Hydrometallurgy 216 (2023) 106022

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Extraction and separation of gallium by solvent extraction with 5-non­

yl-2-hydroxyacetophenone oxime: Fundamentals and a case study
Azza F. El Wakil, Salah A. Zaki, Doaa A. Ismaiel, Hend M. Salem, Ahmed H. Orabi *
Nuclear Materials Authority, P.O. Box 530, Maadi, Cairo, Egypt

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

Keywords: The rapid growth of the electronics and energy industries has necessitated an increased focus on strategic ele­
Gallium ments in recent years. Gallium is one of the most sought-after elements due to its widespread use in electronic
Solvent extraction components as well as nuclear and other energy-related applications. Gallium was extracted and separated using
Stripping
5-nonyl-2-hydroxyacetophenone oxime (NHAO), which was employed for the first time in this study. Traditional
5-nonyl-2-hydroxyacetophenone oxime
Separation
log DM-log [Extractant] analysis shows that the extractant has separated Ga as a complex of 2:1 (extractant:
Ore metal) ratio. Using 0.5 M NHAO in benzene with aqueous / organic ratio of 1/1, extraction of Ga (99.2%) was
completed in about 7 min at room temperature. Based on the McCabe–Thiele diagrams constructed, 2 stages are
sufficient for the extraction and stripping of Ga. The selectivity or separation factor (Ga /M) > 63 was obtained
for all interfering metal ions examined. Additionally, 0.5 M H2SO4 selectively stripped almost 98.8% of the Ga
from the loaded NHAO. The thermodynamic analysis demonstrated that Ga extraction by NHAO is an exothermic
process. Finally, the best extraction parameters for separating gallium from reference (NIM-L) and black mica
(BM) source materials bearing gallium were applied with good accuracy.

1. Introduction
Recently, novel approaches to recover so-called strategic elements,
like Ga, which are necessary in new technologies, have been investi­
gated (Macías-Macíasa et al., 2019) which benefitted the fields of au­
tomobiles, aerospace, and electronics industry (EC, 2010). Electronics,
nuclear, energy, and medicine all employ gallium, making it a critical
strategic component (Headlee and Richard, 1953; Habashi, 1997). The
use of gallium resources has received considerable attention because of
the predicted growth in demand for gallium in various domains in the
future (Frenzel et al., 2016). Gallium is found and extracted as a trace
component in bauxite, coal, diaspore, germanite sphalerite and zinc
minerals (Lemos et al., 2007; Wu et al., 2013; Liu et al., 2016; Lu et al.,
2017; Cheng et al., 2018; Zhang et al., 2019; Wang et al., 2020; Zhou
et al., 2020; Zhang et al., 2020). The gallium contents in granitic rocks
vary within a wide range (20–80 mg/kg). In sedimentary rocks, gallium
is substituting aluminium in clay minerals, and the gallium content
reaches 30–40 mg/kg. In carbonates and sandstone rocks, gallium rea­
ches about 3 mg/kg. Metal values such as REE, U, Nb, Ta, Th, Zr, and Ga
are found in abundance in the Abu Rushied region of Egypt’s Southern
Eastern Desert where black mica is abundantly found. Resources with
gallium grades of 190 mg/kg were found in southern Abu Rusheid
(Ibrahim et al., 2020). Obtaining gallium, a critical metal for the elec­
tronics industry, from multiple sources is critical from both economic
and environmental standpoints. Gallium recovery methods, including
ion flotation, ion exchange, fractional precipitation, electrochemical
extraction, solvent extraction, and liquid membrane, have been studied
in the literature (Rao et al., 2003; Kinoshita et al., 2004; Kumbasar and
Tutkun, 2006; Kinoshita et al., 2013; Thakare and Malkhede, 2014). The
traditional techniques for extracting gallium, such as chemical precipi­
tation and electrolysis (Chang, 2010; Hou, 2011; Mochalov et al., 2021),
are only useful for a limited number of purposes. On the other hand, the
products involved in chemical precipitation are often not friendly to the
environment. Electrolysis is a laborious, time-consuming, and costly
process that is utilized solely for the purpose of obtaining gallium in its
purest form. Other methods, such as emulsion liquid membrane sepa­
ration, resin adsorption foam separation, and flotation separation (de
Castro Dantas et al., 2002; Liu et al., 2006; Kinoshita et al., 2011; Luong
and Liu, 2014; Asadian and Ahmadi, 2020), are also effective, but their
preparation conditions are relatively harsh, and their costs are generally
high. Currently, solvent extraction is the most effective technique for
gallium recovery. In this context, research into the extraction of gallium

* Corresponding author.
E-mail address: A_orabi_chem@yahoo.com (A.H. Orabi).

https://doi.org/10.1016/j.hydromet.2023.106022
Received 17 July 2022; Received in revised form 16 January 2023; Accepted 16 January 2023
Available online 20 January 2023
0304-386X/© 2023 Elsevier B.V. All rights reserved.
A.F. El Wakil et al. Hydrometallurgy 216 (2023) 106022

