Hydrometallurgy 164 (2016) 90–96

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Hydrometallurgy

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Solid phase extraction of uranium (VI) from phosphoric acid medium

using macroporous silica-based D2EHPA-TOPO impregnated
polymeric adsorbent
Afshin Khayambashi a, Xiaolong Wang a, Yuezhou Wei a,b,⁎
a
Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, PR China
b
Guangxi University, 100 Daxue East Road, Nanning, P. R. China

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

Article history: This paper describes uranium extraction from aqueous phosphoric acid medium using a silica/polymer based
Received 16 February 2016 D2EHPA-TOPO adsorbent. The mixture of di-2-ethyl-hexylphosphoric acid (D2EHPA) and tri-n-octylphosphine
Received in revised form 10 May 2016 oxide (TOPO) was impregnated and immobilized into the pores of SiO2-P particles. The various experimental pa-
Accepted 25 May 2016
rameters such as the synergistic mixture ratio of extractants, phosphoric acid concentration, the contact time and
Available online 26 May 2016
the temperature were investigated. The results showed that 95% uranium extraction was achieved after 10 min
Keywords:
contacting time using D2EHPA-TOPO/SiO2-P (mass ratio = 3:1 w/w) adsorbent from 1 M phosphoric acid solu-
Uranium tion containing 165 ppm U (VI), 5000 ppm Fe (III), 1000 ppm Ca (II) and 1000 ppm Al(III) at 25 °C. Also, the ob-
Phosphoric acid tained results displayed the high adsorption capacity for Uranium as high as 48 mg g−1 at the mentioned
Solid phase extraction conditions. The rate constant (1.62 g mg−1 min−1) was calculated by the pseudo-second order equation and it
D2EHPA-TOPO/SiO2-P shows that reaction rate was controlled by the chemical adsorption of uranium. Furthermore, D2EHPA-TOPO
(3:1)/SiO2-P has a good selectivity for U(VI) among the co-existing elements (Fe, Al and Ca). The adsorption iso-
therms were well described by the Redlich–Peterson equation, closely followed by the Langmuir equation which
confirms the mechanism is chemical monolayer adsorption. Obtained thermodynamic parameters
(ΔH° .ΔS° and ΔG°) reveal that the U(VI) adsorption to be an exothermic and spontaneous process.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction synergistic mixture of di-ethylhexyl phosphoric acid (D2EHPA) and

Uranium is a key material in generation of nuclear power. However,
its limited primary resources are depleting fast. Among the secondary
resources of uranium, phosphate rocks are known as an important sus-
tainable source of uranium because the phosphoric acid (PA) produced
from phosphate rocks contains uranium in the range of 50–
300 ppm(Singh et al., 2004, 2009). In addition, in nuclear industries a
large quantity of radioanalytical phosphoric acid wastes containing ura-
nium is produced during the analysis of uranium by volumetric tech-
niques such as the Davies and Gray method. This method as well as
the ammonium vanadate titrimetric method are applicable in the fuel
reprocessing plants and are commonly used in the uranium conversion
facilities (Chitnis et al., 1978; Hassell, 1981).
Solvent extraction has been reported to be a successful process for
industrial recovery of hexavalent uranium from phosphoric acid medi-
um. The most common extractant used in this technique is the
⁎ Corresponding author.
E-mail address: yzwei@sjtu.edu.cn (Y. Wei).
trioctyl phosphine oxide (TOPO) in Kerosene (Hurst, 1989, Singh et al.,
2001).
Although liquid-liquid solvent extraction is widely used in industry,
this process is being applied with limitations due to the heavy usage of
organic solvents and diluents. Solid phase extraction is one of the effec-
tive separation methods because it usually combines the selectivity of
solvent extraction with the simplicity and multistage character of col-
umn chromatographic system. It has many advantages such as minimal
organic solvent utilization, compact equipment, simultaneous recovery
process and less radioactive waste accumulation (Wei et al., 2004;
Zhang et al., 2008; Mayyas et al., 2014).
The main aim of this study was to develop a silica/polymer based
D2EHPA-TOPO adsorbent for selective recovery of uranium from

