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513 Binary Extract Ant Slim G
513 Binary Extract Ant Slim G
Research Article
the global lithium resources are found in salt lake brines, but
lithium is always accompanied by magnesium. It is a challenge
to efficiently separate lithium from magnesium in brines. The
state-of-the-art processes for lithium/magnesium separation
Downloaded via 81.244.213.242 on January 15, 2020 at 17:56:17 (UTC).
■ INTRODUCTION
The transition from fossil fuel-based cars to electric (and
The Mg/Li ratio is a key parameter determining whether a
brine can be exploited for lithium. The current commercial
hybrid electric) cars is an important measure to reduce CO2 process for lithium recovery from the brines with low Mg/Li
emissions and hence to counteract global warming. Lithium- ratios (<8) consists of several steps: (1) concentration of
ion batteries (LIBs) are nowadays commonly used in electric brines by evaporation in a solar pond for about 1 year, (2)
vehicles due to their high energy density and lightweight removal of magnesium by lime milk (Ca(OH)2), (3) removal
compared to other types of batteries.1,2 The improved of calcium by addition of Na2CO3/Li2CO3, and finally (4)
performance of the new generations of LIBs is an additional precipitation of Li2CO3 by addition of Na2CO3.12,13 This
incentive to electrification of transportation.3,4 The large process creates a heavy environmental burden because of the
amounts of lithium (as battery-grade Li2CO3) needed for the high consumption of precipitation reagents, generation of large
production of LIBs lead to a sharply increasing demand of amounts of waste, and high consumption of water for washing
lithium.5−7 the precipitate. Furthermore, it suffers from a low recovery
Pegmatites and brines are the two main resources of lithium. efficiency due to the loss of lithium during precipitation.
Although seawater contains huge amounts of lithium, the Recovery of lithium from brines with high Mg/Li ratios (>8,
lithium concentration (about 0.17 ppm) is too low to be and the ratio can sometimes even be >1000) is more
exploitable in the short term.8 The global exploitable lithium challenging, and only a few processes are operated at an
resources are estimated to be 31−34 Mt, with salt lake brines industrial scale worldwide. The West Taijinar Salt Lake in
comprising over 70% of these resources.9 Currently, the China is a representative brine with a high Mg/Li ratio (Mg/Li
majority of the global lithium production is obtained from ≈ 100) and it has been mined by CITIC China since
these brines.6,10,11 Magnesium always accompanies lithium in 2007.14−16 The key operation is the conversion of MgCl2 to
salt lake brines. It is challenging to separate lithium from
magnesium because these elements exhibit similar chemical Received: September 12, 2019
properties because of their diagonal relationship in the periodic Revised: October 28, 2019
table. Published: October 31, 2019
MgO by roasting powder mixtures of chloride salts that are reaction; for the stripping, acids are needed to regenerate the
obtained by spray drying of concentrated brines after extractant. In other words, the extraction and stripping are
extraction of potassium (for production of fertilizers). This driven by acidity (or pH) of the aqueous solution. On the
process is not only energy-intensive and water-consuming but contrary, extraction and stripping of magnesium by a binary
also environmentally detrimental because HCl gas is produced extractant is driven by the common ion effect, that is, the
during the roasting step. The process is economically viable concentration of chloride ions. When the chloride concen-
only when the lithium price is high and it is shut down when tration is high, magnesium is extracted; when the loaded
the lithium price is too low. In conclusion, the state-of-the-art organic phase is contacted with water, magnesium is stripped
processes for the separation of lithium and magnesium in due to the low chloride concentration. Therefore, no acids or
brines have severe limitations, independent of the Mg/Li bases are consumed during the extraction or stripping.