from chloride media has been conducted using a number of different obtained with NH4Cl and NH4OH was filtered, and washed with 1%
reagents, including neutral amine and extractants such as Cyanex 923, ammonium chloride. Subsequently, the precipitate was dissolved in10
tributyl phosphate (TBP), N235 and Cyanex 925 (Gupta et al., 2007a, mL of 0.7 M NaOH and filtered again, to produce the Ga(III) leach
2007b; Geidarov, 2008; Ahmed et al., 2013; Liu et al., 2017; Macías- solution.
Macíasa et al., 2019), and acidic phosphate ester extractants including After preparation of Ga(III) leach solution, NHAO extractant
alkyl phosphate ester extractants such as P507 (EHEHPA), Cyanex 272, (Scheme 1, Merck, Germany) was then used to remove Ga(III) from the
and P204 (D2EHPA) (Lee et al., 2002; Zhang and Liu, 2014; Zhang et al., leach liquor. The extractant was diluted with benzene, and octanol was
2014; Zhang et al., 2019; Zhou et al., 2020; Zhang et al., 2020; Zhang added as a modifying agent to improve the hydrodynamic properties of
et al., 2021). It is difficult to employ these extractants because of their the system and avoid the creation of a third phase.
high operating costs, the requirement for a multi-stage stripping, their
poor application in acidic leach solutions, low selectivity, and the co- 2.2. Analytical procedures
extraction of numerous ions. Among the extractants utilized for gal­
lium extraction, acidic and oxime extractants were shown to be highly The major oxides in the acquired leach liquors (NIM-L and BM) were
effective and selective (Xiao, 2003; Wang et al., 2005; Lin et al., 2009; identified by the analytical methods reported by Harris (2015) and
Jiang et al., 2012; Nusen et al., 2016). Extractants such as hydroxy ox­ Marczenko and Balcerzak (2000) (S1). Meanwhile, other trace elements
imes hold great promise for the efficient separation and recovery of were analyzed using ICP-OES (Teledyne technologies), and Rigaku
gallium from its solutions through extraction. However, the selective EDXRF spectrometer NEX CG. The extractant (NHAO) and chelate (Ga)
extraction and recovery of gallium from the leachate of its ore using were measured using an FTIR spectrometer (Bruker, Germany) from
these oximes has not been extensively examined. Research on the Vector 22.
extractant 5-nonyl-2-hydroxyacetophenone oxime, particularly for co­
balt, nickel, copper and uranium separations, is ongoing (Zaki, 2022). 2.3. Extraction experiments
To the best of our knowledge, this is the first study to look at the 5-nonyl-
2-hydroxyacetophenone oxime as an extraction agent for gallium from In order to achieve the desired pH level in the gallium leach solution,
the leach liquid of a reference material (NIM-L) and black mica raw a 0.1 mol/L solution of sulfuric acid and a 0.1 mol/L solution of sodium
materials from Egypt’s Abu Rushied region in the Southern Eastern hydroxide were added. After achieving equilibrium in the aqueous
Desert. phase, the desired volume of the organic phase was also introduced into
a separating funnel and allowed to remain there for a predetermined
2. Experimental amount of time while shaking. After reaching equilibrium, the aqueous
phase and the organic phase were separated, and the concentration of
2.1. Preparation of leach liquor Ga(III) was determined using the methods described previously. The
distribution ratio (D) was calculated using Eq. (1), where Gai represents
An agitation leaching process with sulfuric acid (Wu et al., 2013; Liu the initial concentration of Ga(III), and Gaaq represents the concentra­
et al., 2016; Ibrahim et al., 2020) was used to produce the pregnant tion of Ga(III) that remains in the aqueous phase after the extraction
leach solutions (PLS) of reference (NIM-L) and Black mica materials (Jeffery et al., 1989). Eq. (2) was used to calculate the percentage of
(BM), which were then re-modified to work at a target pH. The clarified extraction, which is denoted by E. The volumes of the aqueous and
leach liquors (or PLSs) have different chemical compositions, which are organic solutions are denoted by Vaq and Vorg in Eqs. (1) and (2).
shown in Table 1. Solid ammonium chloride (NH4Cl) was added to the
PLS followed by ammonium hydroxide (NH4OH) to adjust the pH to 9.
Then, the gelatinous precipitate was filtered, and washed by 1%
ammonium chloride. The gelatinous precipitate was dissolved in 10 mL
of 0.7 M sodium hydroxide and filtered again, to produce Ga leach so­
lution. The objective of preparing the Gallium leach solution by using
ammonium hydroxide and ammonium chloride is the separation of the
tri-valent elements (see Table 3) from the leach solution by precipita­
tion. The addition of NH4Cl with the precipitating agent NH4OH has two
purposes: (1)- to decrease the ionization of ammonia solution by com­
mon ion (NH+ 4 ) effect and prevent the precipitation of Group IV cations
and Mg as hydroxides with Group III cations (as they require a higher
(OH− ) concentration), (2)- to help the coagulation of the gelatinous
precipitates of Group III.
As Ga(OH)3 is amphoteric it dissolves in excess alkali while other
hydroxides such as Fe(OH)3, and Mn(OH)3 which are less amphoteric do
not dissolve. This allows the separation of these elements in the mixed
precipitated hydroxides, produced by ammonium hydroxide and
ammonium chloride. When treated with excess alkali hydroxide, the
former (Ga) dissolves while the latter does not (Jeffery et al., 1989; El
Wakil, 2011; Harimu et al., 2021). Thus, the gelatinous precipitate
Scheme 1. 5-nonyl-2-hydroxyacetophenone oxime (NHAO).

Table 1
The chemical compositions of the two leach liquors.
Sample Concentration of ions (g/L)

Fe K Al Mn Ca Ti Ga Pb Zn Co Cr V Ni

BM 6.40 6.00 3.20 0.27 1.62 0.065 0.190 0.039 0.30 0.038 0.004 0.005 0.002
NIM-G 0.72 6.20 3.38 0.18 2.70 0.048 0.054 0.006 0.008 0.020 0.012 0.002 0.008

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A.F. El Wakil et al. Hydrometallurgy 216 (2023) 106022

(( ))
Gai − Gaaq Vaq
D= x (1)
Gaaq Vorg
⎛ ⎞
⎜ 100D ⎟
E=⎜ ⎟ (2)
⎝D + Vaq ⎠
Vorg
The investigated parameters utilized are displayed in Table 2.
3. Results and discussion
3.1. Effect of initial pH on gallium extraction
The initial pH value (pH0) of the solution directly affects the valence
or speciation state of metal ions, so the pH value of the solution is an
important factor that affects the interaction process of gallium with
NHAO extractant in aqueous solution. Under strongly acidic conditions,
gallium extraction is not favoured (see Eq. (3)). Consequently, the pH
value (pH0) of the solution in this part was controlled between 0.5 and
4.0. The pH of the mixture was not adjusted through the extraction
processes but the pHeq (equilibrium pH) was monitored after the
extraction experiment. All samples were placed in a shaker for 10 min at
room temperature. As can be seen from Fig. 1a, in the pH range of
0.5–4.0, the extraction % of Ga(III) by NHAO/benzene increases with
the increase of solution pH. Because H+ ions (from the acidic solution)
compete with the NHAO extractant at low pH levels, Ga(III) extraction
decreases. The extraction of Ga(III) by NHAO increases when the pH of
the aqueous media is raised to reach a maximum at pH 2–4. Distribution
of gallium ionic species in aqueous media at several pH values have been
reported: (i) Ga3+ is predominant at pH < 2.0, (ii) Ga(OH)2+ species
peaks at about pH 3, (iii) when pH is about 4, Ga(OH)+
2 reaches its
highest concentration, (iv) at pH 4.5, the neutral species, Ga(OH)03, has a
narrow range of predominance, (v) the negative species, Ga(OH)−4 , is the
dominant species in the pH range of 4–14, especially at alkaline pH
(Luong and Liu, 2014). The above explanation displays that the hydro­
lysis of gallium(III) ions are significantly dependent on pH. So, the
cationic species of gallium predominate in the pH region of 2–4 which
enhances the concentration of metal ions in solution to be extracted
(Dean, 1985; Luong and Liu, 2014; Bahri et al., 2016; Lu et al., 2017).
The result agreed with the use of other extractants reported earlier
(Lee et al., 2002; Zhang et al., 2003; Nusen et al., 2016; Zhang et al.,
2021). This may be attributed to a decrease in the protonation of the
NHAO extractant at higher pH levels. In addition, cationic species of
gallium (Ga3+, Ga(OH)2+, and Ga(OH)+ 2 ) predominate in this region
which enhances metal ions in solution to be extracted (Dean, 1985;
Bahri et al., 2016; Lu et al., 2017). In order to better study the extraction
performance of gallium on NHAO extractant, the pH value of the solu­
tions was set at 2 in the follow-up study. At this optimum pH, the
extraction % of gallium is 99.2% (Fig. 1a). Fig. 1(b) shows the variation
of ΔpH = (pHeq-pH 0) as a function of pH0. The positive deviation of ΔpH
below pH of 1.5 indicates that the H+ ions are consumed by the func­
tional group of the extractant, or by the Ga(III)-hydroxy species during
the extraction causing an increase in pH of the aqueous phase. On the
other hand, the negative deviation of ΔpH above pH 1.5 indicates that
the acidic –OH of oxime group of NHAO extractant lose H+ ions resulting
in decrease in pH of the aqueous phase.
The equilibration of a metal ion and reagent forms a metal chelate
during extraction as described by Nworie et al. (2018). So, the extraction
of gallium from aqueous media into an organic solvent ‘(o)’ containing a
ligand HR can be represented by the following equations:
Ga(OH)2 + + m(HR)(O) ⇌Ga(OH)2 Hm− n Rm(O) + nH+ (3)
where m, and n represent the number of moles and the Kex for the
extraction then becomes
[Ga(OH)2Hm− n Rm ](o)[H + ]n
Kex = (4)
[Ga(OH)2+ ][HR]m (o)
Substituting distribution ratio D in the above equation we get the
following equation.
D [H + ]n
Kex = (5)
[HR]m (o)
Log D = log Kex + m log [HR] + n pH (6)
A plot of log D vs. pH at a constant concentration of NHAO (0.5 M)
gives a straight line whose slope is 1.18 (Fig. 1c). So, the extraction
process using NHAO extractant will release one hydrogen ion in the
aqueous medium, similar to the behavior of gallium described previ­
ously (Nayak and Devi, 2017; Zhou et al., 2019).

