Minerals Engineering 127 (2018) 296–304

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Solvent extraction and stripping of copper in a Y-Y type microchannel T

reactor
Feng Jianga,b,c,d, Jiannan Peia,c,d, Shaohua Yina,c,d, Libo Zhanga,c,d, Jinhui Penga,c,d,
⁎ ⁎⁎
Shaohua Jua,c,d, , Jan D. Millera,b, , Xuming Wanga,b
a
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650093, China
b
Department of Metallurgical Engineering, College of Mines and Earth Sciences, University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114,
USA
c
Key Laboratory of Unconventional Metallurgy, Ministry of Education, Kunming, Yunnan 650093, China
d
Yunnan Provincial Key Laboratory of Intensification Metallurgy, Kunming, Yunnan 650093, China

A R T I C LE I N FO A B S T R A C T

Keywords: The solvent extraction and stripping of copper have been conducted in a Y-Y type microchannel reactor. The
Copper experimental results demonstrate that the Y-Y type microchannel reactor can be used for both Cu extraction and
Solvent extraction Cu stripping. The effects of residence time, aqueous phase pH, and concentration of extractant on the extent of
Y-Y type microchannel extraction were investigated. The results indicated that the extent of extraction and the separation factor using a
DZ988N extractant
Y-Y type microchannel reactor are greater than those obtained with a conventional batch extraction. The
maximum extraction of copper reached 86.02%. Also, the stripping reaction was studied with respect to Cu2+
concentration in the loaded organic phase, H2SO4 concentration, and the organic/aqueous phase ratio. The
maximum stripping of copper reached 98.94%.
The overall volumetric mass transfer coefficients (KL α ) were calculated to evaluate mass transfer char-
acteristics. For comparison, conventional batch extraction experiments were also carried out, in parallel. The
laminar flow pattern through the Y-Y microchannel was investigated by numerical simulation, and by experi-
mental measurements. The maximum separation factors, βCu / Fe and βCu / Zn , were found to be 465.53 and 1249.70,
respectively. Higher KL α values (0.4937–3.3969 s−1) were obtained for Cu within 5 s using a microchannel
reactor compared with values (0.006–0.073 s−1) from batch experiments. Much higher overall volumetric mass
transfer coefficients, KL α values (0.4937–3.3969 s−1) for Cu, and lower KL α values for Fe (0.0477–0.3173 s−1)
and Zn (0.0395–0.2130 s−1), demonstrated an effective separation between Cu and Fe, Zn.

1. Introduction
Copper is one of the most widely-used metals in society. Due to its
unique properties, copper is essential for many economic sectors, in-
cluding uses for infrastructure, wiring, plumbing, transportation, and
consumer and industrial electrical equipment (Elshkaki et al., 2016).
Hydrometallurgical processes are types of technology used for copper
metal production and currently account for approximately 21% of the
world primary copper production (Hiskey, 2014). It should be noted
that 16% of the total copper production was accomplished by leaching/
solvent extraction (SE)/electrowinning (EW) methods in 2014
(Hawkins and Carlson, 2016). There are about 75 copper SX operations
worldwide with cathode production above 10 kt/a. The top ten
producers currently account for about 40% of the global 4.3 Mt/a
SX–EW copper production (Sole and Tinkler, 2016). The solvent ex-
traction step is particularly important to ensure the purity of the metals
(Tang and Steenari, 2015). However, there are some disadvantages,
such as large space requirements, high energy input (Luo et al., 2017),
serious co-extraction (Li, 2017; Li et al., 2013), and phase emulsifica-
tion (Ling et al., 2008; Ning et al., 2009). Therefore, developing a new
environmentally-friendly extraction technology, with a smaller foot-
print, lower energy consumption, and higher efficiency, is necessary to
overcome the above problems associated with copper hydrometallurgy.
In recent years, solvent extraction using microreactors has received
much attention, due to enhanced mass transfer in the microflow process
(Wang and Luo, 2017). Microfluidic solvent extraction has been

*
Corresponding author at: Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650093, China.
⁎⁎
Corresponding author.
E-mail addresses: shj_200801@126.com (S. Ju), Jan.Miller@utah.edu (J.D. Miller).