ratios. Considering the increasing demand for lithium, it is Unfortunately, binary extractants have not found any real
obvious that the development of more environmentally applications so far, despite many studies about magnesium
friendly processes for the recovery of lithium from brines is extraction from seawater mentioned above. The main obstacle
indispensable for the sustainable utilization of lithium for the application of binary extractants is perhaps the lack of
resources. driving force during extraction, that is, the concentration of
Selective solvent extraction of lithium from magnesium-rich chloride in seawater (about 19 g L−1) is not sufficient to drive
brine would be the best solution. However, this is also one of efficient magnesium extraction. By contrast, (concentrated)
the most difficult separation challenges and it has been studied salt lake brine has much higher chloride concentrations (can be
for about half a century without a real breakthrough. The most >150 g L−1); hence, it is very suitable for magnesium
intensively studied solvent extraction system for lithium and extraction using binary extractants.
magnesium separation is the synergistic solvent extraction In this study, we use Aliquat 336 (A336, a mixture of
system consisting of tributyl phosphate and FeCl3 (or ionic methyltrioctylammonium chloride and methyltridecylammo-
liquids).17−19 Despite good lithium selectivity over magnesium, nium chloride, with the former dominating) as the basic
this system suffers from difficult stripping and loss of FeCl3 (or extractant and Cyanex 272 (C272, bis(2,2,4-trimethylpentyl)-
cations of ionic liquids) into the aqueous phase. These phosphinic acid) and Versatic Acid 10 as the acidic extractant,
limitations prevent the application of this extraction system. to prepare binary extractants. These extractants were chosen
Following a different route, selective solvent extraction of because they are commercially available in large scale at
magnesium can be an alternative process for lithium and reasonable prices, and Versatic Acid 10 and Cyanex 272 are
magnesium separation because the extraction of magnesium is known to selectively extract magnesium over lithium.21,32 Two
easier than the extraction of lithium. Acidic extractants are binary extractants, [A336][V10] and [A336][C272] were
known to be able to efficiently extract magnesium. Zhang et al. synthesized and tested for the removal of magnesium from two
used saponified D2EHPA (di-(2-ethylhexyl)phosphoric acid) synthetic brines: concentrated brine (106 g L−1 Mg and 10 g
to extract magnesium from a synthetic brine solution L−1 Li) and original brine (15 g L−1 Mg, 80 g L−1 Na and 0.2 g
containing 19.5 g L−1 Mg and 0.02 g L−1 Li.20 Despite good L−1 Li). We show that [A336][V10] is able to remove
magnesium extraction, the coextraction of lithium was too magnesium quantitatively from the original brine in a three-
high. Following the same concept, Virolainen et al. studied the stage counter-current extraction with about 10% co-extraction
removal of small amounts of calcium and magnesium of lithium, without consumption of any acids or bases.
impurities from concentrated lithium solutions using
D2EHPA and Versatic Acid 10 (V10, a mixture of carboxylic
acids with the common structural formula of C10H20O2) and
■ EXPERIMENTAL SECTION
Chemicals. Aliquat 336 (∼90%) was obtained from Sigma-Aldrich
found that V10 has less co-extraction of lithium.21 Unfortu- (Diegem, Belgium); Cyanex 272 (85%) was obtained from Cytec
nately, the method of Virolainen et al. is not suitable for direct Industries B.V. (Vlaardingen, Netherlands); Versatic Acid 10 (>90%)
removal of magnesium from brine, because magnesium in was obtained from Resolution Europe B.V. (Amsterdam, The
brine is so abundant that the consumption of base during Netherlands); NaOH (analytical reagent), NaCl (≥99.5%), HCl
(37%), toluene (analytical reagent), and ethylenediaminetetraacetic
extraction (to neutralize the protons) and acids during
acid (EDTA, 0.10 M) were supplied by Fisher Scientific (Merelbeke,
stripping (to regenerate the acidic extractant) would be too Belgium); LiCl (≥99.5%) was obtained from Carl ROTH (Karlsruhe,
large. Germany); MgCl2 (99%), p-cymene (>99%), n-heptane (99% for
To avoid the consumption of acids and bases for the HPLC), MIBK (99.5%), n-decanol (98%), and Eriochrome Black T
selective removal of magnesium from magnesium-rich brines, were obtained from Acros Organics (Geel, Belgium); KCl (analytical
this study investigates the use of binary extractants instead of reagent), NH4Cl (analytical reagent), Li, Na, and Mg standard
acidic extractants. Binary extractants consist of an acidic solutions (1000 ± 10 mg L−1) were purchased from Chem-Lab
extractant saponified with a basic extractant.22−29 In other (Zedelgem, Belgium); NH3 aqueous solution (25%) was purchased
words, it is an ionic liquid with the cation being (quaternary) from VWR Chemicals (Leuven, Belgium). Milli-Q water (18.2 MΩ
cm at 298.2 K) was used to prepare the aqueous solutions. All
ammonium and the anion being a de-protonated acidic chemicals were used as received, without any further purification.