Table 2
Main parameters investigated in the experiments.
Unit Test Varied parameter pH NHAO (M) Ga(III) (mg/L) Temp (K) A:O volume ratio Contact time
operation # (min)

Extraction 1 pH 0.5, 1, 2, 0.5 100 298 1:1 10

3, 4
2 NHAO 2 0.02, 0.05, 0.1, 0.2, 100 298 1:1 10
concentration 0.5, 0.7, 0.9
3 Contact time 2 0.5 100 298 1:1 1, 3, 5, 7, 10,
15
4 Ga(III) 2 0.5 25, 50, 75, 100, 125, 150, 175, 298 1:1 7
concentration 200, 250, 275,300
5 Temperature 2 0.5 100 298, 303, 308, 1:1 7
313, 318, 323
6 A: O ratio 2 0.5 100 298 2:1, 1:1, 1:2, 1:3, 7
1:4
Stripping Test Varied parameter Concentration of stripping agent Stripping agent Temp (K) O:A volume ratio Contact time
# (M) (min)
1 stripping agent 0.25 HCl, HNO3, H2SO4 298 1:1 10
type
2 H2SO4 0.1, 0.15, 0.5, 0.75, 1 H2SO4 298 1:1 10
concentration
3 Contact time 0.5 H2SO4 298 1:1 1, 2, 3, 5, 7,
10
4 O:A ratio 0.5 H2SO4 298 1:3, 1:2, 1:1, 2:1, 5
3:1, 4:1

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A.F. El Wakil et al. Hydrometallurgy 216 (2023) 106022

Fig. 1. Effect of pH0 on extraction efficiency (%) and distribution ratio (D) of Ga(III) using NHAO extractant: (a) extraction efficiency versus pH0, (b) ΔpH = pHeq-
pH 0 versus pH0, (c) a plot of log D verus pHeq (extraction condition: 100 mg/L metal ion, room temperature, 10 min contact time, 0.5 M extractant, and 1: 1 A:
O ratio).

3.2. Effect of NHAO concentration on gallium extraction
At first, the impact of 0.02–0.9 M NHAO extractant/benzene on Ga
(III) extraction was investigated using a phase ratio of 1:1 at room
temperature for approximately ten minutes, as shown in Fig. 2. Ac­
cording to the findings of this investigation, the low Ga(III) extraction of
18% with 0.02 M of NHAO extractant increased to 99.2% with 0.5 M of
NHAO extractant. The extraction efficiency did not change significantly
in the NHAO concentration range from 0.5 M up to 0.9 M. The NHAO
concentration of 0.5 M is the most suitable to ensure the complete
extraction of Ga(III).
3.3. Nature of extracted species
By examining both traditional slope analysis methods and experi­
mental data, we were able to analyze the stoichiometry of the mecha­
nism used to extract Ga. The slope value of Log D versus Log C
(concentration of NHAO) was around 2.1 (Fig. 3). Because of this, the
slope analysis method suggests that the extracted species has a compo­
sition of approximately 1:2 (metal to extractant). Based on the slope

Fig. 2. Effect of NHAO concentration on the extraction efficiency percent of Ga Fig. 3. Plot of log D vs. log C [extractant] for Ga extraction (extraction con­
(extraction conditions: 100 mg/L Ga(III), room temperature, 10 min contact ditions: 100 mg/L Ga(III), room temperature, 10 min contact time, 1: 1 A: O
time, 1: 1 A: O ratio, and initial pH =2). ratio, and initial pH =2).

4
A.F. El Wakil et al.
analyses, log D vs. pH (Fig. 1c) or extractant concentration (Fig. 3), the
probable mechanism of extraction is as follows:
2HR + Ga(OH)2 + ⇌Ga(OH)2 HR2 + H+ (7)
Fig. 4 shows a FTIR spectrum of the NHAO before and after Ga
extraction. More specifically the -OH, CH, CH2, CH3, C–C, C– – C, C–N,
and C–– N groups in the NHAO extractant are identified and reported in
Table 3. In addition, the infrared technique was used to further research
into the extraction mechanism as shown in Fig. 4b. After Ga(III) loading
onto NHAO, the peak of OH stretching was reduced and shifted to 3381
cm− 1, which suggests the coordination of the OH of extractant (NHAO)
to metal ions. The group of bands including 678 and 725 cm− 1 is
characteristic of Ga–O bands seen in hydroxo complexes (Hinchclife
and Ogden, 1973; Socrates, 1973; Yang et al., 2009). The vibrations of
the CH2, CH3, and CH groups did not alter, indicating that they are not
involved in the complexation with Ga(III).
3.4. Effect of contact time
In order to examine the effect of contact time on Ga(III) loading to
NHAO/benzene, the extraction experiment was carried out for a period
ranging from 1 to 15 min (Fig. 5). All the other conditions necessary for
extraction were kept the same throughout the process (Table 2). The
findings presented in Fig. 5 show that the extraction efficiency for Ga
(III) reaches 99.2% after only seven minutes; however, the prolonged
shaking duration of fifteen minutes has no effect on the extraction. This
suggests that Ga(III) is able to interact with the extractant and reach
equilibrium in seven minutes which was utilized in further research.
Fig. 4. FTIR spectra of (A) NHAO extractant, and (B) Ga–NHAO complex.
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Hydrometallurgy 216 (2023) 106022
3.5. Effect of initial Ga concentration
The influence of initial Ga concentration on its extraction by 0.5 M
NHAO/benzene at a fixed organic to aqueous phase ratio of 1:1 was
examined across the range of 25 mg/L to 300 mg/L (Table 2) from an
aqueous solution with an initial pH of 2. The collected data indicate that
the concentration of Ga(III) in the organic phase at equilibrium increases
as the initial Ga(III) concentration increases up to 238 mg/L but then
stays the same as the metal ion concentration is raised further (see
Fig. 6). This happens up to the point where the initial Ga concentration
reaches its maximum value.
3.6. Effect of temperature
In order to examine the effect of temperature on Ga(III) loading, the
experiments were carried out at different temperatures ranging from
298 K to 323 K (Fig. 7). All the other conditions necessary for extraction
were kept the same throughout the process (Table 2). An increase in
temperature from 298 to 323 K did not help the extraction of Ga(III), as
shown by the decrease in extraction efficiency from 99.2 to 97.9% when
the temperature was increased. In addition, a greater temperature would
result in a more significant increase in the extractant’s rate of volatili­
zation and degradation. The result agreed with the behavior of another
oxime reported earlier (Cheng et al., 2018). Because of this, subsequent
experiments were carried out at a temperature of 25 ◦ C (298 K) and the
extraction duration of seven minutes in order to achieve increased Ga
(III) extraction as well as good and rapid phase separation. Calculating
the change in relevant thermodynamic parameter can be done with the
help of the equation developed by Van’t Hoff (Suner and Lagos, 1958;
Orabi et al., 2021):
A.F. El Wakil et al. Hydrometallurgy 216 (2023) 106022

