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Solvent Extraction of Gold(III) with Diethyl Carbonate

Stijn Raiguel, Lukas Gijsemans, Arne Van den Bossche, Bieke Onghena, and Koen Binnemans*

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ABSTRACT: Diethyl carbonate (DEC) was evaluated as a green, renewable

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alternative to methyl isobutyl ketone and dibutyl carbitol for the recovery of
gold from copper-rich sources, such as anode slimes, by solvent extraction
from chloride solutions. DEC is a powerful extractant at high chloride
concentrations and can be used to sequester and concentrate gold from large
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volumes of dilute aqueous solutions containing high concentrations of

copper. Stripping can be performed using pure water. Different variables were
investigated: DEC concentration, chloride concentration, chloride source,
phase volume ratio, and equilibration time. The selectivity and phase disengagement times were studied, and possible mechanisms of
extraction are discussed and evaluated. In addition, the stability of DEC against hydrolysis was measured.
KEYWORDS: anode slime, chloride hydrometallurgy, copper, precious metal refining, solvent extraction

■ INTRODUCTION
Because of its high intrinsic value, there is considerable interest
After halide leaching, different techniques are available to
recover the dissolved gold, such as cementation, adsorption
in the recovery of gold from secondary sources, including onto activated carbon (carbon-in-pulp and carbon-in-leach) or
onto a resin (resin-in-pulp and resin-in-leach), ion-exchange
waste electric and electronic equipment (e-scrap), jewelry,
chromatography, and solvent extraction.4 Solvent extraction is
spent catalysts, and copper anode slime.1−6 Developed in the
an effective method for the separation and purification of
mid-19th century, extraction of gold by chlorination was the
precious metals. A variety of extractants have been applied to
first hydrometallurgical gold extraction process available on the
gold in the literature.7,18,19 This includes neutral extractants
commercial scale. By passing chlorine gas over crushed ores,
with oxygen and sulfur donor atoms such as dibutyl carbitol
soluble gold chloride was produced, which could subsequently
(DBC),20,21 methyl isobutyl ketone (MIBK) or dodecylth-
be dissolved in water.7 After the introduction of the
iourea;22 quaternary ammonium basic extractants such as
cyanidation process more than 100 years ago, the latter
Aliquat 336;23 and organophosphorus-based extractants such
became the preferred technology for gold extraction, which
as tri-n-butyl phosphate (TBP)24 and Cyanex 923.25
remains till date due to its robustness, low cost, and high-
A number of studies have been specifically devoted to the
recovery efficiencies.8 Cyanidation uses alkaline cyanide to
recovery of gold from copper anode slimes using halide-based
dissolve gold from primary ores, exploiting the strongly
hydrometallurgical processes. Anode slime is produced during
coordinating nature of the cyanide anion for the complexation
the electrorefining of impure copper anodes to produce pure
of gold. However, the past few decades, research is shifting
copper cathodes.26,27 The insoluble impurities of the copper
toward cyanide-free leaching processes due to a rise in
anodes are collected at the bottom of the electrolysis cell as a
environmental concerns over the cyanidation process and the slime. Depending on the production process of the copper
need for treating more complex and refractory gold ores.9 The anodes, the slime contains copper, nickel, tin, antimony,
cyanide-free alternatives are all based on the selective selenium, tellurium, gold, silver, platinum group metals, lead,
coordination chemistry of gold with a wide variety of simple iron, and barium. One of the challenges in treating the slimes is
ligands, including thiocyanate, ammonium thiosulfate, thiourea to selectively separate the trace elements such as gold from the
and halides, amongst others.10−14 base metals such as copper present in high concentrations.
Halides are known to have much higher leaching rates Xing and Lee applied a combination of hydrochloric acid
compared to cyanides. Except for fluorine and astatine, all
halogens have been applied to the dissolution of gold, as
chloride, bromide, and iodide all form complexes with Au(I) or Received: June 1, 2020
Au(III). Oxidizing conditions are created using acidic solutions Revised: July 27, 2020
of oxidants, such as chlorine in hydrochloric acid or a mixture Published: August 13, 2020
of hydrochloric and nitric acids (aqua regia). Recent advances
in halide-based leaching of gold make use of Cu(II) or Fe(III)
as an oxidizing agent.11,15−17

© 2020 American Chemical Society https://dx.doi.org/10.1021/acssuschemeng.0c04008