https://doi.org/10.1016/j.mineng.2018.08.014
Received 26 April 2018; Received in revised form 30 July 2018; Accepted 6 August 2018
Available online 23 August 2018
0892-6875/ © 2018 Elsevier Ltd. All rights reserved.
F. Jiang et al.
Fig. 1. Schematic diagram of the experimental setup.
investigated for liquid-liquid extraction of uranium (Darekar et al.,
2014b; Hellé et al., 2015), rare earth elements (Chen et al., 2017; Jiang
et al., 2018a; Kolar et al., 2016), cesium (Tamagawa and Muto, 2011),
platinum (Kriel et al., 2015), palladium (Yin et al., 2013), lanthanum
(Yin et al., 2015), silver (Nagai et al., 2009), and plutonium (Yamamoto
et al., 2015). Zhang et al. (2018) studied liquid-liquid extraction for the
separation of Co(II) from Ni(II) using a pilot scale re-entrance flow
microreactor. More than 99.9% of the Co was separated from the
aqueous phase in two-stage countercurrent extraction. Leblebici et al.
(2016) investigated the solvent extraction of rare earth elements using a
milli-channel mixer and phase separator. The entire mixing and phase
separation process was completed in 10–20 s. In contrast, about 25 min
of processing time is usually observed when convectional mixer–settlers
are used in industry. Priest et al. (2011) explored microfluidic solvent
extraction of copper. Microfluidic solvent extraction shows great pro-
mise for the use of smaller equipment footprints, the recycling of vo-
latile liquids, and the reduction of chemical exposure to workers.
Darekar et al. (2014a) carried out experiments to study the extraction of
zinc in microchannels. For the Zinc–D2EHPA system, mass transfer
coefficient KL α values for the microchannels are likely to be much
higher than those for conventional contactors such as mixer settlers,
centrifugal extractors, and spray columns.
The above results reported in the literature indicate that micro-
fluidic solvent extraction has good prospects for the extraction and
separation of metals. The goal of the current research was to apply
microfluidic solvent extraction technology to copper hydrometallurgy.
As is well known, the hydrometallurgy of copper includes the pro-
cesses of leaching, solvent extraction, stripping, and electrowinning
(Marsden, 2006). Compared with a previous study (Jiang et al.,
2018b), this work focuses on solvent extraction and stripping of
copper in a Y-Y type microchannel reactor. In this regard, the Y-Y type
microchannel is evaluated for both copper extraction and copper
stripping. Effects of residence time, aqueous phase pH, and the con-
centration of extractant on the extent of extraction were investigated,
and the overall volumetric mass transfer coefficients (KL α ) were cal-
culated to evaluate mass transfer characteristics. The laminar flow
pattern through the Y-Y microchannel was investigated by numerical
simulation, and by experimental measurements. Also, the stripping
reaction was studied with respect to Cu2+ concentration in the loaded
organic phase, H2SO4 concentration, and the organic/aqueous phase
ratio.
297
Minerals Engineering 127 (2018) 296–304
2. Materials and experimental procedures
2.1. Reagents
The extractant, DZ988N, a mixture of 5-nonylsalicylaldoxime and 2-
hydroxy-5-nonyl-acetophenoneoxime with a volume ratio of 1:1, was
supplied by De Song Technology Co., Ltd, China. The Mextral DT100
(containing > 99% aliphatics and < 0.5% aromatics) was supplied by
the Hallochem Group Co., Ltd, China, and was used as diluent. In all
extraction experiments, the organic phase was obtained by dissolving
the extractant, DZ988N, into the Mextral DT100. The reagents,
CuSO4⋅5H2O, Fe2(SO4)3 and ZnSO4⋅7H2O, were analytical grade and
purchased from Sinopharm Chemical Reagent Co., Ltd., Shanghai,
China. Sulfuric acid solution was used for stripping and was purchased
from Tianjin Fengchuan Chemical Reagents Technologies Co., Ltd.,
Tianjin, China.
In all extraction experiments, the aqueous phase was prepared by
using CuSO4⋅5H2O, Fe2(SO4)3, and ZnSO4⋅7H2O to simulate the solu-
tions of a copper operation in Yunnan Province, China, which contains
3.0 g/L Cu2+, 2.0 g/L Fe3+ and 1.0 g/L Zn2+. The pH value of the
aqueous phase was controlled by the addition of ammonia and sulfuric
acid to the desired value using a PHS-3D meter (INESA Scientific
Instrument Co., Ltd, China).
