
The pseudo first order model is one of the most widely used models
for describing the adsorption kinetics of a solute from aqueous solu-
tions.
The pseudo-first order equation can be expressed in linear form as
follows:
k1
log(Qe − Qt ) = log(Qe ) − t
2.303 (6)
where (Qt) is the amount of uranyl ion adsorbed at time (t) (mg/g); (Qe)
is the amount of uranyl ion adsorbed at equilibrium and k1 is a first
order rate constant for the adsorption (L/min).

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A.M. Soliman et al. Journal of Water Process Engineering 19 (2017) 267–276

Fig. 11. Langmuir (a) and Frendulich (b) adsorption isotherm of uranium on sludge.

Table 1 The pseudo first order and pseudo second order models were ap-
Parameters of Langmuir and Freundlich models. plied for this study to find out which model will best fit. The figure was
removed for seeking of abbreviations. It is found that the adsorption of
Model Unit Value
uranium fit to second order model for all concentration studied. From
Langmuir qm (mg/g) 38.023 the values of correlation coefficients (R2) (Table 2) for pseudo 1st and
Kl (L/g) 0.01837 2nd order kinetic models at different studied concentrations, it is ob-
R2 0.9194
vious that the sorption processes follow pseudo–second order kinetics.
Freundlich Kf (L/g) 2.0375 Overall, sorption data of uranyl ion on the sludge fit better the pseudo-
N 1.9379 second-order kinetics model for all concentrations than the pseudo-
R2 0.8359
first-order kinetics model.

The pseudo second-order equation is based on the sorption capacity
of the solid phase. Contrary to other models (e.g., the 1st order kinetic
model) it calculates the behavior over the whole range of adsorption. It
considers a rate controlling step of the adsorption mechanism.
The pseudo-second order chemisorption kinetic rate equation is
expressed in its linear form as:
t 1 1 creasing temperature and time for attaining equilibrium is decreased.
= + t Additionally, the activation energy of the adsorption process was cal-
Qt kQe2 Qe
where Qt is the amount of uranyl ion adsorbed at time t (mg/g); Qe is
the amount of uranyl ion adsorbed at equilibrium and k is a second
order rate constant for the adsorption (L/min). The sorption capacity of
sludge prepared from refinery wastewater treatment was evaluated for
adsorption of uranyl ion from aqueous solution as a function of time
and the results of the sorption capacity of sludge for uranium at dif-
ferent time interval with different uranyl ion concentration are shown
in Fig. 12.
It is clearly shown that the equilibrium adsorption capacity value
increases with increasing initial uranyl ion concentration. Nevertheless,
the time needed to attain equilibrium increases with increasing initial
uranyl ion concentration.
3.6. Effect of temperature
The adsorption of uranyl ion on the sludge activated with phosphoric
acid followed by sodium phosphate solution was carried out at various
temperatures (6, 21 and 41 °C). Results shown in Fig. 13 indicate that the
capacity of the sludge for adsorption of uranyl ion increases with in-
(7)
culated according to the modified Arrhenius equation [43]:
Ln k = Ln A-Ea/RT (8)
Where K is the adsorption rate constant (calculated from pseudo second
order at different temperatures), Ea is the activation energy, R is the
universal gas constant 8.314 J. (Kmol)−1, T is absolute temperature, A
is the pre-exponential factor. Fig. 14 shows the relation between Ln K
and 1/T from which K was calculated as pseudo second order rate
constant at different temperatures. The activation energy was found to
be 31 kJ/mol. This indicates that uranium is chemically adsorbed on
the surface of activated sludge, where in the chemical adsorption pro-
cess activation energy is above 16 kJ/mol [44].
Furthermore, the increase of adsorption capacity with increasing
temperature is another confirmation of the chemical adsorption pro-
cesses of uranium on the sludge surface. However, in physical adsorp-
tion processes the adsorption capacity decreases with increasing tem-
perature during adsorption processes [45].

3.7. Sorption mechanism

The first challenge for adsorption processes is to use adsorbent of

Fig. 12. Effect of different uranyl ion concentrations on the kinetics and adsorption ca-
pacity of sludge at room temperature and pH 5.5.
low cost and high efficiency. The next significance is to identify the
adsorption mechanism (the interaction occurring at adsorbent ad-
sorbate interface).
Generally, the mechanism for uranium adsorption on the sludge
may be assumed to involve the following four steps: (i) Bulk diffusion:
migration of uranyl ion from the bulk solution to the sludge surface, (ii)
Film diffusion: diffusion of the uranyl ion through the boundary layer to

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Table 2
Comparison of the adsorption rate constants, calculated and experimental Qe values when treating the adsorption processes with 1st and 2nd order kinetics (for different concentrations of
uranyl ion).