13713 ACS Sustainable Chem. Eng. 2020, 8, 13713−13723
ACS Sustainable Chemistry & Engineering
leaching with different oxidizing agents (hydrogen peroxide,
sodium hypochlorite, and nitric acid) to recovery gold and
silver.28−32 Sadeghi and Alamdari applied solvent extraction
with TBP to recover Au(III) from chloride leachates.24 In
addition to halide-based processes, other systems have been
applied to the recovery of gold from anode slimes, including
sulfuric acid leaching, with or without pretreatment by alkali
pressure oxidation,33,34 thiosulfate leaching,13 and leaching
with ionic liquids.35,36
In this paper, diethyl carbonate (DEC) is applied as an
extractant for the separation of Au(III) and Cu(II) from
chloride solutions by solvent extraction, as part of an
alternative flowsheet for the recovery of precious metals from
copper anode slimes. Both the extraction of Au(III) and the
selectivity over Cu(II) were investigated. The hydrolytic
stability of the extractant was also considered because of its
relevance to the recyclability of the solvent in a continuous
process. DEC has been selected as a green alternative for the
commonly used gold extractants, MIBK and DBC. DEC can be
produced by condensation of ethanol and CO2 under
increased temperature and pressure, rendering it a fully non-
fossil fuel-based solvent and even mitigating the emission of
CO2 in the atmosphere. Moreover, it is characterized by low
toxicity and high biodegradability and is therefore classified as
a green solvent.37−39 To the best of our knowledge, no reports
on the use of DEC for solvent extraction of metals have been
published in the peer-reviewed literature. DEC has been used
in analytical chemistry for the extraction of phenols.40,41
Cyclic and open-chain carbonates have been described in
the literature as suitable extractants for various metals,
including molybdenum,42,43 iron,43−46 cobalt,43 uranium,43
and heavy and noble metals.43,47,48 Propylene carbonate has
also been investigated as a diluent for the extraction of indium
and gallium by Kelex 100.49
■
EXPERIMENTAL SECTION
Chemicals. The solvents DEC and D70 were kindly provided by
Shell Global Solutions International (Amsterdam, The Netherlands).
NaCl (99.5%), bis(2-ethylhexyl)phosphoric acid (D2EHPA, 95%),
neodymium chloride hexahydrate (NdCl3·6H2O, 99.9%), hydro-
chloric acid solution (HCl, 37 wt % in water), thiourea (CH4N2S,
99%), sodium thiocyanate (NaSCN, 98%), copper(II) chloride
(CuCl2, 98%), MIBK (99.5%), deuterated dimethyl sulfoxide
(DMSO-d6 for NMR), and glycerol (CH2OHCHOHCH2OH,
>99%) were purchased from Acros Organics (Geel, Belgium).
Sodium tetrachloroaurate(III) dihydrate (NaAuCl4·2H2O, 99%),
sodium sulfite (Na2SO3, 98%), sodium thiosulfate pentahydrate
(Na2S2O3·5H2O, 99.5%), L(+)ascorbic acid (C6H8O6, 99%), sodium
hydroxide (NaOH, 97%), iron(II) sulfate heptahydrate (FeSO4,
99%), oxalic acid, (C2H2O4, >99%), 2-ethyl-1-hexanol (C8H18O,
99.6%), and polyethyleneglycol para-(1,1,3,3-tetramethylbutyl)phenyl
ether (Triton X-100) were purchased from Sigma-Aldrich (Overijse,
Belgium). Gallium standard solution (1000 μg mL−1 in 3−5%
HNO3), ammonium thiocyanate (NH4SCN, >99%), and ammonium
chloride (NH 4 Cl, >99.8%) were obtained from Chem-Lab
(Zedelgem, Belgium). Ammonia solution (NH3, 25% solution in
water) was purchased from VWR, lithium chloride (LiCl, 99%) from
Carl Roth (Karlsruhe, Germany), diethylene glycol dibutyl ether
(DBC, 99%) from J&K Scientific (Lommel, Belgium), and ethanol
(EtOH, 99.8%) from Fisher Scientific (Geel, Belgium). A silicon
solution in isopropanol was obtained from SERVA Electrophoresis
GmbH (Heidelberg, Germany). Ultrapure water deionized to a
resistivity of 18.2 MΩ·cm was produced using a Millipore Reference+
ultrapure water system. All chemicals were used as received without
any further purification.
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Solvent Extraction Tests. Stock solutions of gold and copper
were made by weighing NaAuCl4·2H2O and CuCl2, transferring the
sample quantitatively into a volumetric flask and diluting it with
ultrapure water to the appropriate volume. HCl (37%) was added
dropwise to lower the pH to below 1.5 to prevent hydrolysis. The
speciation of Au(III) in these solutions was modeled using the
software OLI Studio: Stream Analyzer version 9.6.2 using the Mixed
Solvent Electrolyte (MSE) database (OLI Systems Inc., USA). The
stock solutions were then contacted with an organic phase, consisting
of an extractant (DEC, DBC, MIBK, or 2-ethyl-1-hexanol) and a
diluent (DEC, D70, or a mixture thereof) at a certain O/A (organic-
over-aqueous) phase ratio, which is defined as the ratio between the
volume of the aqueous phase Vaq over the volume of the organic phase
Vorg.
The extraction mixtures were shaken horizontally for a certain time
at room temperature (RT) in a Nemus Life TMS-200 Turbo
thermoshaker at 2000 rpm. Afterward, the samples were allowed to
settle gravitationally. The gold and copper concentrations in the
aqueous and organic phase after extraction were measured by total-
reflection X-ray fluorescence (TXRF) spectroscopy on a Bruker
PICOFOX S2 spectrometer. For the sample preparation, an aliquot of
the aqueous or organic phase was mixed with a gallium internal
standard and diluted to 1 mL with 5 vol % glycerol or 5 vol % Triton
X-100 (aqueous samples), or a mixture of 5 vol % glycerol and
ethanol (organic samples). A droplet of 5 μL was spotted on a quartz
glass carrier pretreated with a silicon solution in isopropanol and
analyzed by the TXRF spectrometer. The added amount of the
sample was carefully chosen to have a metal concentration between 0
and 10 mg L−1 of gold and/or copper in the final sample, and the
concentration of the gallium internal standard was matched to be in
the same range. Metal extraction is evaluated using the distribution
ratio DM and the percentage extraction % EM, calculated using eqs 1
and 2
CM,org
D=
C M,aq (1)
nM,aq,0 − nM,aq
% EM = × 100
nM,aq,0 (2)
where CM,org denotes the analytical metal concentration in the organic
phase, CM,aq denotes the analytical concentration in the aqueous
phase, nM,aq,0 denotes the initial molar amount of the metal ion in the
aqueous phase, nM,aq denotes the remaining amount in the aqueous
phase after extraction, and “M” denotes either Au(III) or Cu(II). The
separation between Au(III) and Cu(II) is evaluated by calculating the
separation factor αAu
Cu
Au DAu
αCu =
DCu (3)
All experiments were carried out in triplicate, and each sample was
measured in duplicate. Standard deviations were calculated based on
the measured values of this triplicate.
Determination of the Phase Disengagement Time. The
phase disengagement time of the solvent extraction mixtures was
determined using a fixed setup consisting of a 200 mL glass beaker
with an overhead stirrer, filled with 40 mL of the aqueous phase and
40 mL of the organic phase (Figure 1). The composition of the
aqueous phase was similar to the extraction mixtures but without the
presence of Au(III) or Cu(II) and consisted of 10 mol L−1 LiCl with a
small amount of HCl to fix the pH at 1.5. These conditions were
chosen as they were optimal for the extraction of gold (vide inf ra).
The organic phase consisted of DEC diluted in D70 at varying
concentrations. The impeller of the overhead stirrer was placed in the
aqueous phase (bottom phase) to obtain aqueous phase continuity
and stirred for several minutes until the mixture visually appeared to
be homogeneously mixed. Then, the stirrer was stopped and the
phase disengagement time was recorded with a chronometer. The end
of the phase disengagement time is defined as the moment where the
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

