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Journal of Advanced Research 22 (2020) 153–162

Contents lists available at ScienceDirect

Journal of Advanced Research


journal homepage: www.elsevier.com/locate/jare

Removal and recovery of U(VI) from aqueous effluents by flax fiber:


Adsorption, desorption and batch adsorber proposal
A. Abutaleb a,⇑, Aghareed M. Tayeb b, Mohamed A. Mahmoud a,c, A.M. Daher c, O.A. Desouky c,
Omer Y. Bakather a,e, Rania Farouq d
a
Chemical Engineering Department, College of Engineering, Jazan University, Jazan, Saudi Arabia
b
Minia University, College of Engineering, Chemical Engineering Department, Egypt
c
Nuclear Material Authority, Cairo, Egypt
d
Petrochemical Engineering Department, Pharos University, Alexandria, Egypt
e
Chemical Engineering Department, College of Engineering, Hadhramout University, Mukalla, Yemen

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Removal and recovery of uranium


were investigated in a batch process.
 Adsorbent characteristics were
scientifically analyzed.
 The maximum obtained U(VI)
removal was 94.50% at pH of 4 and
adsorbent dose of 1.2 g.
 Adsorption data were analyzed using
kinetic, isotherm and thermodynamic
models.
 Full scale batch adsorber unit was
recommended.

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

Article history: Flax fiber (Linen fiber), a valuable and inexpensive material was used as sorbent material in the uptake of
Received 25 June 2019 uranium ion for the safe disposal of liquid effluent. Flax fibers were characterized using BET, XRD, TGA,
Revised 10 October 2019 DTA and FTIR analyses, and the results confirmed the ability of flax fiber to adsorb uranium. The removal
Accepted 27 October 2019
efficiency reached 94.50% at pH 4, 1.2 g adsorbent dose and 100 min in batch technique. Adsorption
Available online 11 November 2019
results were fitted well to the Langmuir isotherm. The recovery of U (VI) to form yellow cake was inves-
tigated by precipitation using NH4OH (33%). The results show that flax fibers are an acceptable sorbent
Keywords:
for the removal and recovery of U (VI) from liquid effluents of low and high initial concentrations. The
Adsorption
Uranium
design of a full scale batch unit was also proposed and the necessary data was suggested.
Flax fiber Ó 2019 The Authors. Published by Elsevier B.V. on behalf of Cairo University. This is an open access article
Recovery under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Yellow cake

Introduction human health and environment [1]. Therefore, many countries


have paid considerable attention to avert or treat environmental
Environmental pollution is deemed one of most serious issues pollution [2,3]. Pollutants of water and waste water industries such
that should be taken care of due to its catastrophic influences on as heavy metals have been treated using different physical and
chemical processes. Compared to all the different wastewater
industries, water containing radioactive pollutants (uranium and
Peer review under responsibility of Cairo University.
⇑ Corresponding author at: Chemical Engineering Department, Faculty of Engi- thorium) is the most dangerous wastewater. Thus, researchers
neering, Jazan University, Jazan, Saudi Arabia. are still investigating different methods to remove radioactive ele-
E-mail address: Azabutaleb@jazanu.edu.sa (A. Abutaleb). ments from liquid wastes for safe disposal [4–6]. Uranium (U) is a

https://doi.org/10.1016/j.jare.2019.10.011
2090-1232/Ó 2019 The Authors. Published by Elsevier B.V. on behalf of Cairo University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
154 A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162

