Journal of Water Process Engineering 42 (2021) 102138

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Journal of Water Process Engineering

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

Selective recovery of zinc from mining sulfuric liquor employing aqueous

two-phase systems
Daniela da Silveira Leite a, Roberta Condé de Assis a, Junielly Tomaz Domingues a,
Pablo Luis Gutierrez Carvalho a, Mateus Carvalho Monteiro de Castro b,
Gustavo Henrique da Cruz a, Izabella Cristina Gonçalves Silva a, Guilherme Dias Rodrigues a, *
a
Laboratório de Soluções Analíticas Verdes (LaSAV), Departamento de Química, Instituto de Ciências Exatas (ICEx), Universidade Federal de Minas Gerais (UFMG), Av.
Presidente Antônio Carlos, 6627, Pampulha, Belo Horizonte, MG, 31270-901, Brazil
b
ATPX – Soluções em hidrometalurgia Ltda, Brazil

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

Keywords: Zinc recovery is extremely important due to the chemical and physical properties of this metal. Liquid-liquid
Zinc extraction technique allows the selective recovery of zinc, leading to a high purity product. For the first time,
Magnesium a concentrated mining sulfuric liquor as a stock solution for in situ preparation of an Aqueous Two-Phase System
Recovery
(ATPS) in a hydrometallurgical process. This liquor is an overly complex solution with a high content of metal
Aqueous two-phase systems
Mining liquor
ions, especially Zn2+ and Mg2+. ATPS technique has already shown good results when compared to traditional
Separation solvent extraction techniques and can be considered a greener technique. The proposed method was optimized to
obtain selective Zn2+ extraction by studying the parameters: the nature of the ATPS-forming polymer and their
concentration in the stock solution; the effect of the salt added to the system; the concentration of extractant
agent and the mass ratio between both phases. The optimized methodology made it possible to extract (91.5 ±
0.1)% of Zn2+ and (18.2 ± 0.1)% of Mg2+ from the liquor in three extraction steps. In the stripping step which
used NaOH as the precipitating agent, about 65 % of Zn2+ was selectively recovered at pH = 6.00 and at pH =
9.00 the recovery of Zn2+was close to 80 %. Furthermore, for the first time it was proven that the polymer and
the extracting agent (following the stripping step) are reusable components of the ATPS. A high extraction ef­
ficiency (%EZn ~ 45 %) was achieved in one extraction step using the recycled extraction phase without any
adjustment.

1. Introduction exchange, membrane separation [6,7] and liquid-liquid extraction [8,9].

Zinc is essential as a micronutrient for human health and is the fourth
most used metal in the world, standing behind iron, aluminum, and
copper. It can also be recycled without losing its physicochemical
properties. Around 60 % of the produced zinc is used in galvanizing
processes as a sacrificial metal. The estimated world zinc consumption is
16 million tons per year, in which 12 million tons come from primary
sources and 4 million from recycled sources [1]. According to the Lon­
don metal exchange website, the commercial value of this metal is US$
2585 per ton [2].
There are a variety of metallurgical processes that can be employed
for the recovery of zinc, mainly pyrometallurgical [3,4] and hydro­
metallurgical methodologies [4], such as precipitation [5], ion
Among these processes, solvent extraction (SX) is a strategical hydro­
metallurgical separation process used on a commercial scale, due to the
growing demand for high-purity metals [10], the strict environmental
regulations, the demand of lower production costs and the decreased
production in high-quality ore reserves.
The process of obtaining zinc through hydrometallurgical routes
consists of leaching the metal from primary or secondary sources [11,
12], followed by a precipitation treatment [5,13]. In the solvent
extraction stage, the liquor is held in contact with an organic solvent and
an extracting agent for the selective recovery of zinc [14,15]. Then, the
extracting phase is subjected to the stripping step to allow recovery of
the metal in its free form for later electrodeposition [15,16].
Most SX methodologies use organic solvents such as kerosene [17,

* Corresponding author.
E-mail address: guilhermedr@ufmg.br (G.D. Rodrigues).