AuCl3(aq) + x DEC(org) F AuCl3· DECx(org) (4)

[AuCl4](aq)− + H(aq)+ + DEC(org)

F [HDEC]+ [AuCl4](org)− (5)
Au(III) readily forms complexes with chloride in aqueous
solution. According to the speciation diagram of Au(III), the
neutral AuCl3 species is only present in aqueous solutions with
higher acidities and low chloride concentrations, while the
anionic species [AuCl4]− is dominant at increased chloride
concentrations and lower acidities (Figures 3a,b and 4).

Figure 1. Experimental setup for determination of the phase

disengagement time in aqueous continuous and organic continuous.
The beaker is a 200 mL Berzelius beaker, Vaq = Vorg = 40 mL, b = a =
2 cm.

thickness of the emulsion layer at the interface is decreased to below 2

mm. Next, the same procedure is repeated for the organic continuous
mode by positioning the impellor in the organic phase (top phase).
Hydrolysis Experiments. Experiments were performed in 4 mL
glass vials with a plastic cap, sealed with a Teflon tape to prevent
evaporative losses. DEC (0.5 mL) and aqueous solution (1.0 mL)
were added to the vials. The samples were stirred at 1200 rpm for 7
days. If needed, they were heated in cylindrical aluminium blocks.
Afterward, the samples were cooled to RT and diluted in DMSO-d6
until a homogeneous solution was obtained. The degree of
decomposition was determined by recording a 1H NMR spectrum
of the diluted sample. 1H NMR spectra were recorded on a Bruker
AVANCE III HD spectrometer operating at 400 MHz with d1 = 3 s
and the number of scans = 32. The zg30 pulse program was used. The
spectra were processed using the Spinworks software package by
Fourier transformation into the δ-dimension and the application of
manual phase correction and automatic baseline correction. The
degree of decomposition was determined by integration of the methyl
(CH3) proton signals of DEC and each of the decomposition
products, taking the reaction stoichiometry into account.