2.2. Apparatus and procedures
A schematic diagram of the experimental setup is shown in Fig. 1.
All of the experiments were conducted in a Y-Y type microchannel re-
actor. The microchannel reactor was designed by our research group
and manufactured by Wenhao Chip Tech Co. Ltd., Suzhou, China, as
shown in Fig. 2. Table 1 shows the dimensions of the Y-Y type micro-
channel. The total volume of the microchannel is 1.305 × 10−3 cm3.
The organic phase and aqueous phase were pumped into the Y-Y
type microchannel reactor via the two inlets by two microsyringe
pumps (LSP01-1B, Baoding Longer Precision Pump Co., Ltd., Baoding,
China, accuracy ≤ ± 0.5%). The organic phase and aqueous phase
merged at the beginning of the mixing channel, the inlet Y-junction,
and separated at the end of the mixing microchannel, the outlet Y-
junction. The flow pattern of the two phases was determined using a
high speed camera during the experiments. The mixing microchannel
(the microchannel from inlet Y-junction to outlet Y-junction) is where
F. Jiang et al. Minerals Engineering 127 (2018) 296–304

the distribution ratios for A and B, respectively. [A]org , [A]aq , [B]org and
[B]aq represent the concentration of A in the organic phase and aqueous
phase, and the concentration of B in the organic phase and aqueous
phase, respectively.
The extent of stripping is defined as follows (Liqiu et al., 2012):
Cin, org−Cout , org
Y= × 100%
Cin, org−Cout , eq (5)
where Y represents the extent of stripping, Cin, org refers to the initial
copper concentration in the loaded organic phase, Cout , org is the copper
concentration in the loaded organic phase after stripping, and cout , eq is
the copper concentration in the loaded organic phase at equilibrium.
Fig. 2. Schematic diagram of a Y-Y microchannel reactor (L is the length from The overall volumetric mass transfer coefficient (KL α ) was used to
the inlet Y-junction to the outlet Y-junction).
evaluate the mass transfer characteristics. Since the interfacial area
between phases is not a smooth interface, the interfacial area between
Table 1 the two phases in the microchannel reactor is not measured in the
Dimensions of the Y-Y microchannel. microchannel reactor. The interfacial area can be obtained from the
Inlet and outlet Mixing channel experimental results. KL α values were calculated using the following
equations (Jafari et al., 2017; Zhang et al., 2017):
W/µm H/µm L/mm W/µm H/µm L/mm
1 ⎡ Caq, eq−Caq, in ⎤
KL α = ln
100 50 5 200 50 130.5 t ⎢ ⎥
⎣ Caq, eq−Caq, out ⎦ (6)
V
the extraction and stripping reactions took place. In the extraction ex- t=
Qaq + Qorg (7)
periments, most of the Cu2+ in the aqueous phase was extracted into
the organic phase by DZ988N, while most of the Fe3+ and Zn2+ re- where t represents the residence time of the mixture of the two phases,
mained in the aqueous phase. The procedure for the stripping experi- s; caq, eq represents the mass concentration of the copper ion at equili-
ments was similar to that used for the extraction experiments. Most of brium, and was determined by mixing the aqueous and organic phases
the Cu2+ in the loaded organic phase was stripped into the aqueous in a mechanical shaker for 8 h. caq, in and caq, out represent the mass
phase by sulfuric acid. concentration of copper in the inlet and outlet, respectively, g/L; V
refers to the total volume of the mixing microchannel reactor, mL; Qaq
2.3. Data analysis and Qorg are the volumetric flow of the aqueous phase and organic
phase, respectively, mL/min.
The concentrations of Cu, Fe and Zn in the aqueous phase were
determined using inductively coupled plasma-atomic emission spec- 3. Results and discussion
troscopy (AA240FS ICP-AES spectrophotometer, Palo Alto, CA, USA)
and the concentrations of Cu, Fe and Zn extracted to the organic phase 3.1. Liquid-liquid flow patterns
were obtained by mass balance.