https://doi.org/10.1016/j.jwpe.2021.102138
Received 1 March 2021; Received in revised form 5 May 2021; Accepted 8 May 2021
Available online 18 May 2021
2214-7144/© 2021 Elsevier Ltd. All rights reserved.
D. da Silveira Leite et al.
18], which is very flammable and non-biodegradable, contradicting the
need for more sustainable and environmentally safe processes. In view
of this, the aqueous two-phase systems (ATPS) technique is an inter­
esting strategy to replace traditional solvent extraction, since its effi­
ciency in the recovery of strategic metals from several different matrices
has already been proven [19–23]. ATPS is made up mostly of water and
may contain a polymer [24] or an ionic liquid and an electrolyte in its
composition, which generally have low toxicity and low cost [25–27].
After the phase separation under specific thermodynamic conditions,
ATPS generally have a top phase (TP) which is rich in polymer and poor
in electrolyte and a bottom phase (BP) which is poor in polymer and rich
in electrolyte [28].
ATPS have shown great potential due to the possibility of using both
hydrophobic and hydrophilic extracting agents [29–31]. Many reported
works have applied these systems for the selective recovery of metals
from primary [32,33] and secondary sources [25,34–36]. Leite and
collaborators optimized a separation methodology for Zn2+ and
Mn2+(II) using alkaline battery leachate liquor through ATPS. A sepa­
ration factor (SZn/Mn) of 1.2 × 106 was obtained in just one extraction
step, in an ATPS formed by L64 and Na2SO4, using dithizone as an
extracting agent [37].
Lemos et al. investigated the separation of copper from an ore
leachate employing ATPS as the extraction technique. The developed
method showed that all Cu2+ could be extracted at pH = 3,00, using PAN
(1-(2-pyridylazo)-2-naphtol) as the extracting agent. The other metals
(Fe3+, Co2+, Ni2+ and Zn2+) present in the leachate were mainly
concentrated in the bottom phase (%E ≤ 7,69). The stripping assays
provided recovery of Cu2+ close to 90 %. Therefore, these results
demonstrated the high efficiency of the ATPS technique to recover
metals from a complex sample [32].
Based on the efficiency of ATPS for metal recovery, a mining
concentrated liquor was used for the first time, as a stock solution for the
in-situ preparation of an ATPS. The liquor was a complex solution with a
high content of metal ions, especially Zn2+ and Mg2+. Thus, this work
aimed to recover Zn+2 efficiently, minimizing the reagent consumption
and agreeing with the green chemistry principles, applying ATPS as the
extraction technique.
In view of this, was developed an efficient, applied, and sustainable
methodology for the recovery of zinc from a mining concentrated liquor,
through the optimization of experimental variables such as: the nature
of the ATPS-forming polymer/copolymer and their concentration; the
effect of salt, the effect of the extracting agent and its concentration and
also the mass ratio between both phases. Stripping experiments and
reused reagent studies were also carried out.
2. Experimental
2.1. Equipment
A pHmeter (HI 2221, Hanna) was used to perform pH adjustments;
ATPS stock solutions were weighed using an analytical balance (AUY
220, Shimadzu), with precision ±0.0001 g; a centrifuge (Excelsa II,
FANEN) was used to sediment the sulfuric liquor solids; and a thermo­
static bath of uncertainty ± 0.5 ◦ C (SL 152, Solab) was used to establish
the thermodynamic equilibrium of ATPS assays. The analytical signals
were obtained by flame atomic absorption spectrometry (FAAS - Varian
AA-240).
2.2. Chemicals
The Nexa Mineral Resources S.A. company supplied a sulfuric liquor
containing several metals, mainly Zn2+ and Mg2+, which was used as the
stock solution for the ATPS formation.
All experiments were carried out using deionized water from a
Simplicity UV ultrapure water system (Millipore). The chemicals were of
analytical grade, without any additional purification. The triblock
2
Journal of Water Process Engineering 42 (2021) 102138
copolymers L64 [(EO)13(PO)30(EO)13; molar mass 2900 g mol–1, with 40
% of ethylene oxide (EO)] and L35 [(EO)11(PO)16EO)11, molar mass
1900 g mol–1, with 50 % of EO, where EO means ethylene oxide and PO
means propylene oxide] used in the preparation of the ATPS, were ob­
tained from Sigma-Aldrich (Milwaukee, WI).
The reagents sodium citrate dihydrate (C6H5Na3O7.2H2O, 99.0 %),
sodium sulfate (Na2SO4, 99 %), sodium hydroxide (NaOH), potassium
thiocyanate (KSCN, 98.0 %) were purchased from Vetec (Rio de Janeiro,
Brazil). The anhydrous sodium acetate (NaC2H3O2, 98.0 %) and PEG
1500 were obtained from Synth (São Paulo, Brazil). The sulfuric acid
(H2SO4, 96.0 %) was purchased from Merck (Hesse, Germany).
2.3. ATPS composition and liquid-liquid extraction procedure
The sulfuric liquor containing high concentrations of Zn2+ and Mg2+
was centrifuged at 2500 rpm (560 x g) during 5 min, to separate the
particulate material and obtain a homogeneous and representative
sample. In general, the preparation of the ATPS was performed by
mixing a specific mass of a polymer stock solution (L64, L35 or PEG
1500) with a specific mass of the concentrated liquor in test tubes, which
were manually shaken during 3 min. Then, the ATPS assays were placed
in a thermostatic bath for 30 min at 333.15 K to ensure the thermal
equilibrium.
As can be seen in Fig. 1, the extraction studies were performed in
successive steps, in which a new polymer stock solution was added to BP
1 to prepare a new ATPS. Then, the top phase was collected for mag­
nesium quantification by FAAS, and zinc was quantified by com­
plexometric titration using xylenol orange as indicator.
All experiments were performed in triplicate at 333.15 K, which is
the temperature that the liquor is held after leaching in the industrial
process. The pH value and dilution factor of the pure sulfuric liquor have
not been changed during the procedure.
2.4. Evaluation of extraction procedure
The top phase (TP) of each tube was collected and diluted appro­
priately when necessary. For analysis by FAAS, an analytical curve of
Mg2+ was used to obtain the concentration values. For analysis of Zn2+,