very significant toxic and radioactive element that is utilized in Rð%Þ ¼ ½ðfeed concentration - final concentrationÞ=feed concentration
many nuclear applications. However, it has negative effects on x100 ð1Þ
the environment and needs to be removed from radioactive waste
water[7]. Uranium from nuclear industrial processes seeps into the ½ðfeed concentration -final concentrationÞxðVolume of sampleÞ
qe ¼
environment, pollutes water or soil and enters plants and from Mass of flax fiber
comes in contact with human bodies, causing severe damage to
the kidneys or liver that lead to death [8]. Various processes, such
as precipitation, evaporation, ion exchange, liquid-liquid extrac- Sorption kinetics
tion, membrane separation [9–13], have been used to treat the
radioactive liquid wastes. However, these methods are not suc- Three kinetic models were used to explain and estimate the
cessful or cost-effective, especially when dealing with the great uptake of uranium ions on flax fiber by linear and nonlinear tech-
volumes of liquid waste includes low concentrations of radioactive niques [21]. Non-linear technique is a better system to acquire the
pollutants [14]. For that reason, many researchers considered parameters of kinetic models.
adsorption to be one of the most efficient processes to treat this
limits of pollutants. Adsorption process has been considered to Pseudo-first-order model
be an advantageous technique (simple construction and operation)
and it uses a variety of adsorbent materials such as modified rice This model [22], is explained by the following equations:
stem [15], codoped graphene [16], nanogoethite powder [17],  
Non-linear : qt ¼ qe 1  expðK 1 tÞ ð3Þ
iron/magnetite carbon composites [18] and sporangiospores of
mucor circinelloides [19], to adsorb pollutants from the liquid
phase. Flax fibers are obtained from agriculture as a by-product. Linear : Logðqe  qt Þ ¼ Logðqe Þ  ð1  K 1 =2:303Þt ð4Þ
It is composed of fibers, cellulose, hemicelluloses, lignin containing
functional groups in their chemical composition such as carboxyl,
Pseudo-second-order model
hydroxyl group which have a major role in facilitating adsorption
processes. The current work, deals with the treatment of high con-
The model is explained by equations [23]:
centrations of uranium ions discharged from nuclear processes
(mining, nuclear fuel manufacture and application), which must Non - linear : qt ¼ K 2 q2e t=ð1 þ K 2 qe tÞ ð5Þ
be treated to the lowest concentration before being transferred
to the relevant processing units such as the Hot Labs Center, Linear :t=qt ¼ ð1=K 2 q2e Þ þ ð1=qe Þt ð6Þ
Atomic Energy Authority, Cairo. In this research, the focus was
on the use of natural degradation materials such as flax fibers to where, qe and qt are the sorption capacity at final and any time t
remove and recover the U element from the liquid wastes. The fac- (mg/g) and K1 (L/min) and K2 (g/mg.min) are the constants of the
tors affecting the batch sorption(pH, sorbent dose, initial feed con- pseudo-first and second order models, respectively.
centration, contact time, and temperature) were optimized and the
results were evaluated using isotherm and kinetics models. The Elovich kinetic model