■ RESULTS AND DISCUSSION

Extraction Experiments. As DEC has both Lewis and
Brønsted basic properties, DEC could act both as a solvating
extractant or as a basic extractant. The structure of DEC is
depicted in Figure 2. Extraction as a solvating extractant occurs
via solvation of the neutral AuCl3 salt (eq 4). Extraction as a
basic extractant occurs by ion association of the anionic
complex [AuCl4]− with protonated DEC under acidic
conditions (eq 5). Equation 5 assumes that DEC does not
significantly extract HCl in the absence of Au(III).
Figure 2. Structural formulae of the extractants used in this study:
DEC (1), DBC (2), 2-ethyl-1-hexanol (3), and MIBK (4).
13715
Figure 3. (a) Speciation of 0.1 mol L−1 Au(III) in water at pH 3 as a
function of the LiCl concentration and (b) speciation of 0.1 mol L−1
Au(III) in water at pH 0 as a function of the LiCl concentration.
Considering the speciation data, as shown in Figures 3 and
4, gold will be nearly exclusively present as [AuCl4]− under
working conditions. The solvating mechanism would require
the expulsion of a chloride anion from the [AuCl4]− complex
with formation of the neutral AuCl3 molecule for extraction to
occur and could thus be expected to be disfavored by higher
chloride concentrations. In practice, however, extraction by
both solvating and basic extractants are often promoted by
high salt concentrations, regardless of reaction stoichiometry.
This is due to the salting-out effect, which in this case would be
conferred by chloride salts or hydrochloric acid.31,50
To distinguish between the two mechanisms, the chloride
source can be varied. For a basic extraction mechanism,
stronger extraction is expected from hydrochloric acid media as
compared to other chloride media as hydrochloric acid
provides a source of aqueous protons to be taken up
concomitantly with [AuCl4]−. Experiments were performed
in which the aqueous chloride concentration varied between 0
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Figure 4. Predominance diagram of 0.1 mol L−1 AuCl3 in water as a function of the LiCl concentration and the pH. Sulfuric acid was applied as a
titrant as to not influence the chloride concentration.
Figure 5. Percentage extraction (% EAu) of 0.1 g L−1 Au(III) from
chloride solution with pure DEC as a function of the chloride
concentration in the aqueous phase. Chloride sources are HCl (black
circles), 2 mol L−1 HCl with variable NaCl molarity (black triangles),
NaCl (black squares), LiCl (gray squares), or 0.5 mol L−1 HCl with
variable LiCl molarity (gray circles). Experimental parameters: 30
min; 25 °C; solvent composition = pure DEC; and O/A ratio = 1:1.
and 10 mol L−1 by addition of HCl, NaCl, and/or LiCl (Figure
5). The results showed a significant increase in extraction as a
function of the chloride concentration when using HCl as the
salting-out agent, with up to 73% of Au(III) extraction at 5 mol
L−1 HCl without the addition of alkali chloride salts. Using
NaCl solutions with equal chloride concentrations, the
extraction efficiency was lower, in spite of the fact that NaCl
is known as a stronger salting-out agent.50 This indicates that
the high proton concentrations promote the extraction of
Au(III) by DEC, thus supporting a basic extraction
mechanism. The addition of NaCl and LiCl as salting-out
agents in addition to HCl was also investigated, to further
increase the extraction of Au(III). The combination of HCl (2
mol L−1) and NaCl performed as well as or slightly better than
either chloride source, providing both protons and a strongly
hydrated cation. Reasonably high percentages extraction were
attained from 5 mol L−1 total chloride onward, reaching nearly
100% at 10 mol L−1 LiCl. The HCl/LiCl combination
significantly outperformed pure LiCl at lower chloride
concentrations, but the curves converge toward higher chloride
concentrations. This sequence also runs counter to the
established strength order of salting-out agents, indicating
the importance of the aqueous proton activity.
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While a very strong dependence on the aqueous chloride
concentration was observed, the speciation data shown in
Figure 3 exclude changes in speciation as the cause of this
variability. Xing and co-workers did not observe such strong
variability observed for the more strongly basic extractant
Alamine 336.31 We attribute this behavior to the weak basicity
of DEC. No extraction of HCl is expected to occur at low
hydrochloric acid concentrations in the absence of Au(III) and
a salting-out agent, and hence DEC does not function as a
basic extractant at low chloride concentrations. Upon
increasing the salt concentration, the H+−[AuCl4]− ion pair
is extracted to the organic phase as a result of the salting-out
effect. As will be shown later in this paper, DEC is susceptible
to hydrolysis in strong acidic media. Therefore, high salt
concentrations are preferred over high acid concentrations and
10 mol L−1 LiCl was chosen as the optimal condition for
Au(III) extraction with DEC in further experiments. These
conditions are compatible with gold leaching by copper/iron in
chloride solutions and with leaching by chlorine gas in chloride
solutions. Reuse of the LiCl solution is possible after removal
of impurities by extraction with a less selective extractant for
chloride solutions, such as Alamine 336.
Next, the influence of the O/A ratio and the contact time
was investigated. Studies of the latter were performed by
determining the percentage extraction under identical
conditions with variable contact times. Quantitative extraction
was achieved after 5 min, indicative of fast extraction kinetics.
The O/A ratio was investigated in the range between 1:40 and
1:1 (Figure 6). At an O/A ratio of 1:10, a percentage
extraction of 91% is still observed for Au(III). A strong
decrease in % E did not occur until the O/A ratio was further
decreased, down to a % E of 64% at an O/A of 1:40. This
opens up opportunities for using the system for the
concentration of Au(III) from diluted aqueous solutions. In
the O/A mixture of 1:40, Au(III) is 20 times more
concentrated in the organic phase compared to the initial
aqueous feed solution.
DEC is prone to hydrolysis in acidic solutions. Depending
on the acid concentration and the temperature, it decomposes
to ethanol and carbon dioxide. At low acid concentrations and
ambient temperature, the decomposition is limited and the
decomposition products are not expected to influence the
extraction mechanism. To verify this, the influence of ethanol
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ACS Sustainable Chemistry & Engineering
on the extraction efficiency of DEC was tested (Table 1). The
same % E of Au(III) was obtained as in previous experiments
Table 1. Percentage Extraction (% E) of Au(III) from
Chloride Solution with Pure DEC as a Function of the
Addition of Ethanol (EtOH) to the Diluent in the Organic
Phasea
vol % EtOH O/A = 1:5 O/A = 1:1
0 93.9 ± 0.4 97.7 ± 1.4
0.1 91.7 ± 0.9 97.9 ± 0.1
1 92.5 ± 0.2 98.1 ± 01
5 93.1 ± 0.4 98.7 ± 0.1
a