The solvent extraction and stripping of copper from aqueous solu- In order to determine the preferred flow conditions for extraction
tions with DZ988N dissolved in Mextral DT100 can be written as fol- and stripping, flow simulation was carried out using the commercial
lows: software COMSOL Multiphysics. The simulation results were verified by
flow visualization experiments. According to Bashir et al. (2011), nu-
2RH(org ) + Cu(2aq+) ⇌ R2 Cu (org ) + 2H(+aq) (1) merical simulation of the flow pattern in a microchannel can be carried
The forward reaction is the extraction reaction, and the reverse out in the microchannel using the level set method. During simulation,
the velocity field →
u was obtained through solving the mass conserva-
reaction is the stripping reaction.
The extent of extraction is defined as follows (Chang et al., 2016): tion Eq. (8) and the incompressible Navier-Stokes Eq. (9). Then, the
velocity field →
u was used in the level set Eq. (10).
Cin, aq−Cout , aq
E= × 100% ∂ρ
Cin, aq (2) + ∇∙ (ρ→
u) = 0
∂t (8)
where E represents the extent of extraction, Cin, aq refers to the initial
∂→u →
copper concentration in the aqueous phase, and Cout , aq is the copper ρ + ρ (→
u ∙∇) →
u = −∇p + ∇∙ (μ∇→
u ) + Fst
∂t (9)
concentration in the aqueous phase after extraction.
The distribution ratio is defined as follows: ∂Φ ∇Φ ⎞
+→
u ∙∇Φ = γ ∇∙ ⎛ε∇Φ−Φ (1−Φ )
[M ]org ∂t ⎝ |∇Φ| ⎠ (10)
D=
[M ]aq (3) where ρ is the density, p denotes pressure, γ and ε are the numerical
stabilization parameters such that ε determines the thickness of the
where D represents the distribution ratio, and [M ]org refers to the con-
interface and γ is the reinitialization parameter. As stated by Bashir
centration of metal ion in the organic phase, and [M ]aq refers to the
et al. (2011): “The first term on the right side, that is the divergence of
concentration of metal ion in the aqueous phase.
ε∇Φ , acts as an artificial diffusivity in order to prevent discontinuities at
The separation factor is calculated using the following equation
the interface. The second term on the right is described as a compres-
(Reddy et al., 2009):
sive flux (Olsson and Kreiss, 2005).”
DA [A]org /[A]aq The level set function Φ is used to smooth the fluid properties across
βA / B = =
DB [B]org /[B]aq (4) the interface as described by Eqs. (11) and (12):

where βA / B represents the separation factor for A and B. DA and DB are ρ = ρ1 + (ρ2 −ρ1 ) Φ (11)

298
F. Jiang et al.
Table 2
Physical properties of organic and aqueous phases.
Phases Density ρ (kg/m3) Viscosity μ (mPa s)
Aqueous phase 1000.0 1.0
Organic phase 832.3 3.0
μ = μ1 + (μ 2 −μ1 ) Φ
where ρ1 and ρ2 represent the density of the aqueous phase and organic
phase, respectively. μ1 and μ 2 are the dynamic viscosities of the aqu-
eous phase and organic phase, respectively. The surface tension force,
→ the organic phase and aqueous phase cannot be separated at the outlet
Fst , acting on the interface between two fluids is calculated according to
Eq. (13) (Wong et al., 2017):
→ →
Fst = σκδn
δ = 6 |∇Φ||Φ (1−Φ )|
where σ is the surface tension coefficient, δ is a Dirac delta function
located at the interface between the two fluids and approximated by a
smooth function according to Eq. (14). κ represents the curvature of the
fluid–fluid interface.
The height and width of the microchannel reactor used in the nu-
merical model were the same as those for the experimental system. The
length of the mixing channel in the simulation was 500 μm. The results
showed that 500 μm was enough for the simulated flow pattern to be
stabilized in the microchannel. The physical properties of the organic
and aqueous phases are shown in Table 2.
The organic phase velocity to aqueous phase velocity ratio is de-
fined as the velocity ratio. The velocity ratios of 1:4, 1:2, 1:1, 2:1 and
4:1 were selected to investigate the effect of flow rate ratio on the flow
patterns for numerical simulation. The volumetric flow rate of the
aqueous phase was constant at 0.05 mL/min corresponding to velocity
of 1.7 × 105 μm/s. The velocity of the organic phase was calculated
according to the velocity ratios. The different velocity ratios were
(a) a flow rate ratio of 1:4 (b) a flow rate ratio of 1:2
(d) a flow rate ratio of 2:1
Fig. 3. Flow patterns for Y-Y microchannel in simulation (red-organic phase, blue-aqueous phase). (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
Minerals Engineering 127 (2018) 296–304
achieved by adjusting the velocity of the organic phase. The simulated
flow patterns at different velocity ratios are shown in Fig. 3. It was
found that stable parallel flows were obtained under the experimental
velocity ratios. This is due primarily to the viscous force dominating the
inertial force, which leads to a smaller Reynolds number, defined by the
ratio of the inertial force to the viscous force during microfluidic flow.