Materials & methods The Elovich model is used to illustrate the chemisorption pro-
cess assuming that the sorbent surfaces are vigorously heteroge-
Materials neous, but the equation does not suggest any specific mechanism
for sorbate–sorbent and is explained by equation [24]:
Flax fiber was obtained from flax industry, Tanta, Egypt. Flax Non - linear : dqt =dt ¼ aexpðbdtÞ ð7Þ
fiber was prepared as follows: they were cut into <3–5 mm pieces
and washed by hot water many times to remove wax and foreign The parameters of a and b are the Elovich constants which refer
matters. Washing was continued until all contaminants were to the sorption rate (mg/g. min), and the capacity of flax fiber (g/
removed and clear water was obtained. After that, flax fibers were mg), respectively. The Elovich equation was given in linear form
dried at 378 K to dry the fibers. Liquid samples of experiments by the eq.:
were prepared from uranyl acetate (UO2(OCOCH3)26H2O). Feed Linear : qt ¼ ð1=bÞlnðabÞ þ ð1=bÞlnðtÞ ð8Þ
and finial uranium concentrations (mg/l) were determined spec-
trophotometrically (Shimadzu UV–VIS-1601 spectrophotometer)
using arsenazo (III) [20]. All chemicals and reagents used in this Results & discussion
research were analytical grades.
Characterization
Methods
Chemical composition
To study the adsorption performance of the prepared flax fibers, Cellulose, hemicellulose and lignin (Fig. 1) are the main compo-
sorption of U (VI) ions was investigated in a batch system. A known nents of flax fibers [26]. Lignin acts as a bonding material. The com-
weight of adsorbent was agitated at 250 rpm with 60 mL uranium position (cellulose, hemicelluloses, lignin and ash) of Fax fibers
sample in a thermostatic shaker water bath of type (Julabo, Model were analyzed using the process developed by Aravantinos-
SW 20 °C, Germany) at different conditions (Table 2). 0.1 M HNO3 Zafiris et al. (1994) [25]. The chemical compositions of flax fiber
or 0.1 M NH4OH solutions were utilized to adjust pH (Metrohm E- are shown in Table 1.
632, Heisau, Switzerland). The fiber was separated by filter paper
and the sample was spectrophotometrically analyzed. Maximum BET analysis
uptake capacity qe (mg/g) and adsorption percent [R (%)] were Fig. 2 shows N2 sorption–desorption isotherms (NOVA 2200E
determined by following equations. BET Surface Area Analyzer, Quantachrome Instruments) of flax
A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162 155

Fig. 1. Cellulose, hemicellulose and lignin.

Table 1
Chemical composition (dry basis) of flax fiber.

Component Cellulose Hemicelluloses Lignin Ashes others


Weight (%) 85.3 8.3 3.5 1.03 1.67

Fig. 2. N2 adsorption–desorption isotherm (a) and pore-size distribution (b) of flax fiber and FTIR spectrum of flax fiber before (c) and after uptake (d).

fiber, which is described as IV- style with a hysteresis loop, which at 2910 cm1. The band at 1735 cm1 and 1642 cm1 explains that
indicates a mesoporous nature of flax fiber. The hysteresis loop there is a C@O group of hemicellulose and ketenes, respectively
have a quick adsorption and desorption nature, representing a nar- [15]. The bands at 1465 and 1433 cm1 represent symmetric
row mesopore size distribution. Flax fiber possesses a large surface ACH, ACH2 vibrations and CAH group at 1387 cm1 of methyl
area of 51.54 m2/g and a pore volume of 0.41 cm3/g. The active group. The band near 1165–1130 cm1, refer to asymmetric
sites of flax fiber were provided by a high surface area. The active CAOAC. The bands at 1032 cm1 refer to the ether group of CAO
adsorptive sites result from the mesoporous nature of flax fiber ether [27]. After the process of adsorption, changes were made in
leading to its the high adsorption capacity of uranium ions onto OAH group, CAH bonds and C@O group to 3490, 2923 and
the fiber. 1653 cm1, respectively. These shifts indicate that there is a corre-
lation between the uranium ions and the functional groups that
Fourier transformed infrared spectroscopy analysis (FTIR) make up the flax fibers by the ion exchange of H+ on the surface
The FTIR (Thermo Fisher Scientific, USA) of the flax fiber (Fig. 2) of fibers with UO2+
2 which changes the vibration strength and peak
describes the properties of material components. The band at wavenumber[15]. The shifts in wavelength and the alteration in
3483 cm1 refers to OAH group and CAH bonds in the alkyl groups absorption intensity of OAH group, CAH bonds and C@O groups
156 A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162