the TP was directly titrated with EDTA (ethylenediaminetetraacetic
acid) using xylenol orange as an indicator. The percentage of Mg2+ and
Zn2+ extraction (%E) was calculated from Eq. (1):
%E =
nTP
x 100 (1)
nTotal
where nTP is the amount of substance of metal ions in the top phase and
nTotal is the total mols number of metals ions in the system. Another
parameter used to assess the extraction efficiency was the distribution
coefficient (DM ), obtained from Eq. (2):
%EM
DM = (2)
100 − %EM
where %EM is the metal extraction percentage.
2.5. Parameters optimized in the extraction procedure
ATPS parameters were studied to optimize the extraction conditions
for Zn2+ and Mg2+ separation. Since pure liquor has been used as a stock
solution for the ATPS formation, there are no phase diagrams available
in the literature to describe the exact composition of the system. Thus,
the following parameters were investigated: concentration of the poly­
mer stock solution (40 %, 50 % and 60 % w/w); ATPS-forming polymer/
copolymer (L64, L35 and PEG 1500); the effect of the salt addition to the
liquor (Na3C6H5O2.2H2O); concentration of extractant agent KSCN
(0.00 to 0.50 mol kg− 1); and mass ratio between top (mTP) and bottom
(mBP) phases (mTP/mBP = 0.5, 1.0 and 2.0).
D. da Silveira Leite et al.
Fig. 1. Schematic representation of the successive extraction procedure using ATPS.
3. Results and discussion
3.1. Sample characterization
First, the samples were centrifuged for 10 min at 2500 rpm (560 x g),
to separate the particulate material and obtain a homogeneous and
representative sample. After centrifugation, the pH of the supernatant
was measured, which was equal to 4.28. Subsequently, the constituents
of the liquor were quantified by FAAS. Table 1 summarizes the con­
centration of the main metal ions in the sample.
After characterization, it was possible to confirm the high concen­
tration of zinc and magnesium in the sample in comparison to other
metal ions. Therefore, this liquor was used in subsequent studies to
optimize the separation process between zinc and magnesium in ATPS.
3.2. ATPS-forming polymers
In studies involving the partition of metallic ions, the nature of the
ATPS-forming polymer is an especially important variable, since the
polymers have considerable differences in their hydrophobicity and
molar masses. Their chemical properties can influence the phase vis­
cosity and consequently, the phase separation time. However, the pur­
pose of this study was to use the pure liquor as a stock solution and to
evaluate the formation of the systems with the addition of PEG 1500,
L64 and L35 solutions in different concentrations. These ATPS-forming
polymers were chosen because they have already been widely applied in
other works involving metallic ion partitioning in ATPS [22,25,34,37,
38].
The stock solutions had a concentration between 30 and 60 % w/w of
the polymer. However, the ATPS assays were only formed with stock
solutions of L35 and L64 at 30 and 40 % w/w and PEG 1500 at 40, 50
and 60 % w/w. Among these, the systems formed by PEG 1500 showed a
faster phase separation, in addition to generating systems with less
viscosity, with no need for centrifugation. These technical features
contribute to a shorter processing time, enabling the application of the
Table 1
Quantification of the metals present in the sulfuric liquor.
Metals Concentration (mg kg− 1)
Zn 37800
Mg 5670
Ni 1.46
Cd 24.7
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Journal of Water Process Engineering 42 (2021) 102138
methodology on a large scale. Furthermore, this polymer has a lower
cost compared to the copolymers evaluated; because of this, PEG 1500
was applied as the ATPS-forming polymer in the subsequent studies.
3.3. Effect of salt and extracting agent
The influence of the addition of salt and extracting agent on the
extraction behavior of Zn2+ and Mg2+ in ATPS were studied. As the
bottom phase is rich in electrolyte, the salt added to the system will
probably concentrate in the bottom phase due to strong ion-ion in­
teractions. So, the electrolyte-forming anion can interact with the metal
ions electrostatically or by complexation, inhibiting its partition to the
top phase. In view of this, the effect of the presence of sodium citrate, an
electrolyte commonly used in metal extraction studies in ATPS, was
evaluated [37,39,40].
The analytes extraction behavior was also evaluated in the presence
of the thiocyanate ion (SCN− ) as an extracting agent, which has already
demonstrated significant results for some metals [29,41]. SCN− has high
water solubility, which improves the operating conditions of the system
formed by PEG 1500, a highly hydrophilic polymer.
First, the effect of sodium citrate in the presence of SCN− on the
partition of the analytes in ATPS was studied. Fig. 2 illustrates the
extraction behavior of Zn2+ and Mg2+ in ATPS formed by sulfuric liquor
+ PEG 1500 (60 % w/w), in the presence of SCN- (0.2 mol kg-1) (A); or
SCN- (0.2 mol kg-1) and Na3C6H5O7 (5% w/w) (B).
In the absence of citrate (Fig. 2A), the extraction efficiency of Zn2+
and Mg2+ were %EZn = (40 ± 1)% and %EMg = (14.1 ± 0.7)%, in four
successive extraction steps. The addition of sodium citrate (Fig. 2B)
provided a significant increase in the extraction of Zn2+ and Mg2+. In
four extraction steps %EZn = (48.3 ± 0.2)% and %EMg = (24 ± 5)% were
obtained, while an extra step provided %EZn = (54 ± 3)% and %EMg =
(26 ± 4)%. Thus, the citrate ion contributed to an increase in the
extraction efficiency of both analytes, probably due to the formation of
stable complexes with both, Zn and Mg2+, which are partitioned to the
ATPS top phase.
In order to improve the zinc extraction efficiency and the separation
of the analytes, subsequent studies were carried out in different con­
centrations of SCN− in ATPS formed by sulfuric liquor + PEG 1500 (60
% w/w) in the presence of sodium citrate (5% w/w). Fig. 3 shows the %E
values of Zn2+ and Mg2+ as a function of the SCN− concentration in the
polymer stock solution.
Analyzing Fig. 3, the concentration of SCN− influences the extraction
behavior of both analytes, especially magnesium. There was a gradual
D. da Silveira Leite et al. Journal of Water Process Engineering 42 (2021) 102138