http://dx.doi.org/10.1016/j.hydromet.2016.05.013
0304-386X/© 2016 Elsevier B.V. All rights reserved.
 A. Khayambashi et al. / Hydrometallurgy 164 (2016) 90–96
phosphoric acid medium. In order to investigate the efficiency of the
method, first, the conventional synergistic extractant (D2EHPA–TOPO)
was impregnated and immobilized into the pores of SiO2-P particles
and then, the adsorption experiments using the synthesized adsorbent
were accomplished.
Furthermore, radioanalytical wastes and the phosphoric acid pro-
duced by the wet process usually contain a significant number of ele-
ments which reveals that the uranium selectivity of adsorbent should
be considered. The effect of Mg2+, Al3+, Fe3+, Fe2+, Si4 +, Ca2 +, V5+
and F− on uranium solvent extraction using synergistic mixture of
D2EHPA/TOPO in kerosene has been studied(Hurst and Crouse, 1974,
Arnold et al., 1982; Rafool, 2001, Nazari et al., 2004). Recently, 2-hy-
droxy-4-aminotriazine-anchored activated carbon (ACH) has been syn-
thesized for the solid phase extractive preconcentraton of uranium from
Jordanian phosphoric acid solution with the high loading capacity of
uranium, but the uranium adsorption selectivity among the introduced
metal ions has not been reported(Mayyas et al., 2014). This research fo-
cused on the more common impurities with high concentration (Fe3+,
Al3 + and Ca2 +) in order to evaluate the uranium selectivity of
D2EHPA-TOPO/SiO2-P adsorbent from the impure phosphoric acid
solution.
2. Experimental
The silica/polymer based D2EHPA-TOPO adsorbent was synthesized
in our laboratory by impregnating D2EHPA + TOPO into the pores of the
macroporous SiO2-P particles with a mean diameter of 50 μm. SiO2-P
was utilized as the support of extractants and it contains a
Fig. 1. Schematic diagram of synthesizing the macroporous D2EHPA-TOPO/SiO2-P adsorbent.
91
macroreticular styrene-divinylbenzene copolymer which is
immobilized in porous silica particles by means of a polymerization re-
action taking place inside the SiO2 by an advanced immobilization tech-
nique (Wei et al., 2000; Zhang et al., 2004). The relevant synthesis
procedure was described briefly as follows.
The SiO2-P particles were washed with methanol three times and
dried in vacuo at 333 K overnight. 3.34 g of synergistic extractant
(with specific mass ratio of D2EHPA and TOPO) was placed in a conical
flask and dissolved using 90 cm3 of dichloromethane as a diluent. Sub-
sequently, 6.66 g of the dried SiO2-P particles was added to the solution
and the mixture was rotated vigorously for 1 h at 298 K. Then, the mix-
ture was settled for 1 h. after wards the diluent was removed at 323 K
under reduced pressure by a rotary evaporator to impregnate and im-
mobilize D2EHPA and TOPO into the pores of SiO2-P particles. The re-
mainder was dried in vacuum overnight at 323 K and the colorless
silica-based polymeric composite, D2EHPA-TOPO/SiO2-P, was obtained.
The schematic diagram of synthesizing adsorbent is depicted in Fig. 1.
The SEM images of SiO2–P and D2EHPA-TOPO/SiO2-P are illustrated in
Fig. 2.
Extraction efficiency (E) and distribution coefficient (Kd) of U (VI)
into the adsorbent were measured by batch adsorption experiment. A
weighed amount of adsorbent (0.1 g or 0.25 g) was combined in a
glass vial with Teflon stopper with a measured volume (typically
5 cm3) of a simulated aqueous solution containing 165 ppm U (VI),
5000 ppm Fe (III), 1000 ppm Ca (II), 1000 ppm Al(III) at different acidity
of H3PO4(Hurst et al., 1972). The solution was separated from the adsor-
bent by vacuum filtration and sampled for analysis. The concentration of
uranium and metal impurities were determined by ICP-AES. The
92 A. Khayambashi et al. / Hydrometallurgy 164 (2016) 90–96

Fig. 2. (a) SEM image of SiO2-P, (b) SEM image of D2EHPA-TOPO/SiO2-P.