Experimental parameters: 30 min; 25 °C; aqueous composition = 0.1
g L−1 Au(III), 10 mol L−1 LiCl; organic composition = 0.1−5 vol %
EtOH in DEC; O/A ratio = 1:5 or 1:1; and pHin ± 1.5.
without the presence of ethanol. Furthermore, the % E remains
unchanged with increasing concentrations of ethanol up to 5
vol %. This confirms that the influence of the decomposition of
DEC on the chemistry of extraction of Au(III) is negligible.
Decomposition does have an important impact on industrial
solvent extraction installations because it means that the
solvent needs to be reloaded frequently. However, generally,
loading of fresh solvent is required regardless of decom-
position, due to physical losses because of entrainment of the
solvent in the raffinate. Buildup of ethanol by decomposition
can be prevented by removal of ethanol from DEC by
distillation.51
Phase Disengagement Time. The phase disengagement
time, which is the time required for the organic and aqueous
phase to settle after mixing, influences the design and
dimensions of the solvent extraction equipment used to run
the process in a continuous mode, for example, the settling
chamber of mixer settlers. If the phase disengagement is not
completed at the exit of the settling chamber, undesirable
losses occur because of entrainment of the phases and lower
flow rates will have to be used to prevent flooding of the
settler. For Au(III) extraction with DEC, the phase disengage-
ment time was determined as a function of the DEC
concentration in D70 to investigate whether the addition of
a diluent could improve the settling. The aqueous solution
contained 10 mol L−1 LiCl and initial pH of 1.5. No Au(III)
was added as it is not expected that low concentrations of
Au(III) would have a significant effect on the phase
disengagement time. A 200 mL Berzelius beaker with a
diameter of approx. 8 cm was used. Both phases had a volume
of 40 cm and a height of 2 cm in the beaker. Both the aqueous
continuous and the organic continuous phase disengagement
time were determined, but no significant difference was
observed (Figure 7). Phase continuity was altered by
submerging the stirrer in the other phase.
The fastest phase disengagement time was observed at a low
DEC concentration of 25 vol %. The phase disengagement
time rose slowly with increasing DEC concentrations, but pure
D70 exhibited a longer disengagement time than 20 vol %
DEC as well. All measured times were below 1 min, which is a
reasonable time to apply the system to a mixer-settler setup
with standard settling chambers allowing phase disengagement
times of several minutes.
Separation of Au(III) and Cu(II). Selectivity of Au(III)
over Cu(II) is important because mostly gold occurs as a trace
metal in copper-rich streams, including anode slime and ores.
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Figure 6. Percentage extraction (% E) of Au(III) from chloride
solution with pure DEC as a function of the O/A ratio. Experimental
parameters: 30 min; 25 °C; feed composition = 0.1 g L−1 Au(III), 10
mol L−1 LiCl; solvent composition = pure DEC; O/A ratio = 1:40−
1:1; and pHin = 1.5.
Figure 7. Phase disengagement time of a mixture of a 10 mol L−1 LiCl
solution (pH = 1.5) with DEC diluted in D70 at varying vol %
between 0 and 100 in a O/A ratio of 1:1 at RT, both in the aqueous
continuous (solid line) and organic continuous mode (dashed line).
In the first selectivity experiment, the separation of Au(III) and
Cu(II) was tested from a solution containing the same
concentration of Au(III) and Cu(II), namely 0.1 g L−1, and the
influence of the LiCl concentration was determined (Figure 8a,
solid line). A high selectivity of Au(III) over Cu(II) was
observed. The concentration of Cu(II) in the organic phase
was below the detection limit (<0.1 mg L−1), while Au(III)
extraction remained uninfluenced with 100% extraction at 10
mol L−1 LiCl. The separation factor αAu Cu was estimated to be
larger than 1000. The same experiment was repeated using 10
and 100 times more Cu(II) in the feed solution (Figure 8a,
dashed and dotted line, respectively). The Cu(II) concen-
tration in the feed solution did not show any significant
influence on the selectivity and % E of Au(III). Again, the
concentration of Cu(II) in the organic phase was below the
detection limit (<0.1 mg L−1), and the separation factor αAu Cu
was estimated to be larger than 1000. This result is very
important because gold-containing materials often have a
much lower concentration of gold than copper. Being able to
achieve a high selectivity for Au(III) even at a large excess of
Cu(II) indicates the applicability of the system to recover
Au(III) from copper-rich streams.
The performance of DEC was compared with three
commonly used extractants for gold, namely, MIBK, 2-
ethylhexanol, and DBC. A similar experiment was performed
to compare the selectivity and extraction of Au(III) and
Cu(II). Comparison of MIBK and DEC showed that MIBK is
a stronger extractant for both metals than DEC. Hence, the %
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Figure 8. Percentage extraction (% E) of Au(III) and Cu(II) from chloride solution with (a) pure DEC, (b) pure MIBK, (c) pure DBC, and (d) 2-
ethylhexanol as a function of the LiCl concentration and the Cu(II) concentration in the aqueous phase: 0.1 (solid), 1 (dashed), and 10 (dotted) g
L−1 Cu(II). Experimental parameters: 30 min; 25 °C; aqueous composition: 0.1 g L−1 Au(III), 0.1−10 g L−1 Cu(II), 5−10 mol L−1 LiCl; organic
composition: pure DEC; pHin = 1.5; and O/A ratio = 1:1.
E of Au(III) to MIBK was higher compared to DEC at low salt
concentrations (e.g., 5 mol L−1). When the metals are present
in equimolar ratios, no co-extraction of Cu(II) was observed
(Figure 8b). Conversely, at higher salt concentrations and
higher Cu(II)/Au(III) ratios, Cu(II) started to co-extract to
MIBK, resulting in a low purity of Au(III) in the organic phase.
At 10 g L−1 Cu(II); 0.1 g L−1 Au(III) and 10 mol L−1 LiCl, the
organic phase contained almost four times more Cu(II) (0.45
g L−1) than Au(III) (0.13 g L−1). Thus, at lower salt
concentrations (e.g., 5 mol L−1) and small Cu(II)/Au(III)
ratios in the feed solution, MIBK outperforms DEC, but
selective recovery of Au(III) from a copper-rich material will
be more challenging with MIBK compared to DEC. The
comparison of DEC and DBC showed that both extractants
behave in a similar manner (Figure 8c). For both extractants,
the % E of Au(III) increased with increasing salt concen-
trations until 100% extraction is reached at 10 mol L−1 LiCl. At
lower salt concentrations and lower Cu(II)/Au(III) ratios,
DBC shows a higher %E for Au(III) than DEC. However, the
Au(III) extraction is significantly influenced by the Cu(II)
concentration in the feed, in particular, at lower salt
concentrations. While the percentage co-extraction of Cu(II)
is low (0−2%) for both extractants, values for DBC are
universally higher, resulting in a significant contamination of
the DBC extract with copper: at 10 g L−1 Cu(II); 0.1 g L−1
Au(III) and 10 mol L−1 LiCl, the organic phase contained 0.05
g L−1 Cu(II) (0.45 g L−1) and Au(III) 0.13 g L−1. Therefore,