Fig. 2. Effect of the presence of sodium citrate on successive extractions of Zn2+ and Mg2+ in ATPS formed by sulfuric liquor + PEG 1500 (60 % w/w) in the presence
of SCN− (0.2 mol kg-1) (A); and Na3C6H5O7 (5% w/w) and SCN− (0.2 mol kg-1) (B).

procedure was performed in five stages, except in phase mass ratio,

stripping, and precipitation studies, in which different numbers of
extraction steps were applied.

3.4. Effect of polymer concentration

As ATPS was formed through a mixture of pure liquor with a polymer

stock solution, the effect of the PEG 1500 concentration on the extrac­
tion behavior of Zn2+ and Mg2+ was evaluated. It is known that the
polymer is mainly concentrated in the ATPS top phase; as the amount of
PEG increases it causes variations in the viscosity of the TP, influencing
the phase separation time, as well as the partition of the analytes [42].
Fig. 4 shows the %E of Zn2+ and Mg2+ as a function of the polymer
concentration in the stock solution, in ATPS formed by sulfuric liquor +
PEG 1500 in the presence of SCN− (0.5 mol kg-1) and sodium citrate (5%
w/w).
According to Fig. 4, the PEG concentration considerably influenced
the analytes partition in ATPS. The extraction percentage obtained for

Fig. 3. Influence of SCN− concentration on the extraction behavior of Zn2+ and

Mg2+ after five extraction steps in ATPS formed by sulfuric liquor + PEG 1500
(60 % w/w) in the presence of sodium citrate (5% w/w).

drop in extraction efficiency with an increase in the thiocyanate amount.