distribution coefficient and extraction efficiency were calculated by Eqs. D2EHPA/TOPO mass ratio was studied. The results are shown in Fig. 3,
(1) and (2), respectively: depict that the recovery of uranium increases when the mass ratio of
D2EHPA to TOPO is increased from 0 to 3 (w/w) and decreases with fur-
  C −C V
3 −1 0 S S ther increase of its mass ratio, at constant composition of extractant
Kd dm kg ¼ ð1Þ
CS WS (33.3 wt.%). The mass ratio of D2EHPA/TOPO = 3 was selected in this
work since it resulted in the optimum efficiency for uranium recovery
C0 −CS from phosphoric acid medium.
Eð%Þ ¼  100 ð2Þ
C0 The synergistic effect of D2EHPA–TOPO in uranium recovery from
impure phosphoric acid solution containing Fe, Ca and Al is shown in
Where, C0 and CS denote the concentration of each element in initial Fig. 4. It shows using the mixture of extractants for uranium extraction
and final solutions respectively. WS indicates the weight of the dry ad- from impure phosphoric acid mediums has an obvious synergistic effect
sorbent (kg) and VS is the volume of the aqueous phase (dm3). in uranium adsorption efficiency compared with the pure ones in Fig. 3.
In addition, stock solution of uranium (1650 ppm) in water medium In addition, Figs. 3 and 4 represent the effect of phosphoric acid con-
was prepared from uranyl nitrate hexahydrate (UO2(NO3)2 · 6H2O). centration on uranium adsorption from pure and impure mediums. In-
Also, dichloromethane, phosphoric acid, methanol and other reagents crease in phosphoric acid concentration led to decrease in uranium
employed were of analytical grade and were used without further adsorption efficiency. The decrease in E values with increase in acid con-
treatment. centration is mostly like due to the exchange of hydrogen ion of extract-
ant molecule with the uranium metal ion following a cation exchange
3. Results and discussion mechanism (Mondal et al., 2014).
These findings disclose that the uranium adsorption was reasonable
3.1. Effect of D2EHPA-TOPO mass ratio in adsorbent at different phosphoric when the concentration of phosphoric acid is less than 3 M and the ura-
acid concentration nium adsorption has the excellent efficiency when the acidity is less

The uranium adsorption from varying concentration of phosphoric

acid medium using D2EHPA-TOPO/SiO2-P adsorbents with different

Fig. 3. Variations of the uranium adsorption efficiency versus the H3PO4 concentration (M) Fig. 4. Variation of the uranium adsorption efficiency versus the H3PO4 concentration (M)
in presence of different mass ratio of D2EHPA-TOPO in D2EHPA-TOPO/SiO2-P adsorbent at by the three types of silica based adsorbents in impure H3PO4 solutions at 25 °C. (Contact
25 °C. (Contact time: 180 min, adsorbent dose: 0.25 g/5 cm3. C0: 165 ppm.) time 180 min, adsorbent dose: 0.25 g/5 cm3).
 A. Khayambashi et al. / Hydrometallurgy 164 (2016) 90–96 93

Fig. 5. Effect of Contact time on uranium adsorption, C0: 163 ppm, Adsorbent dose: 0.25 g/ Fig. 6. Lagergren pseudo-second order plot used for determination of (k2ads) and (qe) and
5 cm3, [H3PO4]: 1 M, at 25 °C. C0 = 165 ppm. Adsorbent dose: 0.25 g/5 cm3 at 25 °C. [H3PO4]: 1 M.