selective recovery of Au(III) from copper-rich materials will be
more challenging with DBC, and DEC is preferable. DEC was
also compared to 2-ethylhexanol for a feed solution containing
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10 g L−1 Cu(II) and 0.1 g L−1 Au(III) (Figure 8d). 2-
Ethylhexanol did not extract Au(III) well, and selectivity of
Au(III) over Cu(II) was very poor, which showed that DEC is
preferred over 2-ethylhexanol as an extractant.
Stripping Experiments. The stripping of Au(III) from the
loaded DEC organic phase was tested by screening several
stripping agents: (1) reducing agents that remove Au(III) by
reduction to Au(I) or Au(0) (ascorbic acid, iron(II) sulfate,
and oxalic acid), (2) complexing agents that transfer Au(III) to
the aqueous phase by formation of a hydrophilic complex
(ammonia solution, sodium thiosulfate, sodium sulfite,
thiourea, sodium thiocyanate, and ammonium thiocyanate),
and (3) low-concentration chloride solutions that transfer
Au(III) to the aqueous phase by the back-extraction, that is, a
reversal of the extraction process (water, hydrochloric acid,
sodium chloride, and ammonium chloride). The organic phase
was always analyzed to calculate the percentage stripping % S.
All stripping agents performed well for the removal of Au(III),
with % S above 80%, except for NH4Cl (Table 2). Water is of
particular interest because of the low cost and good
performance. Because Au(III) is prone to hydrolysis at pH 3
and higher, a small concentration of HCl is added (0.01 mol
L−1) to the stripping solution.
Furthermore, the stripping of MIBK and DBC loaded with
Au(III) was tested and compared with DEC. Thiourea, HCl
(0.01 mol L−1), water, and ammonia solution were selected as
stripping agents because they showed good performance for
the stripping of Au(III)-loaded DEC. Thiourea and ammonia
solution, two commonly used Au(III) stripping agents nearly
quantitatively stripped Au(III) from the loaded MIBK and
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Table 2. Overview of the Tested Stripping Agents for the Table 4. Literature Values of the Vapor Pressure, Boiling
Removal of Au(III) from a Loaded DEC Organic Phasea Point, Flash Point, and Solubility in Water and Relative
Density of DEC, MIBK, and DBCc
concentration
stripping agent (mol L−1) %S pHin pHeq property DECa,e MIBKa,d DBCb,d
ascorbic acid 1 99.6 ± 0.2 1.9 1.8 vapour pressure (mm Hg) 10.8 19.9 0.02 (at 20 °C)
FeSO4 1 99.2 ± 0.6 3.0 2.8 (at 25 °C) (at 25 °C)
oxalic acid 1 97.5 ± 0.6 0.6 0.2 boiling point (°C) 126 116 256
thiourea 1 100.0 ± 0.0 6.5 2.7 flash point (closed cup) 25 18 118
NH3(aq) 1 100.0 ± 0.1 11.9 10.9 solubility in water (g L−1) 18.8 19.0 <1
at 25 °C
Na2S2O3 1 100.0 ± 0.0 7.1 6.1
relative density (water = 1) 0.98 0.80 0.885
Na2SO3 1 100.0 ± 0.0 11.1 9.0
viscosity 0.749 0.6 2.39 cPa
NaSCN + NaOH 1 + 0.01 88.3 ± 2.4 11.8 8.7 (at 25 °C) (at 20 °C) (at 20 °C)
NH4SCN 1 87.6 ± 0.2 4.9 2.9 a
Data collected from PubChem, U.S. National Library of Medicine.
NaCl + NaOH 1 + 0.01 99.4 ± 0.2 11.8 8.7 b
Data collected from CAMEO Chemicals, U.S. National Oceanic and
water 97.5 ± 0.6 7.0 3.1 Atmospheric Administration. cData provided by ThermoFisher. dData
HCl 0.01 98.6 ± 0.5 2.1 2.1 provided by The Dow Chemical Company. eRef 51
NH4Cl 1 67.5 ± 0.7 5.2 3.0
a
Experimental parameters: 60 min; 25 °C; organic composition = 0.1
g L−1 Au(III) in DEC; and O/A = 1:1. could lead to the reversal of the decomposition reaction (the
formation of DEC). Under these conditions, the system would
reach a gas−liquid equilibrium. This would not be
DBC, as was observed for DEC. Water and 0.01 mol L−1 HCl, representative for a process that occurs in open reactors.
which are mild stripping agents, resulted in poor stripping However, full decomposition of DEC was observed under the
efficiencies for both MIBK and DBC, while they performed rather severe conditions of contacting with 12 mol L−1 HCl at
well for DEC (Table 3). This is probably explained by the 60 °C, in spite of the reaction being carried out in a sealed vial
weaker extraction of Au(III) by DEC, which allows for easier (entry 9 in Table 5). This demonstrates that the reformation of
stripping. DEC from ethanol and CO2 is negligible as no DEC was
An overall comparison of the characteristics of DEC, MIBK, present in spite of the high concentration of ethanol and the
and DBC showed that DEC and MIBK have very similar high partial pressure of CO2. The equilibrium constant of the
physical properties: a relatively high vapor pressure (although decomposition of DEC is thus very high. The value for the
that of MIBK is nearly twice that of DEC), a low flash point, equilibrium constant is equal to the ratio of rate constant of the
and a significant solubility in water (Table 4). By contrast, forward reaction to that of the reverse reaction (Keq =
DBC shows more favorable physical properties: low vapor kdecomposition/kformation). Hence, the rate constant of the reverse
pressure, high flash point, and a low solubility in water. The reaction (DEC formation), kformation, is negligibly small, and the
advantage of DEC is its green character: DEC can be produced rate of decomposition in sealed vessels can be considered
by condensation of ethanol and CO2 under increased representative for those in open reactors.
temperature and pressure, rendering it a completely non-fossil The degree of decomposition was determined by integration
fuel-based solvent. of the methyl 1H NMR signal of DEC (1.20 ppm), ethanol
Stability of DEC. It is known that the carbonate diester (1.06 ppm), diethyl ether (1.10 ppm), and chloroethane (1.41
functional group of DEC hydrolyzes in the presence of water, ppm). Samples were prepared by diluting the biphasic reaction
yielding two ethanol molecules and one CO2 molecule. This mixture in DMSO-d6 until homogeneous. As the hydrolysis of
reaction is catalyzed by protons or hydroxide ions in acidic or one molecule of DEC yields two molecules of ethanol or
alkaline solutions, respectively (Figure 9a,b). As solvent chloroethane or one molecule of diethyl ether, the reaction
extraction of metals is generally performed in moderately stoichiometry was taken into account when calculating the
acidic conditions, potential acid hydrolysis of DEC should be percentages of DEC decomposition.
taken into account. Almost all tested samples, even with pure water, showed
The decomposition was quantified by contacting DEC with signs of DEC decomposition. However, the temperature, type
aqueous solutions containing varying concentrations of acids of aqueous solute, and concentration have a drastic influence
(HCl and H2SO4), base (KOH) or salts (NaCl and LiCl), and on the extent. The decomposition of DEC by pure water at 60
also with pure water (Table 5). These experiments were °C, 0.4%, was set as a reference point to compare the other
performed in sealed vials to avoid evaporative losses of acids, bases, and salts. The addition of HCl to the solutions
decomposition products. In sealed vials, the buildup of CO2 strongly promoted hydrolysis: adding 0.01 mol L−1 resulted in