The interface position of the two phases inside the microchannel shifts
with changes in the ratio of flow rate. It should be noted that the ve-
(12) locity ratios have a significant effect on phase separation at the outlet Y-
junction. For example, at a velocity ratio of 1:4, one of the outlets was
the aqueous phase (blue) and the other was the parallel flow of the
organic phase (red) and the aqueous phase (blue), as shown in Fig. 3(a);
Y-junction. When the velocity ratio of 1:2 was used, the two phases
started to separate well in the outlet section, as shown in Fig. 3(b). A
perfect phase separation was achieved at a velocity ratio of 1:1, as
(13)
shown in Fig. 3(c). At a constant aqueous phase flow rate, increased
organic phase flow rates to a velocity ratio of 2:1 led to the interface
(14)
position of the two phases inside the microchannel reactor deviating off
the microchannel reactor center, and the phase separation could not be
achieved, as shown in Fig. 3(d). A mixed organic phase and aqueous
phase flowed out from one of outlets, and the other outlet was the or-
ganic phase when the velocity ratio was 4:1, as shown in Fig. 3(e).
Surface tension and pressure gradients are not sufficient to break down
the dispersed phase into slug, and the two phases flowed side by side in
parallel flow under experimental conditions, which is consistent with a
previous report (Dessimoz et al., 2008). Zhao et al. (2006) have in-
dicated that parallel flow is a way to perform solvent extraction and
purification. Therefore, the flow rate ratio of 1:1 was selected as the
preferred operational condition for the experiments.
The experimental flow patterns of the aqueous phase and organic
phase are shown in Fig. 4. It was found that the aqueous phase and
organic phase each maintained stable parallel flow inside the micro-
channel reactor including in the inlet zone, straight microchannel,
corner and outlet section. The flow patterns in the experiments were
consistent with the simulation.
(c) a flow rate ratio of 1:1
(e) a flow rate ratio of 4:1
299
F. Jiang et al.
Fig. 4. Parallel flow for Y-Y microchannel reactor during experiments. (a) Inlet Y-junction; (b) straight microchannel; (c) corner of microchannel; (d) outlet Y-
junction.
3.2. Extraction of copper
Extraction of copper from sulfate solution containing Fe3+ and
2+
Zn was carried out with the Y-Y type microchannel reactor. Effects of
residence time, aqueous phase pH, and the concentration of the ex-
tractant on the extent of extraction and the overall volumetric mass
transfer coefficient (KL α ) were studied.
3.2.1. Residence time
As commonly and conveniently done, residence time is controlled
by setting different flow rates in the microchannel reactor. The flow
rate of the aqueous phase (Qaq ) was equal to that of the organic phase
(Qorg ). The flow rates for both the aqueous phase and organic phase
were equal and set at 0.01, 0.03, 0.05, and 0.10 mL/min in the mi-
crochannel reactor to investigate the influence of flow rate on the
extraction and separation of copper from iron, and zinc. The corre-
sponding residence times were 3.915 s, 1.305 s, 0.783 s, 0.392 s, re-
spectively. The effects of residence time on the extents of extraction
and separation factors are shown in Fig. 5(a) and (b).
The extraction of copper increased with an increase in residence
time, but there was no significant increase when the residence time was
greater than 0.783 s. The extraction of copper reached 80.61% at a
residence time of 0.783 s. The corresponding flow rate of both the
aqueous and organic phase was 0.05 mL/min. There was an increase in
the extraction of iron and zinc when the residence time was less than
0.783 s and there was no significant increase when the residence time
was greater than 0.783 s. The extraction of iron was less than 1.1% and
of zinc was less than 0.5%. However, the extent of the extraction for
copper increased as the residence time increased from 20 s to 60 s for
the conventional batch experiment. A maximum of 77.72% copper
extraction was observed at the residence time of 60 s for the batch
testing, which was obviously lower than 80.61% for the microchannel
reactor extraction, at a residence time of 0.783 s. The results indicate
300
Minerals Engineering 127 (2018) 296–304
that copper extraction kinetics in the batch extraction is much slower
than that in the microchannel reactor extraction. The co-extraction of
iron and zinc in the batch test was obviously higher than that in the
microchannel extraction.