can be correlated to the mechanism of adsorption. The presence of increasing time until it reaches a certain time (100 min), no notice-
OAH stretching vibration may be attributed to the components of able change occurs with increase in time due to saturation of
cellulose and lignin that may required in UO2+
2 binding during ion adsorption sites [32,33]. The pH parameter is very important in
exchange and/or complexation mechanisms [28]. the adsorption of U(VI) ions because of its ability to change the
ionic forms of uranyl ions. Uranium uptake was raised with
X-ray diffraction (XRD) analysis increasing the pH until reaching a maximum value at pH 4 and
Fig. 3 (a and b), shows the XRD pattern of flax fiber before and then decreased (Table 2). Lower adsorption of uranium ions at
after adsorption was performed by X-ray diffractmeter (Philips low pH values is due to the competition with H+ on the surface
instrument PW 1730). In the raw flax fiber four patterns of diffrac- of flax fiber [34]. When pH values increase beyond pH 4 the per-
tion are presented at 2h = 14.82°, 16.56°, 22.76°, and 33.99°, which centage removal decreases due to the creation of other forms
refer to the planes of ( 1 1 0), (1 1 0), (2 0 0), and (0 0 4), respec- (UO2(OH)2) or precipitation. Also, the effect of ionic strength on
tively, indicating the crystalline structure of cellulose after adsorp-
tion[29]. Similar diffraction peaks were observed, and additionally
new peaks at 2h = 33.22°, and 74.55° referred to planes of (1 1 1) Table 2
Parameters of U (VI) uptake by flax fiber.
and (3 1 1), respectively. The appearance of new peaks and
decreasing of the crystal structure after the uranium uptake may Parameter Removal percent (R
owe to the uptake of U(VI) by flax fibers, which causes part of %)
the particle construction to modify from crystal to amorphous[11]. pH: 2.0 42.32
(Conditions: 700 mg/l, 1.0 g, 100 min, 3.0 75.24
303 K)
Thermal analysis 4.0 92.21
Thermal analysis was performed by DTA-50 Differential Ther- 5.0 89.31
mal Analyzer, Japan. Thermogravimetric analysis (TGA) shows a 6.0 83.50
degradation percent of 3.3% within 304–501 K, of dehydration 7.0 65.11
8.0 51.50
reactions of water content [30]. The degradation percent of flax
fiber begin at 502 K and increase with increasing the temperature Initial concentration (mg/l): 50– 100
500
to 80% between 502 K and 683 K (Fig. 3C). The degradation percent Conditions: pH = 4, 1.0 g, 100 min, 303 K) 600 100
within 684–798 K was 6.3%, of char degradation [31]. Differential 700 92.2
thermal gravimetry analysis (DTG) shows two peaks at 565 and 800 80.5
648 K which corresponding to light and heavy materials, respec- 900 71.6
1000 64.4
tively. DTG curve indicates that the maximum degradation hap-
pened at the temperature 648 K with the rate of 0.68 mg/min. Adsorbent dose (g) : 0.2 56.45
Conditions: 700 mg/l, 100 min, pH = 4, 0.4 65.34
Thermal analysis indicates that there are two steps are involved
303 K)
in the degradation of flax fiber. The first step is the hemicellulose 0.8 73.40
degradation [31], between 565 K and 598 K of percent 18.6% 0.9 92.20
(Fig. 3C). The second step of degradation begin at 598 K and is fin- 1.0 94.50
ished at 648 K. 1.2 94.58
1.4 94.32
Temperature (K) : 301 94.50
Sorption studies Conditions: 700 mg/l, 100 min, 1.0 g, 313 95.33
pH = 4)
Sorption time, pH, initial U(VI) concentration, dose and temper- 323 97.41
ature were optimized and expressed as removal percent (R%) of U 328 90.22
333 80.90
(VI) ion on the adsorbent. The uptake of uranium increases with

Fig. 3. XRD spectra of flax fiber before (a) and after (b) adsorption (C) TGA and DTG curves of raw flax fiber (N2 atmosphere at 283 K).
A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162 157