Table 3. Comparison of Different Stripping Agents in the Stripping of Au(III)from MIBK, DEC, and DBCa
MIBK DEC DBC
%S pHin pHeq %S pHin pHeq %S pHin pHeq
thiourea (1 M) 99.2 ± 0.1 6.4 3.2 100.0 ± 0.0 6.5 2.7 100.0 ± 0.0 6.3 2.3
HCl (0.01 M) 14.1 ± 2.7 2.0 2.2 98.6 ± 0.5 2.1 2.1 32.3 ± 15.7 2.2 1.9
water 54.1 ± 2.1 7.0 3.7 97.5 ± 0.6 7.0 3.1 53.2 ± 9.3 7.0 2.5
NH3 (1 M) 99.9 ± 0.3 12.0 11.7 100.0 ± 0.1 11.9 10.9 94.6 ± 0.2 11.9 11.6

a
Experimental parameters: 60 min; 25 °C; organic composition = 0.1 g L−1 Au(III) in MIBK, DEC, and DBC; and O/A = 1:1.

13719 https://dx.doi.org/10.1021/acssuschemeng.0c04008
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Figure 9. Reaction scheme of DEC decomposition: (a) acid-catalyzed and (b) base-catalyzed.

Table 5. DEC Decomposition and Reaction Products after Contact with Different Aqueous Phasesa
entry aqueous solute concentration (mol L−1) temperature (°C) DEC decompositionb (%) reaction productsc
1 water 60 0.4 ethanol
2 HCl 0.01 30 0.17 ethanol
3 HCl 0.1 30 0.20 ethanol
4 HCl 1 30 0.99 ethanol
5 H2SO4 1 60 11 ethanol
6 HCl 0.01 60 19 ethanol + diethyl ether
7 HCl 0.1 60 12 ethanol + diethyl ether
8 HCl 1 60 10 ethanol
9 HCl 12 60 100 ethanol + chloroethane
10 KOH 0.01 60 1.4 ethanol
11 KOH 0.1 60 7 ethanol
12 KOH 1 60 15 ethanol
13 NaCl 6.2 60 0.0
14 LiCl 10 60 0.0
a
Experimental parameters: O/A ratio = 1:2; duration: 7 days; and stirred at 1200 rpm. bEstimated relative error: 3% (samples without diethyl
ether) or 10% (samples containing diethyl ether). cThe products listed here are those found by NMR analysis. Therefore, CO2 is not listed,
although it is a reaction product of DEC together with ethanol. The presence of CO2 was evident from a buildup of pressure and effervescence
upon opening of the reaction vials.