extractant molecule. It is worth mentioning that quaternary General Synthesis Procedure of the Binary Extractants. The
phosphonium compounds work in the same way as quaternary synthesis of the binary extractants was based on literature
ammonium compounds although the former is much more procedures.22,26,33 The following general reaction scheme is applicable
expensive. Some phosphonium-based binary extractants (e.g., for the synthesis
trihexyl(tetradecyl)phosphonium bis-2,4,4-(trimethylpentyl)
phosphinate, also known as Cyphos IL 104) have also been [NR3R′]+ Cl− + HA + NaOH V [NR3R′]+ A− + NaCl + H 2O
studied for extraction of metal ions.30,31 In the extraction of (1)
magnesium using acidic extractants, bases are needed to with R′ = methyl, R = octyl or decyl and HA is the acidic extractant.
neutralize the released protons in order to drive the extraction NaOH was used to deprotonate the acidic extractant and to drive the
equilibrium to the right. No toxic byproducts were produced during concentrations by ICP-OES and EDTA titration (only for
the synthesis, just NaCl and water. magnesium).
Calculated amounts of the basic (Aliquat 336) and the acidic The percentage extraction % E, percentage stripping % S,
extractants (Cyanex 272 or Versatic Acid 10) were added together in distribution ratio D, and separation factor α are defined as
a 1:1 stoichiometric ratio. The amounts (in moles) added were corg ·Vorg
estimated taking the purity of the commercial products into account. %E = × 100%
A freshly prepared NaOH solution (4.0 mol L−1) was added to the corg ·Vorg + caq ·Vaq (2)
mixture before it was cooled down completely. The still warm NaOH
solution (51 °C) helped to decrease the viscosity of the mixture and corg − corg,S
%S = × 100%
increased the stirring efficiency. The mixture was agitated vigorously corg (3)
for 4 h. Afterward, the mixture was left for phase separation. The
organic layer was collected and washed three times with Milli-Q water corg
to remove chloride ions. The complete removal of chloride ions was D=
caq (4)
checked with an acidified silver nitrate solution. Any entrained water
in the organic phase after washing was removed using a rotary DA
evaporator. The 1H (Figures S1 and S3) and 13C NMR spectra α=
(Figures S2 and S4) together with the elemental analysis of the DB (5)
compounds can be found in the Supporting Information. The yield of where corg and caq and Vorg and Vaq are concentrations and volumes of
[A336][C272] was 94% and that of [A336][V10] was 96%. The the organic and the aqueous phase at extraction equilibrium,
structures of [A336][C272] and [A336][V10] are shown in Figure 1. respectively; corg,S is the concentration of the organic phase after
stripping; DA and DB are the distribution ratios of metals A and B,
respectively.
Extraction Rate. A series of reaction vials (4.0 mL) with 2.0 mL
of aqueous phase and 2.0 mL of organic phase were shaken on the
Thermo Scientific 2000 shaker at 300 rpm, and samples were taken
out and analyzed at a certain time interval. The loading profile of
metals as a function of time was established.