Table 3
Assignments peaks in FTIR spectra for NHAO extractant.
1
Assignment Wavenumber, cm− Ref.

O-H (stretching) 3396 James et al., 2009; Xiao-teng et al., 2019; Mohamed et al., 2019; Orabi, 2019
C–H (stretching) 2925 James et al., 2009; Xiao-teng et al., 2019; Mohamed et al., 2019; Orabi, 2019
CH3 (stretching) 2861 James et al., 2009; Xiao-teng et al., 2019; Mohamed et al., 2019; Orabi, 2019
CH2 (asymmetric) 1461 Nakanishi and Solomon, 1977; Mohamed et al., 2019; Orabi, 2019
C–N (stretching) 1294–1353 Salama et al., 2015, Nakanishi and Solomon, 1977; Mohamed et al., 2019; Orabi, 2019
C=N (stretching) 1613 Nakanishi and Solomon, 1977; Mohamed et al., 2019; Orabi, 2019
C=C (stretching) 1509 Timur and Paşa, 2018
C–C (stretching) 834–1111 Timur and Paşa, 2018

3.7. Loading capacity

The ability of NHAO to load gallium was evaluated by repeatedly

contacting a solution of 0.5 M NHAO in benzene with the same volume
of aqueous solutions containing 100 mg/L Ga(III) at a pH of 2 until there
was no further increase in the amount of gallium found in the organic
phase. By determining the differences in concentration found in each
contact, we were able to determine the overall concentration of Ga(III)
present in the organic phase (Fig. 9). After four interactions, it was

Fig. 5. Effect of contact time upon Ga(III) extraction efficiency by NHAO

extractant (extraction conditions: 100 mg/L Ga(III), room temperature, 0.5 M
extractant / benzene, 1: 1 A: O ratio, and initial pH = 2).

Δ logD/Δ(1/T) = –ΔH◦ /(2.303R), (8)

where R is the ideal gas constant (8.314 J mol− 1 K− 1); T is the absolute
temperature (K).
The line with 1537.6 slope for Ga(III) given in Fig. 8, corresponds to a
ΔH◦ value of − 29.44 kJ mol− 1. This value shows that Ga extraction by
NHAO is an exothermic process. Fig. 7. Effect of temperature upon Ga extraction efficiency by NHAO extractant
(extraction conditions: 7 min, 0.5 M NHAO/benzene, 100 mg/L Ga(III), initial
pH = 2, and 1: 1 A: O ratio).

Fig. 6. Effect of initial Ga concentration on its extraction by 0.5 M NHAO extractant / benzene; (O/A) =1; initial pH = 2; 7 min contact time; T = 298 K.

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A.F. El Wakil et al. Hydrometallurgy 216 (2023) 106022

Table 4
Effect of O/A ratio on the efficiency of Ga extraction with 0.5 M NHAO
extractant in benzene after equilibration*.
O/A ratio Ga concentration, mg/L Ga extraction efficiency, %

Aqueous phase Organic phase

2/1 0.5 49.8 99.5

1/1 0.8 99.2 99.2
1/2 10.5 197.0 89.5
1/3 20.5 238.5 79.5
1/4 40.0 240.0 60.0
*
Extraction conditions: 7 min, 100 mg/L Ga(III), initial pH = 2, at room
temperature.

Fig. 8. Plot of log D vs. reciprocal temperature for the Ga(III) extraction with
NHAO extractant in benzene.

discovered that the organic phase almost reached its saturation point
with Ga(III). This implies that the respective maximum loading of 0.5 M
NHAO is 240 mg/L in Fig. 9, which is slightly higher but consistent with
238 mg/L obtained in Fig. 6.

3.8. Influence of O/A phase ratio

In order to examine the effect of changing O/A ratio on the treatment

process, a series of experiments was carried out for O/A ratios ranging
from 2/1 to 1/4 (Table 4, and Fig. 10). An increase in O/A ratio from 1/1
to 1/4 did not help the extraction of Ga(III), as shown by the fact that the
efficiency of Ga(III) extraction decreased from 99.2 to 60% when the O/ Fig. 10. Effect of O/A ratio on the efficiency of Ga extraction with 0.5 M NHAO
extractant in benzene (extraction conditions: 7 min, 100 mg/L Ga(III), initial
A ratio was increased. Table 4 shows that, when the O/A ratio is set to 2/
pH = 2, at room temperature).
1, the extraction efficiency is extremely close to reaching its maximum
possible value.
ions loading: Ga > Cu > Fe > Ni > Al > Zn > Cd > Mg > Mn by the
NHAO extractant. Table 5 shows that NHAO can extract up to 97% of Ga
3.9. Effect of co-existing ions
(III), while extracting <35% of other metals. The separation factors (SF)
of Ga(III) to impurities using NHAO is above 63 for all the metal ions
Effect of other metal ions in the leach liquor must be studied in order
examined. This can be ascribed to the intrinsic properties of different
to determine which metal ions can be extracted by the extractant
metal ions and their affinity and stability with NHAO extractant. In
(NHAO) and compete with gallium. The common metal ions (Fe3+, Al3+,
addition, competitive effects play a role in the separation process with
Mn2+, Cu2+, Mg2+, Zn2+, Co2+, Ni2+, Cd2+) in leach liquor were selected
NHAO, which has a high extraction efficiency for Ga(III) at the opti­
as co-existing competitive ions, and the concentration of each metal ion
mized conditions. The same behavior was also observed in the extraction
species was set at 10 mg in a solution of 100 mL (100 mg/L). The ICP-
of Ga(III) with other extractants (Zhang et al., 2003; Vartak and Shinde,
OES was used to track the variations in the concentration of each
1998). Also, the reason for the higher extraction of Cu(II) compared to
metal ion. The results in Table 4 indicate a descending order of metal
other elements (such as Fe, Ni, Co, Zn, Cd, Mn) may be due to the high
ability of oxime type extractants (such as NHAO) for Cu(II) extraction
compared to other elements (Lasheen et al., 2014; Reddy et al., 2007;
Sahu et al., 2004; Panigrahi et al., 2009; Kordosky, 1987; Parija and
Sarma, 2000; Reddy and Priya, 2005; Ocio and Elizalde, 2006; Owusu,
1999). These earlier research works found that the co-extraction of other