U(VI) adsorption was studied and the result indicates that the Redlich-Peterson model
uptake of U(VI) ions on flax fibers is feebly reliant on ionic strength This model describes adsorption equilibrium in excess of adsor-
along the pH range. Table 2, demonstrates that the removal per- bate concentration which is appropriate in either homogenous or
cent of uranium ions remains at its maximum value; 100%, heterogeneous processes and expressed by the following eq. [37]:
between 100 and 600 mg/l initial concentration and then it
decreases as U (VI) concentration is raised, due to a decrease in Non - linear : qe ¼ K RP C e =ð1 þ AC e b Þ ð15Þ
the adsorption sites on the surface of flax fiber [35]. The effect of
flax fiber dose on the U(VI) uptake was explained in the range
0.2 to 1.6 g. Table 2, shows that the removal percent increased with Linear : ln½K RP ðC e =qe Þ  1 ¼ lnA þ blnC e Þ ð16Þ
increasing the dose due to the increase in sorption sites. Until it
reaches a certain limit (1.0 g) there will be no further increase in where KRP (L/g) and A (L./mg)b are the constant of Redlich-Peterson
the uptake percentage [36,37]. Keeping all other parameters con- model. The item b is the exponent related to adsorption energy
stant, the uptake of uranium increased slightly with increasing
the temperature up to 323 K and then it started decreasing at tem-
peratures from 323 to 333 K as shown in Table 2. This refers to Jovanovic model
both endothermic from 301 to 323 K and exothermic in nature Jovanovic model is predicated on the assumptions limited in the
from 323 to 333 K. Langmuir model, but also the option of a little mechanical associ-
ates among the sorbate and sorbent and expressed by the follow-
ing eq. [40]:
Isotherms studies
Non - linear : qe ¼ qmax ð1  expðK J C e Þ ð17Þ
Five isotherm models (Langmuir, Freundlich, Temkin, Redlich-
Peterson and Jovanovic model) were used to explain the equilib-
rium uptake of uranium ions on flax fiber and the isotherm param- Linear : lnqe ¼ lnqmax  K J C e ð18Þ
eters were estimated by linear and nonlinear systems. The
achieved isotherm parameters determined by nonlinear methods where qmax is maximum uptake of sorbate (mg/g), and KJ is the
are good fitting than those acquired by linear methods because Jovanovic constant (L/mg).
the non linear methods overcome the inaccuracy of the results The linear and nonlinear parameters of adsorption isotherms
using the original isotherm equations [38,39]. are listed in Table 3. The results of the linear analysis show that
the Langmuir model appears to be the best fitting model for U
(VI) uptake on flax fiber with higher correlation coefficient (R2)
Langmuir model
than other models indicating that U(VI) ions are adsorbed onto flax
This isotherm is used to determine the monolayer uptake of U
fiber as monolayer surface adsorption. Fig. 4 shows the plot of non-
(VI) onto flax fiber and is described by the following equations
linear isotherms obtained at 323 K. The results obtained by the
[35]:
non-linear method confirmed that the Langmuir model is the most
Non - linear : qe ¼ ðQ L K L C e Þ=ð1 þ K L C e Þ ð9Þ suitable model than other models for the adsorption process as the
adsorption capacity results are consistent with the results of
experiments and also the value of correlation coefficient (R2) and
Linear : C e =qe ¼ 1=ðQ L K L Þ þ C e =Q L ð10Þ
chi-square analysis (v2) are greater than other isotherms.
where, Ce is the U(VI) concentration at equilibrium (mg/L). QL (mg/
g) and KL (L/mg) are constants of Langmuir isotherm. Table 3
Parameters of adsorption linear and nonlinear isotherm models at 323 K (pH4,
100 min, 1.2 g, 700 mg/l).
Freundlich model
This isotherm [40] explain the intensity of U (VI) adsorption on Experimental qe (mg/g) Isotherms Linear Non-linear
the adsorbent by eq.: Langmuir isotherm
QL (mg/g) 42.721 41.221
Non - linear : qe ¼ K F C e 1=n ð11Þ KL (L/mg)
2
0.0511 0.0612
R 0.949 0.984
v2 3.210
1 Freundlich isotherm
Linear : lnqe ¼ lnK F þ lnC e ð12Þ KF (mg(11/n)L1/ng1) 2.577 4.680
n
n 3.481 3.410
KF (mg(11/n)L1/ng1) is Freundlich constant and n is a value that 40.90 R2 0.921 0.935
refers to the intensity of U(VI) adsorption onto flax fiber. v2 17.75
Temkin isotherm
KT (L/g) 1.110 1.055
Temkin model H (J/mol) 334 338
R2 0.912 0.930
Temkin model supposes that adsorption heat reduces with the
v2 9.709
decline of adsorption capacity and described by the following eq. Redlich-Peterson isotherm
[15,40]: KRP (L/g) 8.541 11.23
A (L./mg)b 0.622 0.891
Non - linear : qe ¼ ðRT=HÞlnK T C e ð13Þ b 0.791 0.780
R2 0.885 0.901
v2 6.231
Linear : qe ¼ ðRT=HÞlnK T þ ðRT=HÞlnC e ð14Þ Jovanovic isotherm
KJ (L/mg) 0.0002 0.0451
where KT (L/g), R, T and H (J/mol) are constants of Temkin model (L/ qmax 35.760 37.430
2
g), universal gas constant (8.314 J/mol/K), temperature (K) and con- R 0.413 0.831
v2 18.82
stant related to sorption heat (J/mol), respectively.
158 A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162