than 1 M H3PO4. Therefore, 1 M H3PO4 medium was used to study the

kinetics of the adsorption. It is apparent from the error functions which are shown in Table 1
that the kinetic data of the uranium adsorption onto the adsorbent
3.2. Adsorption kinetics studies were not well described by the pseudo first order model. Therefore,
pseudo-second order was applied to analyze the experimental data at
The adsorption kinetic of D2EHPA-TOPO/SiO2-P toward U (VI) in 1 M ten initial uranium concentrations as shown in Fig. 6. The accurate pre-
H3PO4 was studied. The adsorption efficiency of U (VI) as a function of diction of the kinetic data by the pseudo second order model reveals
contact time is presented in Fig. 5, which interprets that the uranium that the rate of uranium adsorption by D2EHPA-TOPO/ SiO2-P might
adsorption kinetic was relatively fast. In other words, the duration of be controlled by chemisorption mechanism(Ho and McKay, 1999).
10 min is enough to achieve the 95% of uranium adsorption.
Kinetics study provides valuable information such as the solute up- 3.3. Uranium selectivity of the adsorbent
take rate and mechanism of adsorption reactions that they are neces-
sary to design the column parameters in uranium recovery process. To study the influence of impurities on the uranium selectivity of ad-
Two adsorption kinetic models, i.e. the pseudo-first-order model and sorbent, adsorption efficiency of uranium, aluminum, calcium and iron
the pseudo-second order model were applied to interpret the experi- onto D2EHPA-TOPO (3:1)/SiO2-P adsorbent from the simulated medi-
mental data(Inbaraj et al., 2006). The linear forms of the models are um with different H3PO4 concentrations has been stablished as given
given as follows: in Fig. 7, which shows that D2EHPA-TOPO (3:1)/SiO2-P has a good selec-
The pseudo-first-order model (Lagergren, 1898): tivity for the uranium extraction among other typically impurities.
Fig. 8 shows the plot of adsorption efficiency of simulated elements
ln ðqe −qt Þ ¼ ln ðqe Þ−k1ads t ð3Þ versus the contact time at H3PO4 concentration of 1 M. It is clear that the
adsorption efficiency of Fe3+ and Ca2+ increase slightly when the con-
tact time is increased from 30 to 180 min while the uranium adsorption
The pseudo-second order model(Ho and McKay, 1998):
efficiency is almost constant after 30 min. Therefore, the contact time for
the simulated medium should not be more than 30 min to avoid from
t 1 t the more adsorption of impurities. In addition, we found that adsorption
¼ þ ð4Þ
qt k2ads qe of impurities was negligible when the adsorbent amount decreased
from 0.25 g to 0.1 g during the 30 min of mixing time, while the uranium
Where k1ads (min− 1) is the first-order rate constant and k2ads adsorption efficiency remained constant.
(g mg−1 min−1) is the second-order rate constant. qe and qt (mg g−1)
are the amount of adsorbed uranium at the equilibrium and at time t 3.4. Adsorption isotherms
(min), respectively(Lv et al., 2015).
In order to study the adsorption isotherms, several models such as
Langmuir, Freundlich and Redlich–Peterson models were attempted to
describe the adsorption phenomena. The Freundlich isotherm (Eq.
Table 1 (5)) is an experiential adsorption isotherm occurring on the heteroge-
Kinetic parameters of uranium adsorption onto D2EHPA-TOPO/SiO2-P at 25 °C. neous surface and can well describe the experimental data in a wide
range of concentration. The Langmuir isotherm (Eq. (6)) suggests that
Lagergren pseudo-first Lagergren pseudo-second order
order model model the adsorption occurs on a homogeneous surface without any lateral in-
teraction between the adsorbed molecules (Freundlich, 1906; Weber
qexp
e qcal
e k1ads r2 qcal
e k2ads r2
mg g−1 mg g−1 min−1 mg g−1 g mg−1 min−1 and Chakravorti, 1974; Anirudhan and Radhakrishnan, 2008).
Redlich–Peterson isotherm (Eq. (7)) approaches to Freundlich or Lang-
3.220 0.988 0.9232 0.342 3.219 1.623 0.9999
muir isotherm and it mainly depends on the model's exponent values
94 A. Khayambashi et al. / Hydrometallurgy 164 (2016) 90–96