Thus, with a SCN− concentration equal to 0.5 mol kg-1, in five extraction
steps the extraction percentage obtained was %EZn = (58 ± 2)% and %
EMg = (2.28 ± 0.03)%, with CZn ~ 7300 mg kg-1 and CMg ~ 40 mg kg-1 in
the top phase. This corresponds to a concentration ratio (CZn/CMg) of
approximately 187.
An increase of the SCN− concentration causes the Mg2+ extraction to
decrease. The Mg2+ concentration in the liquor is much lower than the
Zn2+ concentration (Table 1), so it is expected that the extraction effi­
ciency of magnesium will be more influenced by the SCN− variations,
while the increments in %EZn it is not so pronounced. As thiocyanate
forms stable complexes with Zn2+ and has greater affinity for the ATPS
top phase, a competition between Mg2+ and SCN− species for the
interaction sites present in TP can take place, resulting in a lower
extraction efficiency of Mg+2.
Therefore, the best separation condition between Zn2+ and Mg2+ Fig. 4. Influence of polymer concentration in the stock solution (40, 50 and 60
obtained and fixed for subsequent experiments was in the presence of % w/w) on the extraction behavior of Zn2+ and Mg2+ in ATPS formed by sul­
SCN− (0.5 mol kg-1) and sodium citrate (5% w/w). The extraction furic liquor + PEG 1500 in the presence of SCN− 0.5 mol kg-1 and sodium
citrate 5% w/w, in five extraction steps.