Fig. 4. Non-linear isotherm models for U (VI) adsorption by flax fiber at 323 K.

Adsorption kinetics
Table 4
Results of linear and nonlinear kinetic models at 323 K.
The results of the linear and non linear kinetic studies (Table 4),
Experimental qe (mg/g) Kinetic models Linear Non-linear
show that the value of theoretical adsorption capacity (qe) of
pseudo first order kinetics and Elovich model do not fit the exper- Pseudo-first-order kinetics
qe (mg/g) 24.81 36.99
imental result. But, a good agreement was obtained with pseudo
K1 (L/min) 0.0051 0.088
second order rate (Fig. 5). For pseudo second order model, the R2 0.5985 0.913
parameters are similar to those achieved by the linear technique. v2 2.750
The These results explain that the process of uranium uptake on 40.90 Pseudo-second-order kinetics
flax fibers corresponds or follows the pseudo second order model qe (mg/g) 41.6 41.42
K2 (g/mg min) 0.0023 0.003
and the higher value of correlation coefficient confirm this result. 2
R 0.995 0.996
v2 0.329
Thermodynamic studies Elovich model
a (mg/g min) 0.398 0.455
b (g/mg) 6.912 6.905
Enthalpy change (DHo), Free energy change (DGo) and entropy
R2 0.9607 0.954
change (DSo) were calculated from the following eqs. [32,35]: v2 1.618
DGo ¼ RTlogK C ð19Þ

Fig. 5. Non-linear kinetic models for U (VI) adsorption by flax fiber at 323 K.
A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162 159

Fig. 6. Van’t Hoff plot of U (VI) adsorption by flax fiber: (a) at (301–323 K) and (b) at (323–333 K).

DGo ¼ DHo  T DSo ð20Þ between UO2+2 and the functional groups responsible for bonding.
The positive DH° from 301 to 323 K, refers to an endothermic
logK c ¼ DSo =2:303R  DHo =2:303RT ð21Þ behavior, and negative DH° in the range 323 to 333 K, indicates

where:

T: Temperature (K)
R: Gas constant (8.314 J/mol. K)