equilibrium constant, respectively; KR (dm3 g−1), aR (dm mg−1)αR and

Fig. 7. Variations of the adsorption efficiency of U, Al, Ca and Fe versus the H3PO4
concentration (M) into D2EHPA-TOPO (3:1)/SiO2-P adsorbent at 25 °C. Contact time:
180 min, adsorbent dose: 0.25 g/5 cm3.
αR are the Redlich–Peterson constants.
Eqs. (5)–(7) were fitted to the isotherm data in Fig. 9 by a non-linear
regression analysis to obtain the constants of the introduced models and
the results are listed in Table 2. The best-fit model was selected based on
a maximum correlation between the experimental and the regressed
values for each model. Relatively, the maximum r2 values and minimum
X2 values as shown by the Redlich–Peterson model at 298 K revealed
this model to fit the equilibrium data well when compared to
Freundlich model and closely followed by the Langmuir. This observa-
tion confirmed that Redlich–Peterson is a special case of Langmuir iso-
therm when the exponent in Redlich–Peterson model equals to 1
(Inbaraj et al., 2006).
Therefore, the uranium adsorption onto D2EHPA-TOPO/ SiO2-P
would be chemical monolayer adsorption. These outputs suggest that
the mechanism of solid-liquid extraction of uranium by D2EHPA-
TOPO/ SiO2-P from phosphoric acid medium might be similar with the
mechanism of liquid-liquid extraction by synergistic mixture of
D2EHPA and TOPO in kerosene.
Different mechanisms have been established for uranium extraction
from phosphoric acid using D2EHPA-TOPO in different working condi-
tions and the following reactions are the common mechanisms of the
uranium extraction from phosphoric acid solution (Girgin et al., 2002):

being much lower than or closely to unity, respectively(Inbaraj et al., UO2 ðH2 PO4 Þ−4
6ðaqÞ þ 3ðHAÞ2ðorgÞ þ nTðorgÞ ↔UO2 A2  2ðHAÞ2 ðH3 PO4 Þ2
2006). The equations of the models are described as follows:  nTðorgÞ þ 4H2 PO− 4 ð8Þ

1
=n UO2 ðH2 PO4 Þ2ðaqÞ þ 2HAðorgÞ þ nTðorgÞ ↔UO2 A2  ðH3 PO4 Þ2  nTðorgÞ ð9Þ
qe ¼ K F Ce F ð5Þ
where HA and T represent D2EHPA and TOPO, respectively.
KL Ce Furthermore, the dimensionless constant separation factor (RL) is
qe ¼ ð6Þ
1 þ Ke Ce the essential features of Langmuir isotherm that brought by the follow-
ing equation.
KR Ce
qe ¼ ð7Þ 1
1 þ aR Cα R RL ¼ ð10Þ
e ð1 þ Ke C0 Þ

Where KF ((dm3)nF(mg)1 − nFg− 1) and nF are the Freundlich con- Where C0 is the initial concentration (mg dm−3) and Ke is the Lang-
stants indicating adsorption capacity and intensity of adsorption, re- muir constant (dm3 mg−1). The RL value demonstrates that the adsorp-
spectively; KL (dm3 g− 1) is the product of qm (mg g− 1) and Ke tion could be irreversible (RL = 0) or favorable (0b RL b 1) or linear (RL =
(dm3 mg−1), which represent the maximum adsorption capacity and 1) or unfavorable (RL N 1) (Hall et al., 1966; Inbaraj and Sulochana,

Fig. 8. Variations of the adsorption efficiency of U, Al, Ca and Fe into D2EHPA-TOPO (3:1)/ Fig. 9. Adsorption isotherm of uranium on D2EHPA-TOPO (3:1)/ SiO2-P at 25 °C with the
SiO2-P adsorbent versus the contact time at 25 °C. Adsorbent dose: 0.25 g/5 cm3, related fitted models. Contact time: 180 min, [H3PO4]: 1 M., adsorbent dose: 0.1 g/5 cm3,
[H3PO4] = 1 M. C0 = 50–2750 mg/lit.
 A. Khayambashi et al. / Hydrometallurgy 164 (2016) 90–96 95

Table 2
Isotherm parameters and error functions for Uranium adsorption on (D2EHPA-TOPO)/SiO2-P at 25 °C.