Batch Counter-Current Extraction Test. A batch counter-
current extraction (BCE) test was conducted to simulate a counter-
current multistage solvent extraction. The flowsheet can be found in
Figure 10. Up to 12 series of extraction (10 mL of aqueous phase and
17.5 mL (or 15 mL) of organic phase in each extraction) were carried
out to attain a stable state in the system. Each batch was shaken for 30
min, and the phase disengagement was accelerated by centrifugation
for 5 min at 4000 rpm. The last batches (nos. 11 and 12) were used to
determine the concentration of magnesium, lithium, and sodium in
the three extraction stages of the counter-current extraction test.
Mixer−Settler Test. Based on the results of the BCE test, the
feasibility to run the extraction in a continuous mode was tested using
a small mixer−settler battery (Rousselet Robatel, model UX 1.1).
Each mixer−settler stage is made of polytetrafluoroethylene (PTFE)
and has an effective volume of 35 mL for the mixer and 143 mL for
the settler. The settler is provided with a removable baffle and two
Figure 1. Structures of (a) [A336][C272] and (b) [A336][V10]. The coalescence plates made also of PTFE to accelerate the phase
main component of [A336] and [C272] is shown. For [V10], one disengagement. A glass window at the end of the settling chamber
isomer of the mixture is shown. allows checking the O/A ratio in the settler. The position of the O/A
interphase in the settler is regulated by adjusting the height of a weir.
Preparation of Synthetic Brine Solutions. Two synthetic feed Two Masterflex L/S Cole-Parmer peristaltic pumps were used to
solutions were prepared based on the composition of the West pump the aqueous and organic phases. For the extraction, the flow
Taijinar Salt Lake in China, which is a representative salt lake with a rate was 1.7 and 1.0 mL min−1 for the organic and aqueous phases,
high Mg/Li ratio that has been mined for lithium. The first feed respectively. On the basis of the flow rates and volumes of the mixer
solution (106 g L−1 Mg, 10 g L−1 Li) mimics the concentrated brine, and settler, the residence time in the mixer and settler is 13 and 53
which would be spray-dried and roasted in the current process. The min, respectively. The total residence time is sufficient for the
second feed solution (15 g L−1 Mg, 0.2 g L−1 Li, 80 g L−1 Na) mimics extraction to reach equilibrium. Samples of both the aqueous and the
the original brine of the West Taijinar Salt Lake. The feed solutions organic phases were taken every hour during the operation of the
were prepared by dissolving weighed amounts of chloride salts in mixer−settler. The aqueous phases and the stripping solutions of the
Milli-Q water. organic phases were analyzed by ICP-OES.
Extraction Experiments. Each extraction experiment was carried EDTA Titration. EDTA titration was used for the determination of
out in a 15 mL centrifuge tube with 5.0 mL of aqueous solution and the magnesium concentrations, in addition to measurement by ICP-
5.0 mL of organic solution, respectively. Mixtures of the two phases OES. The samples were buffered at pH = 10 using an NH3/NH4Cl
were shaken for 30 min at 300 rpm using a Thermo Scientific 2000 buffer. Eriochrome black T was used as an indicator. No interference
shaker to attain equilibrium. Afterward, the samples were centrifuged of lithium and sodium was expected during analysis based on the work
for 5 min at 4000 rpm. Scrubbing and stripping experiments were of Gao et al.34 Samples were analyzed in triplicate.
carried out using the same method. Organic-to-aqueous phase ratios Analytical Instruments. Magnesium, lithium, and sodium were
(O/A) were varied by varying the organic and aqueous volumes analyzed using a PerkinElmer Optima 8300 ICP-OES equipped with a
accordingly. Investigation of the effect of metal concentration was Scott crossflow nebulizer. A Bruker AVANCE NEO 400 nuclear
carried out by varying the metal (salt) concentration of interest, while magnetic resonance spectroscopy device was used to record the 1H
keeping the concentrations of other salts constant. The aqueous NMR (400 MHz) and 13C NMR (100 MHz, decoupled) spectra. A
phases after equilibrium and resultant aqueous solutions after Thermo Scientific FLASH 2000 Elemental Analyzer was used for the
stripping were analyzed for magnesium, lithium, and sodium elemental analysis of the synthesized compounds.