Table 5
Effect of some interfering metal ions upon NHAO extractant*.
Metal Conc. In organic phase, Distribution Separation factor
cations mg/L ratios Ga/M

Ga(III) 97 32.3
Cu(II) 34 0.51 63.4
Fe(III) 26 0.35 92.4
Ni(II) 24 0.32 101
Al(III) 21 0.27 120
Zn(II) 7 0.07 462
Cd(II) 6 0.06 539
Mg(II) 3 0.03 1078
Mn(II) 2 0.02 1617
Fig. 9. Effect of the number of stages on the cumulative extraction of Ga(III)
*
from a 100 mg/L aqueous solution by 0.5 M NHAO extractant / benzene; (O/A) Extraction conditions: 0.5 M NHAO, 7 min, initial pH = 2, initial concen­
=1; initial pH = 2; T = 25 ◦ C. tration 100 mg/L, 1/1 A/O ratio, at room temperature.

7
A.F. El Wakil et al. Hydrometallurgy 216 (2023) 106022

metals such as Fe, Ni, Co, Zn, Cd, Mn at lower pH of 1–3 range was
undetectable or < 2 mg/L.

3.10. The impact of the type and concentration of stripping agent

Quantitative stripping of Ga(III) ions was performed using a variety

of stripping agents (0.25 M) and the NHAO loaded sorbents under
investigation in this study using the stripping conditions described in
Table 2. Gallium was loaded into 0.5 M NHAO / benzene after numerous
interactions with the same amount of the produced aqueous solution.
The proportion of Ga that was removed from the loaded NHAO was
determined. The three acids nitric, hydrochloric, and sulfuric have been
used as stripping agents for this purpose. Compared with the three acids,
sulfuric acid has the best stripping effect on Ga ions (50%) followed by
HCl (38%), and the minimal values by HNO3 (30%). Consequently,
H2SO4 was employed in the ensuing tests.
Fig. 12. Effect of contact time upon gallium stripping efficiency from the
In order to examine the effect of H2SO4 concentration, stripping of
loaded NHAO extractant using 0.5 M H2SO4 at room temperature and 1: 1 A:
Ga(III) from loaded NHAO was carried out with H2SO4 solutions of
O ratio.
concentrations ranging from 0.1 M to 1 M (Table 2). The findings pre­
sented in Fig. 11 show that the stripping efficiency for Ga reaches 98.8%
after using 0.5 M H2SO4; however, the increase in H2SO4 concentration
to 1 M has no further improvement on the stripping efficiency. Clearly,
good gallium stripping was obtained with H2SO4 solutions at low
concentration.

3.11. Effect of contact time and O/A phase ratio

In order to examine the effect of contact time on the stripping pro­

cess, the stripping of Ga(III) from loaded NHAO / benzene phase was
carried out for a period ranging from 1 to 10 min (Table 2). The findings
presented in Fig. 12 show that the stripping efficiency for Ga(III) reaches
98.8% after only 5 min; however, the prolonged shaking duration of ten
minutes has no effect on the stripping. Because of this, the duration of
five minutes was utilized in further studies.
Gallium was stripped under various O/A ratios with respect to
loaded organic phases, ranging from 1/3 to 4/1, in order to explore the
influence of the O/A ratio while maintaining other parameters un­
changed (Table 2). The stripping efficiency decreases from 98.8% to
68% as the O/A ratio increases from 1/3 to 4/1, as shown in Fig. 13. Fig. 13. Effect of organic/aqueous phase ratio upon Ga stripping efficiency
Therefore, a ratio of A:O that is equal to one achieves the highest from the loaded extractant using 0.5 M H2SO4 at room temperature for 5 min
possible level of gallium stripping efficiency. contact time.

3.12. Extraction and stripping distribution isotherms and McCabe–Thiele

diagrams for Ga(III)

The distribution isotherm for gallium extraction was determined by

Fig. 11. Effect of H2SO4 molarity upon gallium stripping efficiency from 0.5 M
loaded NHAO extractant at room temperature for 10 min contact time and 1: 1
A: O ratio.
utilizing the chosen oxime extractant in conjunction with the feed so­
lution that contained 0.95 mg/L Ga(III) and employing O/A ratios of 2:1,
1:1, 1:2, 1:3, and 1:4 at a temperature of 298 K and the pH of the solution
was set at 2.0 (Table 2). By executing solvent extraction experiments
using the different aqueous to organic phase ratios mentioned above, the
equilibrium loading isotherm for gallium was determined. Fig. 14 shows
the concentration of Ga(III) in the organic phase as a function of that in
the aqueous phase. An assumption of the phase ratio (A/O) is necessary
as the slope of the operating line. The red vertical line in Fig. 14 rep­
resents the concentration of Ga(III) in the feed solution. According to the
McCabe–Thiele diagram that was built in Fig. 14, there are two stages
that need to be completed in order to get the concentration of gallium in
the raffinate down to <1 mg/L, saturate the organic extractant phase,
and deplete the gallium in the leach liquor (PLS).
The gallium stripping distribution isotherm was constructed utilizing
a loaded chosen oxime extractant that had 0.942 mg/L Ga(III) in
conjunction with a strip solution that contained 0.5 M H2SO4 and
employing O/A ratios of 4:1, 3:1, 2:1, 1:1, 1:2, and 1:3 respectively
(Table 2). According to the McCabe–Thiele diagram for stripping in
Fig. 15, two steps are required in order to bring the concentration of

8
A.F. El Wakil et al. Hydrometallurgy 216 (2023) 106022

Fig. 14. The McCabe–Thiele diagram for Ga extraction by 0.5 M NHAO/benzene for 7 min contact time at room temperature, initial pH = 2.0 and A/O ratio of 2.5/1.

Fig. 15. The McCabe–Thiele diagram for Ga stripping from loaded selected organic solution consisting of 0.5 M NHAO/benzene with 0.5 M H2SO4 strip solution for
5 min contact time at room temperature and A/O ratio of2.5/1.