K c ¼ C Fe =C Se ð22Þ

where CFe and CSe are uranium concentrations at flax fiber and in
liquid sample (mg/l), respectively at equilibrium.
In this section DHo and DSo were determined from Van’t Hoff
graph (Fig. 6). If DH0 > 0 (positive) the process is endothermic in
nature and the U(VI) uptake increases with rise the temperature.
On the other hand, if DH0 < 0 (negative) the process is exothermic
in nature and the U(VI) uptake decreases with rise in the temper-
ature as a result of breaking the bonds formed by high temperature
[7]. Table 5, shows that DG° was negative and increases by increas- Fig. 7. Effect of different eluting agents on U (VI) desorption from loaded Flax fiber.
ing the temperature from 301 to 323 K (Fig. 6a), then decreased
after 323 K (Fig. 6b), which indicate the favorability of uranium
uptake at lower temperature. The reason for the endothermic nat-
ure (from 301 to 323 K) is the increase in the pores of the fiber by
heating effect, which leads to the emergence of active sites on the
surface of the fiber which increase the interaction of UO2+
2 with the
functional groups (OAH group, CAH bonds and C@O group) of the
cell walls of flax fibers by the ion exchange of H+ on the surface
with UO2+ 2+
2 . Besides, spread free UO2 into the pores of the fibers
(electrostatic interaction) [41]. While the exothermic system (from
323 to 333 K) is due to the release of uranium ions from the active
sites on the fiber surface due to weak or broken in the interaction

Table 5
Thermodynamic results for the adsorption of U (VI) by flax fiber.

Temperature (K) Kc DG o DHo DSo


(kJmol1) (Jmol1) (JmolK1)1
Endothermic 301 17.18 58.43 46.21 176.12
313 18.61 55.07
323 37.61 56.84
Exothermic 323 37.61 56.84 201 574.0
328 9.33 57.72
333 4.29 58.60
Fig. 8. ESEM scanning of sintered precipitate of yellow cake.
160 A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162

an exothermic behavior. Positive DSo refers to random uptake of of desorption process. The HNO3 is also able to dissolve uranium to
uranium ions onto flax fibers. form the soluble form. Desorption process occurs by the replace-
ment of uranium ions on the surface and pores of flax fiber by H+
Desorption process and U(VI) ions are released to the bulk solution. Fig. 7, shows
higher desorption when HNO3 is used. Therefore, HNO3 was
The recovery of U (VI) from loaded adsorbent material (flax selected as the best desorbing agent for recovering U (VI) ions.
fiber) was performed using five different desorption solutions Desorption (%) was calculated according to the following eq.:
(HNO3, HCl, H2SO4, Na2CO3 and H2O) at room temperature
Desorptionð%Þ ¼ ðdesorption ions =adsorption ionsÞ  100 ð22Þ
(Fig. 7). Firstly, loaded flax fiber was treated with 50 mL (1.5 M of
HNO3, HCl, H2SO4, and Na2CO3) of each eluting solution in thermo-
static shaker bath for 1 h at 301 K. Water has a weak effect as elut- Recovering process
ing agent in the desorption of uranium ions from fibers because it Uranium ion in desorption liquid was recovered by adding
removes the uranium ions of very weak interaction with both ammonium solution, NH4OH (35%) until reacheding to pH 8. The
pores and surface. Proton exchanging agent is the main mechanism form product (ammonium diurinate) was then filtered and heated
at 1073 K to obtain uranium oxide [34]. The residue after cooling is
Table 6 screened and examined by environmental scanning electron
Adsorption- desorption cycles of U (VI) ions by flax fiber. microscope (ESEM) (Fig. 8). This analysis indicates that the content
No. of cycle Adsorption (%) Adsorption capacity qe (mg/g) of uranium as U3O8 in the sintered yellow cake reached 98.83%.
1 93.50 27.27
2 88.50 25.80 The regeneration and reuse of the adsorbent material
3 83.71 24.78
The regenerated flax fibers were reused in the recycle process to
4 80.45 23.33
5 78.23 21.44
study the change in its adsorption capacity. The results of adsorp-
tion – desorption cycles are given in Table 6. The results show a

Table 7
Adsorption U (VI) capacities of flax fiber and other sorbents.