Freundich Langmuir Redlich–Peterson

Kf nF r2 X2 KL Ke r2 X2 KR aR αR r2 X2

7.830 3.951 0.911 29.281 1.640 0.0355 0.992 2.612 1.979 0.062 0.945 0.996 1.191

using the following expressions:

ΔSÅ ΔHÅ
ln ðKd mÞ ¼ − ðthe Van’t Hoff equationÞ ð11Þ
R RT

ΔGT ¼ ΔHÅ−TΔS

Å
 
T
þ ΔCP T−Tref T −T ln ðthe Gibbs−Helmholtz equationÞ
Tref T
ð12Þ

Fig. 10. Separation factor (RL) for Uranium Adsorption on (D2EHPA-TOPO)/SiO2-P at 25 °C
according to Langmuir Isotherm parameter.
2006). The values of RL were figured out at 25 °Cover the wide initial
concentration range of uranium and the results are shown in Fig. 10.
All the RL values were satisfied the favorability condition indicating
the favorable adsorption of U (VI) into (D2EHPA-TOPO)/SiO2-P.
Where R (8.314 J mol−1 K−1) is the gas constant, m (kg dm−3) is the
adsorbent dose, T(K) is the absolute temperature and Kd (dm3 kg−1) is
the standards thermodynamic equilibrium constant determined by Eq.
(1) (Tan et al., 2007; Nandi et al., 2009). The values of Δ H° and Δ S°
were calculated from the slope and the intercept of plot of the ln (Kd
m) versus 1/T as given in Fig. 11. The Δ G° values obtained using the
Eq. (12), whereas the heat capacity values (ΔCP,KJ mol−1 K−1) consid-
ered as zero (Δ CP ~ 0) because of the validation of Van't Hoff assump-
tion. Tref T is the reference temperature chosen arbitrarily (Ringot et
al., 2005). The obtained results are presented in Table 3.
In fact, the negative values of ΔH° andΔG° confirm that the process
is exothermic and spontaneous in nature, while the negative value of ΔS
° reflects a reduced randomness at the interface of adsorbent/solution
(Ahmed and Ram, 1992, Inbaraj et al., 2006; Boparai et al., 2011).
4. Conclusions

Solid phase extraction was studied as a good alternative technique

3.5. Adsorption thermodynamics
The thermodynamic parameters such as changes in standard enthal-
py (ΔH°), standard entropy (ΔS°) and standard free energy (ΔG°) must
be considered in order to indicate which process will occur spontane-
ously in adsorption reactions. These parameters ere determined by
for the uranium recovery from phosphoric acid mediums. The
macroporous silica-based D2EHPA-TOPO polymeric adsorbent was syn-
thesized through impregnation of synergistic mixture of D2EHPA and
TOPO into the pores of SiO2-P particles based on the intermolecular in-
teraction. The selected adsorbent dose (0.1 g/5 cm3) and loading capac-
ity of the adsorption (48 mg g−1) indicate that solid-liquid extraction
can be the better technique than liquid-liquid extraction to reach the
minimal organic solvent utilization, compact equipment and less radio-
active waste accumulation.
The obtained results clearly showed that D2EHPA-TOPO (3:1)/SiO2-
P has a good selectivity for uranium among other impurities such as Fe,
Ca and Al. 95% Uranium adsorption reached in 10 min from 1 M H3PO4
solution containing 165 ppm uranium. In addition, Uranium adsorption
was efficient when the concentration of phosphoric acid was less than
3 M. Therefore, the synthesized adsorbent can be employed for the ura-
nium recovery from by-products and radioanalytical phosphoric acid
wastes containing uranium.
The adsorption kinetics was well explained by the pseudo-second
order equation and the calculated rate constant indicate that the ad-
sorption was controlled by the chemical reaction of uranium. The

Table 3
Thermodynamic parameters for uranium adsorption on (D2EHPA-TOPO)/SiO2-P, [H3PO4]:
1 M.

ΔH° ΔS° ΔG° (kJ mol−1)

(kJ mol−1) (J mol−1K−1)
293 K 303 K 313 K 328 K

−12.28 −20.90 −6.15 −5.94 −5.74 −5.42

Fig. 11. Van't Hoff plot for uranium adsorption on (D2EHPA-TOPO)/SiO2-P, [H3PO4]: 1 M.
96 A. Khayambashi et al. / Hydrometallurgy 164 (2016) 90–96
thermodynamic parameters showed that the uranium adsorption is
exothermic process and is favored at lower temperatures.
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