a decomposition of 19% at 60 °C, compared to 0.4% for pure
water. Upon addition of more acid, the degree of
decomposition was first lowered but rose again to reach
100% for 12 mol L−1. This decrease is counterintuitive as
adding more catalyst is expected to increase the reaction rate.
However, the addition of strongly hydrated species such as
chloride ions might induce a salting-out effect, lowering the
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mutual miscibility of DEC and the aqueous phase and lowering
the activity of water. This decreases the exposure of DEC to
the acid and lowers the nucleophilicity of water. At lower
temperatures, the decomposition was drastically suppressed, as
can be seen from entries 2−4 and 6−8 in Table 5. For HCl
solutions, working at 30 °C suppressed the decomposition to
<1% compared to >10% for 60 °C. This is to be expected as
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ACS Sustainable Chemistry & Engineering
reaction rate constants increase with rising temperatures.
When H 2 SO 4 was used instead of HCl, the same
decomposition rate was observed. This is explained by H3O+
being the actual species catalyzing the DEC hydrolysis. At
moderate concentrations, strong acids are fully ionized to
H3O+ and their respective anions. Choosing another strong
acid will therefore not influence the amount of H3O+, if the
same concentration is used.
A remarkable observation is that, in addition to the expected
decomposition products, CO2 and ethanol, other products
were formed as well. When using HCl as a catalyst at 60 °C,
diethyl ether and chloroethane were found in the mixture. The
side product formed depended on the HCl concentration.
Lower HCl concentrations resulted in the formation of diethyl
ether, while using 12 mol L−1 HCl resulted in the formation of
chloroethane. This can be explained by the abundance of
ethanol and hydrochloric acid molecules in the mixtures. Both
side products are formed from ethanol by SN2 reactions in
which the hydroxyl group is protonated and water is expelled.
The expulsion of water occurs concurrently with an attack by a
chloride ion or another ethanol molecule. Therefore, the
abundance of both hydrochloric acid and ethanol will influence
the outcome of the reaction, and the two reaction pathways
will compete with each other. The rate of formation of
chloroethane increases with the concentration of HCl, while
the rate of formation of diethyl ether increases with the
concentration of ethanol. Remarkably, using an intermediate
concentration (1 mol L−1 HCl) yields neither of both side
products. Possibly, the concentration of either species is too
low to react with a protonated ethanol molecule before the
proton is transferred back to water. Working at lower
temperatures (30 °C) also prevented the formation of side
products, although the lower abundance of ethanol in these
mixtures is a large contributing factor as well.
Hydrolysis in alkaline solutions was observed to be similar
overall, although there were some differences. First, the
decomposition was universally more efficient at higher base
concentrations (1 mol L−1) and less efficient at lower base
concentrations (0.01 mol L−1). Second, ethanol was formed
exclusively as a reaction product, together with CO2. This can
be rationalized by the absence of chloride and acidic
conditions, which are requirements for the formation of
chloroethane and diethyl ether, respectively.
The effect of the presence of alkali halides was tested as
these salts are often used in solvent extraction. Remarkably, no
decomposition of DEC was found in these samples, while even
pure water led to 0.4% decomposition of DEC. This
observation can again be explained by the salting-out effect,
decreasing the exposure of DEC to the aqueous phase and
reducing the activity of water. Because the selective extraction
of Au(III) from Cu(II)-containing solutions proceeded best at
high alkali metal chloride concentrations, it is a major
advantage that DEC does not hydrolyze under these
conditions.
■
CONCLUSIONS
DEC is a promising extractant for solvent extraction of Au(III)
from concentrated chloride solutions, characterized by a very
high selectivity over Cu(II) (separation factor >1000) and
facile stripping with pure water. At high chloride concen-
trations, DEC is a sufficiently strong extractant to sequester
gold from large volumes of dilute aqueous solutions.
Quantitative extraction of gold could be achieved with no
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pubs.acs.org/journal/ascecg Research Article
coextraction of copper. These properties allow the use of DEC
to concentrate Au(III) from dilute feed solutions containing
high concentrations of Cu(II). Extraction likely involves the
co-extraction of a proton together with a [AuCl4]− anion, and
hence the extraction is promoted by high acidities and high salt
concentrations (>5 mol L−1). However, as DEC is unstable
with respect to acid-catalyzed hydrolysis, high salt concen-
trations are preferred, which suppress the hydrolysis reaction.
These conditions are relevant to the extraction of gold from
chloride leachates of copper-rich sources, such as anode slimes.
DEC yields higher purity Au(III) extracts than MIBK and
DBC, two extractants which are often used to selectively
extract Au(III) over Cu(II). In addition, stripping is facilitated
using DEC as pure water can be used to effectively strip 98% of
gold in a single step. DEC can be prepared from carbon
dioxide and ethanol, exhibits low toxicity, and is highly
biodegradable, making it both an effective and a green
alternative for MIBK and DBC.
■ AUTHOR INFORMATION
Corresponding Author
Koen Binnemans − Department of Chemistry, KU Leuven, B-
3001 Leuven, Belgium; orcid.org/0000-0003-4768-3606;
Email: koen.binnemans@kuleuven.be
Authors
Stijn Raiguel − Department of Chemistry, KU Leuven, B-3001
Leuven, Belgium
Lukas Gijsemans − Department of Chemistry, KU Leuven, B-
3001 Leuven, Belgium
Arne Van den Bossche − Department of Chemistry, KU
Leuven, B-3001 Leuven, Belgium
Bieke Onghena − Department of Chemistry, KU Leuven, B-
3001 Leuven, Belgium
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.0c04008
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
S.R. and A.V.d.B. thank the Research Foundation Flanders
(FWO) for PhD grant. The authors acknowledge funding by
KU Leuven (project C32/17/011). The authors wish to thank
Rene Wiersma (Shell Global Solutions Int. B.V., Amsterdam,
The Netherlands) for providing samples of the solvents and for
scientific discussions. The authors are also grateful to Rayco
Lommelen for constructing speciation plots using OLI Studios.
■
ABBREVIATIONS
DBC, dibutyl carbitol; DEC, diethyl carbonate; MIBK, methyl
isobutyl ketone
■
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