Adsorbents Adsorption condition Adsorption capacity (mg/g)


pH Time (min) Dose (g) Concentration Range (mg/l) Temperature (K)
Graphene oxide-activated carbon [3] 5.3 30 0.01 50 298 298.0
Orange peels [7] 4.0 60 0.30 25–200 303 15.91
Silicon dioxide nanopowder [14] 5.0 20 0.30 50–100 303 10.15
Modified Rice Stem [15] 4.0 180 0.20 5–60 298 11.36
N, P, and S Codoped Graphene [16] 5.0 25 0.01 5–100 298 294.1
Nanogoethite powder [17] 4.0 120 1.00 5–200 298 104.22
Iron/magnetite carbon composites [18] 5.4 50 0.15 20 298 203.94
Aluminum oxide nanopowder [23] 5.0 40 0.15 50–250 303 37.93
Powdered corncob [36] 5.0 60 0.30 25–100 303 14.21
Natural clay [37] 5.0 120 0.15 5–40 298 3.470
Flax fiber (The present work) 4.0 100 1.00 50–1000 323 40.90

Fig. 9. Block diagram of removal and recovery of U (VI) by flax fibers.


A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162 161

lowering in adsorption percent with increase in desorption cycles. qe was determined from Langmuir equation (6) as follows:
Table 7, shows the U(VI) uptake by flax fiber and other adsorbents
from liquid waste. The comparison of adsorption capacity values
qe ð1 þ K L C e Þ ¼ Q L K L C e ð25Þ
between flax fibers and other materials confirms that flax fibers
exhibit an acceptable absorption capacity of U(VI) from aqueous qe ¼ Q L K L C e =ð1 þ K L C e Þ ð26Þ
solutions. The block diagram of U(VI) uptake using flax fiber in By substituting qe in Eq. (15) the following equation is obtained:
the batch technique was shown in Fig. 9.
M=V ¼ ðC 0  C e Þ=ð1 þ K L C e Þ=ðQ L K L C e Þ ð27Þ
Design of batch adsorber
Eq. (22) is used to determine both flax fiber doses and the vol-
ume of wastewater introduced in the full scale batch unit
The data required to design a full scale of batch unit for removal
(Fig. 10b). Design data indicated that flax fiber has a good potential
of uranium ion from liquid wastes were determined from the
for adsorbing high concentrations of U (VI) ions from liquid wastes.
results of the best adsorption isotherm model which [36]. In this
work, a full-scale unit of batch technique was designed from data
of Langmuir isotherm. Fig. 10a shows a technique of batch-unit Conclusion
for U (VI) adsorption using flax fiber.
If that a liquid volume V (m3) of U (VI) of initial concentration C0 Flax fiber showed to be an acceptable adsorbent material for
(mg/l), was treated to a finial concentration Ce (mg/l) using adsor- removal and recovery of U (VI) with higher liquid concentrations.
bent mass M (g). Adsorption capacity of flax fiber was increased Equilibrium uranium capacity of flax fiber was 40.9 mg/g at pH 4
from q0 at time 0 to qe at equilibrium. The balance equation of and 323 K. Thermo studies showed that the uptake of U(VI) is an
batch-unit, was determined as follows: endothermic process between 301 K and 323 K and exothermic
in nature from 323 K to 333 K. The adsorption data obtained by lin-
VðC 0  C e Þ ¼ Mðqe  q0 Þ ¼ Mqe ð23Þ
ear and nonlinear showed both the Langmuir and pseudo second
When, q0 = 0, Eq. (14) be in the form: order models are the best fitting models. Regeneration process of
flax fibers have proved a lowering in adsorption percent with
M C0  C1
¼ M=V ¼ ðC 0  C e Þ=qe ð24Þ increase in desorption cycles. A full scale batch adsorber unit is
V q1 designed using the best adsorption isotherm model.

Fig. 10. Schematic diagram of a single-unit batch absorber.


162 A. Abutaleb et al. / Journal of Advanced Research 22 (2020) 153–162

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