Table 6
Comparison between the behavior of impurities in the two leaching solutions NIM-L and BM before and after treatment for purification and stripping.
Sample Concentration of ions (mg/L)

Ga Fe Al Mn Ca Ti Pb Zn Co Cr V Ni

BM before purification 190 6400 3200 270 1620 65 39 300 38 4 5 2

BM after purification 190 0.06 256 50 0.4 5 8 111 8 0.5 0.6 0.05
BM raffinate after extraction 2.7 0.04 202 49 0.3 3.9 7.4 103 5.3 0.3 0.4 0.04
BM after stripping 185 0.02 53.8 1 0.1 1.1 0.6 7.8 2.7 0.2 0.2 0.01
NIM-G before purification 54 7200 3380 180 2700 48 6 8 20 12 2 8
NIM-G after purification 54 0.06 277 30 0.8 4 1 3 4.5 2.6 0.03 0.8
NIM-G raffinate after extraction 0.5 0.04 219 29.4 0.6 3.2 0.9 2.8 3 1.7 0.02 0.6
NIM-G after stripping 53 0.03 58.2 0.6 0.2 0.8 0.1 0.2 1.5 0.9 0.01 0.2

9
A.F. El Wakil et al.
gallium in the stripped organic solution down to <1.5 mg/L.
3.13. Case study
It was decided to conduct a case study of extraction through utilizing
1 L of NIM-L and BM sulfate leach liquors (Table 1) with Ga(III) con­
centrations of 54 mg/L and 190 mg/L, respectively. To reduce the matrix
interferences before extraction process, the two leach liquors were firstly
treated as follows; solid ammonium chloride was added to each leach
liquor followed by ammonium hydroxide to adjust the pH to 9. The
gelatinous precipitate was filtered and washed with 1% ammonium
chloride and dissolved in 10 mL of 0.7 M sodium hydroxide to produce
purified Ga(III) solution with the least contaminants as shown in
Table 6. The purified Ga(III) solutions were contacted with 0.5 M 5-
nonyl-2-hydroxyacetophenone oxime (NHAO) extractant in benzene
under optimal conditions of an aqueous / organic ratio of 1/1 at room
temperature for about 7 min in 2 stages. A Ga(III) extraction efficiency of
99% and 98.6% were achieved from the purified NIM-L and BM sulfate
leach liquors, respectively. A solution of 0.5 M H2SO4 was used to strip
Fig. 16. A technological flow sheet for the extraction of gallium from Black mica raw material (a case study of extraction through utilizing 1 L of BM sulfate leach
liquors with Ga(III) concentrations of 190 mg/L (Tables 1 and 6).
10
Hydrometallurgy 216 (2023) 106022
the extracted Ga under optimal conditions of an aqueous-organic-phase
one at room temperature for about 5 min in 2 stages. As a consequence,
it was discovered that the 5-nonyl-2-hydroxyacetophenone oxime
(NHAO) was capable of successfully separating Ga(III) from the actual
leach liquors. The flow chart (Fig. 16) summarizes Ga separation process
steps with NHAO from Black mica leach liquor. The concentration of Ga
(III) in the final strip liquors were 0.053 g/L and 0.185 g/L in the two
streams from NIM-L and BM.
4. Conclusion
5-nonyl-2-hydroxyacetophenone oxime (NHAO) is used for extract­
ing and separating Ga(III) during the chemical treatment of Black mica
raw material. The factors of extraction and stripping of Ga(III) have been
optimized. Extraction of Ga(III) is shown to have taken place in a 2:1
(Extractant: metal) ratio according to slope analysis. Using 0.5 M NHAO
in benzene, one aqueous-organic-phase extraction of 99.2% Ga(III) was
completed in about 7 min at room temperature. All interfering metal
ions were found to have a selectivity or separation factor (SF of Ga/M) >
A.F. El Wakil et al.
63. Additionally, 0.5 M H2SO4 selectively removed almost 98.8% of Ga
from the loaded NHAO using 5 min shaking time. The exothermic nature
of NHAO’s Ga extraction was revealed through thermodynamic analysis
(ΔHo = − 29.44 kJ mol− 1). Finally, the best extraction parameters for
separating gallium from reference (NIM-L) and black mica (BM) source
materials bearing gallium were applied with good accuracy.
Credit authorship contribution statement
Azza F. El Wakil: Methodology, Conceptualization, Investigation,
review & editing. Salah A. Zaki: Data curation, Writing -review & edit­
ing. Doaa A. Ismaiel: Project administration, Investigation, Formal
analysis, Writing -review & editing. Hend M. Salem: Formal analysis,
Data curation, Conceptualization, Writing - original draft. Ahmed H.
Orabi: Conceptualization, Methodology, Validation, Investigation, Su­
pervision, Project administration, Formal analysis, Writing -review &
editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge the support and assistance
provided by our institution (Nuclear Materials Authority).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.hydromet.2023.106022.
References
Ahmed, I., El-Nadi, Y., El-Hefny, N., 2013. Extraction of gallium (III) from hydrochloric
acid by Cyanex 923 and Cyanex 925. Hydrometallurgy 131-132, 24–28.
Asadian, H., Ahmadi, A., 2020. The extraction of gallium from chloride solutions by
emulsion liquid membrane: optimization through response surface methodology.
Miner. Eng. 148 (15), 106207.
Bahri, Z., Rezai, B., Kowsari, E., 2016. Selective separation of gallium from zinc using
flotation: effect of solution pH value and the separation mechanism. Miner. Eng. 86,
104–113. https://doi.org/10.1016/j.mineng.2015.12.005.
Chang, L., 2010. Study on Extraction of Rare Metal Ge and Ga by Complexation of
Tannic. Chinese Academy of Forestry, Beijing, China.
Cheng, B., Zhang, T., Zhang, K., Cao, Z., Zeng, L., 2018. Recovery of germanium from
acid leach solutions of zinc refinery residue using an oxime extractant of HBL101.
Metall. Res. Technol. 115 (5), 510–515.
de Castro Dantas, T., de Lucena Neto, M., Dantas Neto, A., 2002. Gallium extraction by
microemulsions. Talanta 56, 1089–1097.
Dean, J., 1985. Lange’s Handbook of Chemistry, 13th ed. McGraw-Hill Book Co., New
York.
EC, European Commission, 2010. Critical Raw Materials for the EU, Report of the Ad-Hoc
Working Group on Defining Critical Raw Materials, European Commission,
Enterprise and Industry, 2010. https://ec.europa.eu/growth/toolsdatabases/eipra
wmaterials/en/system/files/ged/79%20report-b_en.pdf/.
El Wakil, A., 2011. Development of a Derivative Spectrophotometric Method for the
Determination of Gallium in Geological Materials. Ph D Thesis,. Chemistry
Department, Faculty of Science, Ain Shams University, Cairo, Egypt.
Frenzel, M., Ketris, M., Seifert, T., Gutzmer, J., 2016. On the current and future