4
D. da Silveira Leite et al.
Zn2+ and Mg2+ when applied to a polymer concentration equal to 40 %
w/w was practically the same – close to 60 %. At PEG concentration
equal to 60 % w/w the extraction efficiency were %EZn = (58 ± 2)% and
%EMg = (2.28 ± 0.03)%, but under these conditions, a gelatinous solid
was formed and deposited at the bottom of the tube. However, a higher
extraction efficiency, %EZn = (79 ± 1)%, was obtained for Zn2+ in five
extraction steps using PEG (50 % w/w). The concentration in the
extracting phase was CZn ~ 7000 mg kg-1 and CMg ~ 160 mg kg− 1, as can
be seen in Figure S1 in the supporting information.
Two distinct effects on the extraction behavior of Zn2+ and Mg2+ can
be observed. Firstly, when the PEG 1500 concentration in the stock
solution was equal to 40 % w/w, the extraction percentage of both
analytes was close to 60 %. However, in systems with a polymer con­
centration equal to 50 % w/w, a significant improvement in the sepa­
ration between the analytes was observed. The Zn-SCN− complex tends
to partition at a higher rate into the ATPS top phase with an increasing
polymer concentration. Because of the greater Zn-SCN− partition, there
may be competition with the Mg+2 ion for the interaction sites in the
extracting phase, thereby decreasing the %EMg.
Another effect observed when increasing the polymer concentration
to 60 % w/w was the decrease in the efficiency of the %EZn and %EMg. As
the concentration of Mg2+ in the liquor is much lower than Zn+2, the
variation in extraction efficiency with increasing polymer concentration
is more pronounced. In higher polymer concentrations, the ATPS phases
become more distinct, which may increase the top phase viscosity and
consequently, the surface tension between phases. These factors can
affect the analytes partition and inhibit the transfer to the top phase.
This phenomenon has also been observed in other works involving
metallic ion partitioning in ATPS [43,44].
Thus, the subsequent studies were carried out employing ATPS
formed by sulfuric liquor + PEG 1500 at 50 % w/w in the presence of
SCN− (0.5 mol kg-1) and sodium citrate (5% w/w).
3.5. Study of phase mass ratio
The effect of the mass ratio between top and bottom phases (mTP/
mBP) of the ATPS was evaluated. It is worth mentioning that there are no
phase diagrams available in the literature to describe the exact
composition of this particular system formed by mining liquor solution.
Therefore, we consider that the masses of the ATPS phases corresponded
to the polymer stock solution and liquor masses, if this methodology is
adopted, these results will be obtained and will be reproducible.
The expectation of this study was to find a compromise condition
between extraction efficiency and pre-concentration of Zn2+ in the top
phase. Therefore, a decrease in the cost of the process is expected,
especially in the consumption of the polymer, which is the most
expensive component used in ATPS.
Fig. 5 shows the %E of Zn2+ and Mg2+ as a function of the mass ratio:
Fig. 5. Extraction behavior of Zn2+ and Mg2+ in successive steps using ATPS formed by sulfuric liquor + PEG 1500 (50 % w/w) in the presence of SCN− 0.5 mol kg-1
and sodium citrate 5% w/w as a function of phase mass ratio (A) mTP/mBP = 0.5; (B) mTP/mBP = 1.0 and (C) mTP/mBP = 2.0.
5
Journal of Water Process Engineering 42 (2021) 102138
(A) mTP/mBP = 0.5, (B) mTP/mBP = 1.0 and (C) mTP/mBP = 2.0, in ATPS
formed by sulfuric liquor + PEG 1500 (50 % w/w) in the presence of
SCN− (0.5 mol kg-1) and sodium citrate (5% w/w).
The mass ratio studies (mTP/mBP) were performed with the
maximum possible number of steps in the system, aiming for a high %E
of Zn2+ and a better separation between analytes. Fig. 5A and B show a
saturation of the system TP from the 7th successive extraction step when
using mTP/mBP = 0.5 (%EZn ~ 60 %) and mTP/mBP = 1.0 (%EZn ~ 90 %),
respectively. However, in the study of mTP/mBP = 2.0, approximately
100 % of Zn2+ had been recovered in four extraction steps.
In systems where the TP mass is lower than the BP mass, a pre-
concentration of the analytes in the TP and a low extraction efficiency
are expected, since a lower number of interaction sites between the Zn-
SCN species and the macromolecules of the copolymer were available in
the extracting phase. On the other hand, in systems with a mass ratio
greater than one (mTP/mBP ≥ 1.0), it is possible to obtain a greater
extraction capacity of analytes in fewer successive extraction steps.
Therefore, the mass ratio system equal to 2.0 showed better results for
the %E of Zn2+.
Although the Zn2+ recovery was close to 100 % in four extraction
steps with mTP/mBP = 2.0, with distribution factors DMg = 0, 36 and
DZn = 2905, the formation of a precipitate occurred in this system,
which can be an obstacle when the methodology is scaled-up. However,
in three extraction steps, a high extraction efficiency was obtained, %EZn
= (91.4 ± 0.1)%, with distribution factors DMg = 0, 22 and DZn = 48, 50,
and an overall concentration of Zn2+ equal to (5742 ± 29) mg kg− 1 and
Mg2+ equal to (164 ± 1) mg kg− 1 in the extracting phase, as can be seen
in Figure S2 in the supporting information. Under this condition, the
concentration ratio between Zn2+ and Mg2+ (CZn/Mg) was approximately
52, a value considerably higher than the one found in the original sul­
furic liquor (CZn/Mg ~ 7). Therefore, the subsequent study was carried
out with a mass ratio equal to 2.0, applying three extraction steps in