Pseudo-1st order Pseudo-2nd order

Uranyl ion Conc.mg/ Experimental adsorption capacity Rate constant (k1) Theoretical adsorption R2 Rate constant (k) Theoretical adsorption R2
L (Qe) capacity (qe) capacity (qe)

60 50 0.020497 64.94 0.93 0.000737 56.1798 0.96

100 72 0.021879 56.17 0.96 0.000989 75.1880 0.98
140 80 0.000134 84.64 0.94 0.000344 90.0901 0.93
180 90 0.012206 71.38 0.97 0.000681 84.7458 0.98
220 115 0.015660 109.06 0.93 0.000382 117.6471 0.96
260 120 0.024411 120.17 0.97 0.000360 129.8701 0.97

the surface of the adsorbent, (iii) Pore diffusion or intraparticle diffu-
sion: transport of the metal ion from the surface to the pores of the
particles, (iv) Chemical adsorption of the uranyl ion on the surface of
the sludge via ion- exchange, complexation and/or precipitation.
Providing sufficient stirring will avoid creating difference in con-
centration between metal ions and the sludge particles (concentration
gradient) in the batch system which helps to ignore bulk diffusion,
especially when it is known that the last step (ion exchange, com-
plexation or precipitation) takes place very fast. Accordingly, the ad-
sorption mechanism is controlled by intraparticle diffusion [46], film
diffusion [47] or both. Intraparticle diffusion depends on various fac-
tors like initial concentration of adsorbate, physical properties of the
adsorbent and rate of agitation [48]. The following equation is used to
determine the intraparticle diffusion parameter:
controlling mechanism of adsorption processes. Also, the diffusion
coefficient for intraparticle diffusion was calculated by applying the
following equation:
Di = 0.03 × r 2/ t 0.5 (10)
2 0.5
Where (Di) is the diffusion coefficient with the unit cm /s, t is the
time in (s) for the high adsorption of uranium species and (r) is the
average radius of sludge particle in cm.
The solid particle diameter of the sludge used in this study is 410 μm
and it has been assumed that the sludge particles are spherical in shape.
The value of diffusion coefficient (1.528 × 10−6 cm2/s) indicates that
the adsorption is chemically controlled, since it is more than
1.5 × 10−8 cm2/s for physical adsorption processes [49].

Q = Ki t0.5 + C (9) 3.8. Comparison of the adsorption capacity of the sludge with other
adsorbents

Where (Q) is the amount of uranyl ion adsorbed (mg/g) at time (t), (Ki) is
the intraparticle diffusion constant and (C) is the intercept which pro-
portional to the film thickness in the boundary layer diffusion me-
chanism. The rate of adsorption is controlled by intraparticle diffusion
for all the adsorption period if the value of (C) is equal to zero. The
intraparticle diffusion plot of experimental data q versus t0.5 for different
uranyl ion concentrations at 25 °C is shown in Fig. 15. The plot is not a
straight line for all concentrations, which indicates that intraparticle
diffusion is the controlling mechanism of adsorption at the first stage.
It is also apparent that the straight line does not pass through the
origin, which also confirm that intraparticle diffusion is not the only
Table 3 shows the adsorption capacity of many adsorbent for ur-
anium from literature. The activated sludge which is very cheap and
possesses considerable adsorption capacity as compared to other che-
micals and nanomaterials, considered as an efficient adsorbent with
high thermal and chemical stability.
3.9. Column study (Sorption and resorption of UO2++)
The data of column adsorption are shown in Fig. 3S. The actual
uranium breakthrough point has been observed at 2000 min (33.3 h)
while the exhaustion point of the column was attained at 2880 min

Fig. 13. Effect of the temperature on adsorption kinetics of uranyl ion

on activated sludge.

274
A.M. Soliman et al. Journal of Water Process Engineering 19 (2017) 267–276

Fig. 14. The linear relationship between 1/T and ln K2 at 6 °C, 21 °C and 41 °C.

(48 h). The elution of the adsorbed uranium in the column was carried Table 3
out using 1 M HNO3. The elution curve is shown in Fig. 4S clearly in- Comparison of the U(VI) sorption capacity on sludge prepared from refinery of waste-
dicated that 15 ml of 1 M nitric acid are sufficient to clean the column water with other adsorbents

and remove the adsorbed uranyl ions on the sludge surface. The column Sorbents Qmax Reference
could be regenerated for three cycles of sorption and desorption effi- (mg g−1)
ciently.
Magnetic Fe3O4@SiO2 52.0 [50]
Nanoporous alumina 11.6 [51]
3.10. Conclusions Multi-walled carbon nanotubes 26.2 [52]
Oxidized multi-walled carbon nanotubes 33.3 [53]
The highest adsorption capacity and selectivity for uranium was Akaganeite 90.44 [54]
found for sludge activated by H3PO4 followed by Na3PO4. The equili- Modified chloromethylated polystyrene-divinyl 18.78 [55]
benzene polymer
brium and kinetic studies showed that the adsorption fits to Langmuir Hematite 5.50 [56]
adsorption isotherm with pseudo second order kinetic. Thermodynamic Modified carbon CMK-5 65.40 [57]
studies showed that the adsorption is endothermic and uranyl ion is Sludge prepared from refinery of wastewater 34.00 Present Study
chemically adsorbed on the surface of activated sludge with activation Sepiolite 34.60 [58]
Tendorek Volcanic toff 2.70 [59]
energy of 31 kJ/mol. In addition, the mechanism of adsorption was
found to be controlled by both intraparticle and film diffusion

Fig. 15. Intraparticle diffusion mechanism of uranyl

ion on the sludge.

275
A.M. Soliman et al.
mechanisms.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.jwpe.2017.08.007.
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