availability of gallium. Res. Policy 47, 38–50.
Geidarov, A., 2008. Extractive recovery of gallium(III) from acid sulfate solutions with
primary amines. Russ. J. Appl. Chem. 81, 2084–2087.
Gupta, B., Mudhar, N., Begum, Z., Singh, I., 2007a. Extraction and recovery of Ga(III)
from waste material using Cyanex 923. Hydrometallurgy 87 (1–2), 18–26.
Gupta, B., Mudhar, N., Singh, I., 2007b. Separations and recovery of indium and gallium
using bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272). Sep. Purif. Technol.
57 (2), 294–303.
Habashi, F., 1997. Handbook of Extractive Metallurgy. Die Deutsche Bibliothek, 3rd ed.
Wiley-VCH, Germany.
Harimu, L., Lamuru, A., Nurlansi, Tisan, Rudi, La, Mulyana, W., Haeruddin, 2021.
Effectiveness of ammonium hydroxide precipitate iron and dimethylglyoxime
precipitate nickel in ferronickel and limonite soil samples. AIP Conf. Proc. 2360,
050021 https://doi.org/10.1063/5.0060295.
11
Hydrometallurgy 216 (2023) 106022
Harris, D., 2015. Quantitative Chemical Analysis, 9th edition. Freeman, W. H, p. 272.
Headlee, A., Richard, G., 1953. Elements in coal ash and their industrial significance. Ind.
Eng. Chem. 45 (3), 548–551.
Hinchclife, A., Ogden, J., 1973. J. Phys. Chem. 2537.
Hou, J., 2011. The Experimental Study of Contain Gallium Pig iron Electrolysis
Separation. Xihua University, Chengdu, China.
Ibrahim, M., Orabi, A., Falila, N., Ismaiel, D., Salem, D., 2020. Processing of the
mineralized Black Mica for the recovery of uranium, rare earth elements, niobium,
and tantalum. Hydrometallurgy 197, 105474. https://doi.org/10.1016/j.
hydromet.2020.105474.
James, D., Venkateswaran, G., Rao, T., 2009. Removal of uranium from mining industry
feed simulant solutions using trapped amidoxime functionality within a mesoporous
imprinted polymer material. Microporous Mesoporous Mater. 119, 165–170.
https://doi.org/10.1016/j.micro meso. 2008. 10. 011.
Jeffery, G., Bassett, J., Mendham, J., Denney, R., 1989. Vogel’s Textbook of Quantitative
Chemical Analysis, 5th ed. John Wiley and sons Inc., New York.
Jiang, Y., Zhao, L., Wang, H., Jiang, X., 2012. Experimental study on recovering gallium
and germanium from gallium and germanium-leaching solution at high-pressure.
China Res. Comp. Utili. 30 (6), 25–27.
Kinoshita, T., Akita, S., Nii, S., Kawaizumi, F., Takahashi, K., 2004. Solvent extraction of
gallium with non-ionic surfactants from hydrochloric acid solution and its
application to metal recovery from zinc refinery residues. Sep. Purif. Technol. 37,
127–133.
Kinoshita, T., Ishigaki, Y., Shibata, N., Yamaguchi, K., Akita, S., Kitagawa, S.,
Kondou, H., Nii, S., 2011. Selective recovery of gallium with continuous counter-
current foam separation and its application to leaching solution of zinc refinery
residues. Sep. Purif. Technol. 78 (2), 181–188.
Kinoshita, T., Ishigaki, Y., Shibata, N., Akita, S., Kondou, H., Nii, S., 2013. Selective
recovery of gold (III) via continuous counter-current foam separation from
hydrochloric acid solution – effects of foam and column sizes on separation
performance. Sep. Purif. Technol. 116, 335–341.
Kordosky, G., 1987. The Chemistry of Metals Recovery Using lix Reagents. Henkel
Corporation, Mineral Industry Division.
Kumbasar, R., Tutkun, O., 2006. Selective separation of gallium from acidic leach
solutions by emulsion liquid membranes. Sep. Sci. Technol. 41, 2825–2847.
Lasheen, T., Ibrahim, M., Hassib, H., Helal, A., 2014. Recovery of molybdenum from
uranium bearing solution by solvent extraction with 5-Nonylsalicylaldoxime.
Hydrometallurgy 146, 175–182.
Lee, M., Ahn, J., Lee, E., 2002. Solvent extraction separation of indium and gallium from
sulphate solutions using D2EHPA. Hydrometallurgy 63, 269–276.
Lemos, V., Santos, M., Santos, E., Santos, M., Santos, W., Souza, A., Jesus, D., Virgens, C.,
Carvalho, M., Oleszczuk, N., 2007. Application of polyurethane foam as a sorbent for
trace metal pre-concentration-a review. Spectrochim. Acta Part B 62, 4–12.
Lin, J., Wang, H., Gao, Y., Zhao, L., Zhang, L., 2009. Preparation and application of a
novel extractant for Ga and Ge. Nonferrous Met. 61 (2), 84–87.
Liu, J., Chen, H., Chen, X., Guo, Z., Hu, Y., Liu, C., Sun, Y., 2006. Extraction and
separation of In(III), Ga(III) and Zn(II) from sulfate solution using extraction resin.
Hydrometallurgy 82, 137–143.
Liu, F., Liu, Z., Li, Y., Liu, Z., Li, Q., Li, Z., 2016. Extraction of gallium and germanium
from zinc refinery residues by pressure acid leaching. Hydrometallurgy 164,
313–320.
Liu, F., Liu, Z., Li, Y., Wilson, B., Liu, Z., Zeng, L., Lundstrom, M., 2017. Recovery and
separation of gallium (III) and germanium (IV) from zinc refinery residues: part II:
solvent extraction. Hydrometallurgy 171, 149–156.
Lu, F., Xiao, T., Lin, J., Ning, Z., Long, Q., Xiao, L.H., Huang, F., Wang, W.K., Xiao, Q.X.,
Lan, X.L., Chen, H.Y., 2017. Resources and extraction of gallium: a review.
Hydrometallurgy 174, 105–115.
Luong, H., Liu, J., 2014. Flotation separation of gallium from aqueous solution-effects of
chemical speciation and solubility. Sep. Purif. Technol. 132, 115–119.
Macías-Macíasa, K., Ceniceros-G’omeza, A., Guti’errez-Ruiza, M., Gonz’alez-Ch’avezb, J.
L., Martínez-Jardinesc, L.G., 2019. Extraction and recovery of the strategic element
gallium from an iron mine tailing. J. Environ. Chem. Eng. 7, 102964.
Marczenko, Z., Balcerzak, M., 2000. Separation, Preconcentration and
Spectrophotometry in Inorganic Analysis. Elsevier, Amsterdam, pp. 85–440.
Mochalov, L., Logunov, A., Vorotyntsev, V., 2021. Preparation of gallium of the special
purity for semiconductors and optoelectronics. Sep. Purif. Technol. 258 (1), 118001.
Mohamed, B., Guirguis, L., Orabi, A., Khalil, L., 2019. Extraction of thorium (IV) with N-
methyl-N, N, N-trioctylammonium chloride from monazite acidic leach liquor and its
use for spectrophotometric determination. Radiochemistry 61 (5), 569–578.
Nakanishi, K., Solomon, P., 1977. Infrared Absorption Spectroscopy, , 2nd ed.1977.
Holden-Day, Oakland, CA, p. 34.
Nayak, S., Devi, N., 2017. Studies on extraction of gallium (III) from chloride solution
using Cyphos IL 104 and its removal from photodiodes and red mud.