Figure 2. Influence of the [A336][V10] concentration on the loading Figure 3. Effect of the acid concentration on the stripping of
and the percentage extraction of magnesium and lithium. The phase magnesium and lithium. The loaded organic phase composed of 13.5
ratio was 1/1. g L−1 Mg and 0.5 g L−1 Li. The phase ratio was 1/1.
loading of magnesium scrubs lithium and sodium, which is an phase ratio was performed when constructing a McCabe−
important observation. Thiele diagram.
In terms of percentage extraction, the values decreased for McCabe−Thiele Diagram. A McCabe−Thiele diagram
all of the three metal ions. The decrease of percentage could be constructed based on the results of magnesium
extraction of magnesium from 97 to 54% is because extraction with various O/A phase ratios. The McCabe−Thiele
magnesium increased too much in the feed solution, although diagram including the operating line can be found in Figure 8.
the loading of magnesium also increased. However, the
decrease of lithium and sodium percentage extraction from
25 and 9.6 to 5.5 and 1.5%, respectively, is due to the decrease
in the absolute loading caused by the scrubbing effect of
magnesium.
Effect of the Phase Ratio. The phase ratio variation method
was used to construct a McCabe−Thiele diagram for the
extraction of metals from the original brine using
[A336][V10]. The results can be found in Figure 7 in terms
cumulative, and the sum is 100%. In the first stage, 90% of the
loaded lithium and 46% of the loaded magnesium were
stripped. In the second stage, most of the remaining lithium
was stripped, together with 22% of magnesium. In the
subsequent stages, no additional amounts of lithium were
stripped because it had already been completely stripped in the
first two stages. 13% magnesium was stripped in the third stage
and complete stripping of magnesium was achieved using 1.0
mol L−1 HCl in the last stage. In short, 81% magnesium can be
stripped in three stages using water with an O/A phase ratio of
3/1, which is higher than a single-stage stripping using water
with an O/A phase ratio of 1/1 (62%). These two stripping
approaches consume the same amount of water. The stripping
of magnesium regenerates [A336][V10], which in principle
Figure 12. Effect of phase ratio on the percentage scrubbing (% Scr) can be used for the next extraction cycle.
of the loaded organic phase obtained after the BCE. Mixer−Settler Experiments. To check the practical
potential of the separation of lithium and magnesium using
[A336][V10], mixer−settler experiments were carried out.
Pictures of the setup are given in Figure S15. Only the
extraction step (not including scrubbing or stripping) was
studied in mixer−settlers because it represents the core of the
separation process presented in this work. In the mixer−settler
test, coalescence plates were used in the settler to aid the
separation of the phases. Good phase disengagement was
achieved in each of the extraction stages and formation of
emulsions or the third phase was not observed during the total
duration of the experiment.
After running the experiment for 7 h, 94% magnesium was
extracted with 11% lithium co-extraction. The results are
presented in Figure 14 and they are consistent with the results
obtained for the batch counter-current test (Figure 11). The
results show that the aqueous lithium concentration remained
practically constant in the extraction stages EX 1 and EX 2 and
slightly decreased in stage EX 3. The aqueous magnesium
concentration decreased with the increasing number of
extraction stages: from 14.51 g L−1 in the feed until 0.19 g
L−1 Mg left in the raffinate at EX 3, with >98% removal of
magnesium. The loading of magnesium in the organic phase
increased from 1.32 g L−1 at EX 3 to 7.81 g L−1 at EX 1. While
the loading of lithium in the organic phase decreased from
0.032 g L−1 at EX 3 to 0.014 g L−1 at EX 1, due to the
scrubbing effect by loaded magnesium.