ATPS formed by sulfuric liquor + PEG 1500 (50 % w/w) in the presence
of SCN- (0.5 mol kg− 1) and sodium citrate (5% w/w).
3.6. Stripping
In traditional SX plants, after the separation stage, the extracting
phase is submitted to a stripping process to recover the analyte in its
ionic free form in solution or as pure solid. For this, the stripping study
was performed in two ways: by placing the extracting phase in contact
with a Na2SO4 solution or using NaOH as the precipitating agent.
Fig. 6A shows the results of the percentage of stripping (%S) in
successive stripping steps of Zn2+ and Mg2+ in ATPS formed by PEG
1500 (50 % w/w) + Na2SO4 (20 % w/w) in the presence of SCN− (0.5
mol kg-1) and sodium citrate (5% w/w), as a function of the number of
extraction steps in ATPS. Fig. 6B illustrates the percentage of precipi­
tation (%PPT) of Zn2+ and Mg2+ from the extracting phase, as a function
D. da Silveira Leite et al.
Fig. 6. Successive stripping of Zn2+ and Mg2+ in ATPS formed by PEG 1500 (50 % w/w) + Na2SO4 (20 % w/w) in the presence of SCN− 0.5 mol kg-1 and sodium
citrate 5% w/w (A) and precipitation of Zn2+ and Mg2+ from the extracting phase as a function of pH (B), after three extraction steps.
of the medium pH (after three extraction steps).
The results for stripping in ATPS using a stock solution of Na2SO4 (20
% w/w) show that in the second extraction step, all magnesium was
recovered for the electrolyte-rich phase, while for Zn2+, after five steps
of extraction the recovery was close to 40 %. In the precipitation study,
at pH = 9.00, the recovery percentage for Zn2+ was approximately 80 %
and was close to 55 % for Mg2+.
Despite increasing the pre-concentration of Zn2+ in the stripping
study with Na2SO4, the recovery was less than 40 %. However, at pH =
6.00 about 65 % of Zn2+ was precipitated in the form of hydroxide,
while Mg2+ remained in the supernatant. This behavior generated a
solid with a high purity of Zn and therefore provided a better separation
between the analytes. These results are satisfactory since the objective of
this work was to recover zinc selectively.
3.7. Reuse of the extracting phase
To reduce process costs and make the methodology even more sus­
tainable, after the precipitation study, the supernatant was reused to
evaluate the performance of ATPS in one more extracting step without
Fig. 7. Reuse of the extracting phase as a function of pH in ATPS formed by
sulfuric liquor + PEG 1500 (50 % w/w) in the presence of SCN− 0.5 mol kg-1
and sodium citrate 5% w/w, with mTP/mBP = 2.0, in one extraction step.
6
Journal of Water Process Engineering 42 (2021) 102138
any addition of further reagents. The extracting phase was placed in
contact with pure liquor to allow the formation of a new ATPS. Fig. 7
illustrates the %E of Zn2+ and Mg2+ as a function of the pH of the top
phase, in ATPS formed by sulfuric liquor + PEG 1500 (50 % w/w) in the
presence of SCN− (0.5 mol kg-1) and sodium citrate (5% w/w), with
mTP/mBP = 2.0.
At pH = 9.00, %EZn = (54 ± 2)% was obtained in just one extraction
step. However, precipitate formation occurred probably due to the high
pH value. At pH = 7.00, %EZn = (46 ± 2)% and %EMg = (11 ± 1)% were
obtained. Under this condition, the separation between the analytes had
decreased in comparison with the extraction efficiency in a system with
new TP (Fig. 5C, 1 st step), although the top phase still had a great
extractive capacity, even without the addition of SCN− and sodium
citrate.
These results prove that it is possible to reuse the system components
in a simple way, with satisfactory extraction efficiency results. There­
fore, the ATPS technique is sustainable, as there is low residue pro­
duction, the ability to reuse reagents - mainly the polymer and
extracting agent, in addition to the saving of water, which can greatly
decrease production costs.
4. Conclusion
A low cost and low environmental impact methodology were
developed for the selective recovery of Zn2+ from a concentrated sul­
furic liquor, which was used without dilution in the formation of the
ATPS.
The optimized ATPS composed of sulfuric liquor + PEG 1500 (50 %
w/w) in the presence of SCN− (0.5 mol kg-1) and sodium citrate (5% w/
w), in a mass ratio equal to mTP/mBP = 2.0, proved to be an efficient
system for separating the main analytes present in the liquor (Zn2+ and
Mg2+). Under these conditions, it was possible to extract (91.5 ± 0.1)%
of Zn2+ and (18.2 ± 0.1)% of Mg, with distribution factors DMg = 0, 22
and DZn = 48, 50, resulting in a final concentration ratio CZn/Mg = 52.
Finally, about 65 % of Zn2+ was recovered in the hydroxide form by
precipitation, while the Mg2+ remained in its totality in the supernatant,
using NaOH as a precipitating agent.
For the first time, it was proven that it is possible to reuse the com­
ponents of the ATPS, mainly the polymer and the extracting agent, to
still achieve a high extraction efficiency (%EZn ~ 45 %). Therefore, there
is the possibility of a significant reduction in process costs, as well as in
the generation of waste.
In this perspective, the method developed proved to be suitable for
the selective recovery of zinc in a complex matrix, making the metal ion
in the form of hydroxide available at the end of the process, which can be
easily solubilized for later electrodeposition. Consequently, the ATPS
D. da Silveira Leite et al. Journal of Water Process Engineering 42 (2021) 102138

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