Hydrometallurgy 171, 191–197.
Nusen, S., Chairuangsri, T., Zhu, Z., Cheng, C., 2016. Recovery of indium and gallium
from synthetic leach solution of zinc refinery residues using synergistic solvent
extraction with LIX 63 and Versatic 10 acid. Hydrometallurgy 160, 137–146.
Nworie, F., Nwabue, F., John, J., 2018. Extraction of chromium(III) and manganese(II)
with N, NI-ethylenebis(salicylimine)(H2EBSI) in acid medium: determination of
stability constant and thermodynamic parameters of the extracted species. Chem.
Sci. Int. J. 24 (3), 1–7.
Ocio, A., Elizalde, M., 2006. Copper (II) extraction from phosphoric acid media by 5-
dodecylsalicylaldoxime (LIX 622). Solvent Extr. Ion Exchange 24, 861–875.
Orabi, A., 2019. Extraction of uranium from carbonate solution using synthesized Schiff
base and its application for spectrophotometric determination. Chem. Pap. 73,
1713–1730. https://doi.org/10.1007/s11696-019-00724-x.
A.F. El Wakil et al.
Orabi, A., Mohamed, B., Ismaiel, D., Elyan, S., 2021. Sequential separation and selective
extraction of uranium and thorium from monazite sulfate leach liquor using
dipropylamine extractant. Miner. Eng. 172, 107151 https://doi.org/10.1016/j.
mineng.2021.107151.
Owusu, G., 1999. Selective extraction of copper from acidic zinc sulfate leach solution
using LIX 622. Hydrometallurgy 51, 1–8.
Panigrahi, S., Parhi, P., Sarangi, K., Nathsarma, K., 2009. A study on extraction of copper
using LIX 84-I and LIX 622N. Sep. Purif. Technol. 70, 58–62.
Parija, C., Sarma, P., 2000. Separation of nickel and copper from ammoniacal solutions
through co-extraction and selective stripping using LIX84 as the extractant.
Hydrometallurgy 54, 195–204.
Rao, K., Sarangi, D., Dash, P., Chaudhury, G., 2003. Preferential extraction of gallium
from Bayer liquor using ion exchange chelating resin containing hydroxamic acid
functional group. J. Chem. Technol. Biotechnol. 78, 555–561.
Reddy, B., Priya, D., 2005. Process development for the separation of copper (II), nickel
(II) and zinc (II) from sulphate solutions by solvent extraction using LIX 84-I. Sep.
Purif. Technol. 45, 163–167.
Reddy, B., Park, K., Mohapatra, D., 2007. Process development for the separation and
recovery of copper from sulphate leach liquors of synthetic Cu–Ni–Co–Fe matte
using LIX 84 and LIX 973N. Hydrometallurgy 87, 51–57.
Sahu, S., Agrawal, A., Pandey, B., Kumar, V., 2004. Recovery of copper, nickel and cobalt
from the leach liquor of a sulphide concentrate by solvent extraction. Miner. Eng. 17,
949–951.
Salama, H., Saad, G., Sabaa, M., 2015. Synthesis, characterization and biological activity
of Schiff bases based on chitosan and arylpyrazole moiety. Int. J. Biol. Macromol. 79,
996–1003. https://doi.org/10.1016/j.ijbiomac.2015.06.009.
Socrates, G., 1973. Infrared Characteristic Group Frequencies. Wiley, New York.
Suner, A., Lagos, A., 1958. Recovery of uranium from the Malargue, Merdoza, mineral by
ionic exchange. In: Proc.Int. Conf. on the Peaceful Uses of Atomic Energy, Geneva,
p. 3.
Thakare, Y., Malkhede, D., 2014. Solvent extraction and separation of gallium (iii) using
hexaacetato calix (6) arene. Sep. Sci. Technol. 49, 1198–1207.
Timur, M., Paşa, A., 2018. Synthesis, characterization, swelling, and metal uptake studies
of aryl cross-linked chitosan hydrogels. ACS Omega 3, 17416–17424.
Vartak, S., Shinde, V., 1998. An extraction study of gallium, indium and thallium using
TPASO as an extractant. Talanta 45, 925–930.
12
Hydrometallurgy 216 (2023) 106022
Wang, H., Lin, J., Wang, C., Zhang, L., Liu, S., 2005. Study on application of a new
extractant G315 for gallium and germanium. J. Guangdong Non-Ferrous Met. 15,
8–11.
Wang, Y., Wang, H., Li, X., Zheng, C., 2020. Study on the improvement of the zinc
pressure leaching process. Hydrometallurgy 195, 105400.
Wu, X., Qin, W., Wu, S., Ma, X., Niu, Y., Yang, C., 2013. Recovery of gallium from zinc
concentrate by pressure oxygen leaching. Rare Metals 32 (6), 622–626.
Xiao, H., 2003. Study of recovery of gallium from indium residue. Rare Metals Cemented
Carbides 31 (2), 5–7.
Xiao-teng, Z., Dong-mei, J., Yi-qun, X., Jun-chang, C., Shuai, H., Liangshu, X., 2019.
Adsorption of uranium (VI) from aqueous solution by modified rice stem.
J. Chemother. 2019, 1–10. https://doi.org/10.1155/2019/6409504.
Yang, J., Zhao, Y., Frost, R., 2009. Spectrochimica acta part a: molecular and
biomolecular spectroscopy infrared and infrared emission spectroscopy of gallium
oxide-GaO(OH) nanostructures. Spectrochim. Acta A 74, 398–403.
Zaki, S., 2022. Extraction of uranium with 2-Hydroxy-5-nonylacetophenone Ketoxime.
Radiochemistry 64 (1), 23–29. https://doi.org/10.1134/S1066362222010040.
Zhang, K., Liu, Z., 2014. Extraction and separation of gallium ion with iron and zinc ions
in sulfuric acid system with P507. Chin. J. Process. Eng. 14 (3), 427–432.
Zhang, X., Yin, G., Hu, Z., 2003. Extraction and separation of gallium, indium and
thallium with several carboxylic acids from chloride media. Talanta 59, 905–912.
Zhang, K., Cao, Z., Xiao, L., Liu, Z., 2014. Extraction of gallium from sulfuric acid
solutions with extractant P507. Min. Metall. Eng. 34 (6), 90–93.
Zhang, K., Liu, Z., Liu, Y., Cao, H., Zhu, W., 2019. Recovery of gallium from strong acidic
sulphate leach solutions of zinc refinery residues using a novel phosphate ester
extractant. Hydrometallurgy 185, 250–256.
Zhang, K., Liu, Z., Liu, Y., Cao, H., 2020. Study on extraction performance of gallium
from sulfuric acid medium by P204. Nonferrous Metals 3, 50–54.
Zhang, K., Qiu, L., Tao, J., Zhong, X., Lin, Z., Wang, R., Liu, Z., 2021. Recovery of gallium
from leach solutions of zinc refinery residues by stepwise solvent extraction with
N235 and Cyanex 272. Hydrometallurgy 205, 105722. https://doi.org/10.1016/j.
hydromet.2021.105722.
Zhou, X., Zhang, Z., Kuang, S., Li, Y., Ma, Y., Li, Y., Liao, W., 2019. Recovery of Ga(III)
from chloride solutions by solvent extraction with Cextrant 230. Hydrometallurgy
185, 76–81.
Zhou, M., Li, D., Tian, Q., Guo, X., Xu, Z., Yue, X., 2020. Research progress on separation
and recovery of gallium from secondary resources. Nonferrous Metals Sci. Eng. 11
(5), 45–51.