After 7 h of extraction, the system was shut down and
restarted again the next day. Analysis of the samples taken at
Figure 13. Percentage stripping of magnesium and lithium with HCl the 15th h show that 97% of magnesium had been extracted
solution or water using different phase ratios in single-stage stripping with 13% of lithium coextraction (Figure S16). These results
(a); percentage stripping of magnesium and lithium with water (ST 1, prove that the binary extractant [A336][V10] extracts
ST 2 and ST 3) and 1.0 mol L−1 HCl (ST 4) with an O/A phase ratio magnesium efficiently and selectively from the lithium-
of 3/1 in multistage cross-current stripping (b). containing brine solutions and the process can be safely and
easily carried out in a continuous mode. The complete metal
reduction in stripping efficiency for both lithium and loading profile as a function of time is given in Figure S17.
magnesium. An O/A phase ratio of 3/1 seems to be a good Lithium in the extraction raffinate after removal of
compromise between stripping efficiency and consumption of magnesium could be concentrated by a synergistic solvent
water. extraction system containing a beta-diketone (e.g., LIX 54) and
Multistage Stripping with Water. An O/A phase ratio of 3/ a neutral ligand (e.g., Cyanex 923). Plenty of studies have
1 was further tested for multistage cross-current stripping using investigated this extraction system.39,40 The loaded lithium in
water. Four stripping stages were investigated. In the first three the organic phase after extraction from the raffinate can be
stages, water was used as the stripping agent, followed by stripped and concentrated in an aqueous solution, which can
complete stripping of the remaining magnesium, lithium, and subsequently be treated by Na2CO3 to produce Li2CO3. The
sodium using 1.0 mol L−1 HCl (for analysis purpose). The concentration of lithium by solvent extraction would require
mass balance was used to calculate the percentage stripping, base and acids for adjustment of pH. However, the amount of
and the results are shown in Figure 13b. The amounts stripped chemicals required is much smaller than the precipitation of
can be found in Figure S14. The stripping percentages are magnesium in the existing process. Besides, the MgCl2
19232 DOI: 10.1021/acssuschemeng.9b05436
ACS Sustainable Chem. Eng. 2019, 7, 19225−19234
ACS Sustainable Chemistry & Engineering Research Article
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.9b05436.
Characterizations of [A336][V10] and [A336][C272];
properties of [A336][V10]; more tests data on
magnesium extraction from concentrated brine; loading
of magnesium, lithium and sodium in the organic phase;
scrubbing and stripping of magnesium and lithium under
various conditions; batch counter-current tests with O/
A ratio of 1.5; and results of mixer−settler test (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: zheng.li@kuleuven.be.
ORCID
Figure 14. Metal loading profiles of magnesium and lithium in the Zheng Li: 0000-0002-7882-5999
aqueous phase (a) and in the organic phase (b), and percentage Xiaohua Li: 0000-0003-4555-8705
extraction of magnesium and lithium relative to the feed solution (c), Sofía Riaño: 0000-0002-1049-6156
during the three-stage counter-current mixer−settler experiment at
the 7th h. The phase ratio O/A was 1.7/1. Koen Binnemans: 0000-0003-4768-3606
Notes
obtained in the new process has a high purity (>99%) and The authors declare no competing financial interest.
hence might be a marketable byproduct.
Sustainability of the Process. The proposed new process
for separation of magnesium and lithium by selective removal
■ ACKNOWLEDGMENTS
The research was supported by the European Research
of magnesium using the binary extractant [A336][V10] is Council (ERC) under the European Union’s Horizon 2020
more sustainable than the state-of-the-art processes. The Research and Innovation Programme: grant agreement
sustainability of the new process includes (1) no consumption 694078solvometallurgy for critical metals (SOLCRIMET).
■
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