A higher separation factor for the microchannel reactor extraction
was observed and is much higher than that for the batch testing, as
evidenced by the results in Fig. 5(b). From Fig. 5(b), the copper/iron
separation factor, βCu / Fe , and copper/zinc separation factor, βCu / Zn ,
show a similar trend with respect to residence time in the microchannel
reactor extraction. The βCu / Fe and βCu / Zn values reached maximums of
465.53 and 1089.17 at the residence time of 0.783 s, respectively, while
a βCu / Fe value of 86.20 at 180 s and a βCu / Zn value of 123.40 at 300 s
were obtained for the batch extraction. The βCu / Fe and βCu / Zn initially
decreased and then approximately kept constant in the microchannel
reactor when the residence time was above 0.783 s. A much higher
extent of extraction for copper was obtained, with a higher separation
factor, using the microchannel reactor compared with the batch ex-
traction. This is due to a larger specific surface area and shorter diffu-
sion distance in the experiments using microfluidic extraction
(Abraham et al., 2017; Jiang et al., 2018a). Therefore, the residence
time of 0.783 s was considered as the preferred residence time for the
microchannel reactor extraction. The corresponding flow rate was
0.05 mL/min.
The variation of the overall volumetric mass transfer coefficient
(KL α) is shown in Fig. 6 as function of residence time. It can be seen
from Fig. 6, that the overall volumetric mass transfer coefficient de-
creased as residence time increased. This trend has been reported in
previous publications (Darekar et al., 2014a, 2014b). This is mainly
because residence time was decreased by increasing the flow rate. The
increase in flow rate caused a subtle increase in the interfacial mass
transfer area between the two phases due to the wavy interface of the
two phases in the microchannel (Zhao et al., 2007). From Fig. 6, much
higher KL α values (0.49–3.39 s−1) for Cu have been obtained compared
F. Jiang et al.
Fig. 5. Effect of residence time on (a) extraction of copper and (b) separation of copper from iron, zinc (conditions: [Fe3+] = 2.0 g/L, [Zn2+] = 1.0 g/L,
[Cu2+] = 3.0 g/L, [DZ988] = 10%, pH = 2.00).
to KL α values for Fe (0.05–0.32 s−1) and KL α values for Zn
(0.04–0.21 s−1). Comparing Fig. 6(a) with (b), it can be seen that a
much higher overall volumetric mass transfer coefficient, KL α of
0.49–3.39 s−1, for Cu can be achieved within 5 s compared to a KL α
value of 0.006–0.073 s−1 for the batch testing within 300 s. From the
KL α values of Cu, Fe, and Zn, it can be concluded that the Cu was more
easily extracted than the Fe and Zn, using DZ988N as an extractant in
the Y-Y type microchannel reactor. The higher KL α value of Cu and
lower KL α values for Fe and Zn lead to a better separation of Cu from
the mixed solution containing Fe and Zn.
3.2.2. Aqueous phase pH
The pH value is an important factor for extraction and separation of
copper using the DZ988N extractant. Experiments were carried out at
room temperature to study the effect of varied pH values (a range of
0.58–2.00) on the extraction of copper using 10% (v/v) DZ988N in
Mextral DT100. The hydrolysis of Fe3+ will take place when the pH of
the aqueous phase is higher than 2.00. Therefore, the pH value of the
aqueous phase was controlled to a pH value of 2.00 or less. The ex-
traction of efficiency and separation factors were plotted as a function
of pH values in Fig. 7(a) and (b).
The extraction efficiency of copper increased with an increase in the
pH value from pH 0.58 to pH 2.00, with the extraction efficiency of
copper increasing to 80.61% at a pH of 2.00. This is shown in the
forward reaction of Eq. (1) resulting in an increase of extraction effi-
ciency with an increase of pH (Li et al., 2017). There was no significant
change in the extraction of iron and zinc in the pH range from 0.58 to
2.00, the extraction being less than 0.9% for iron and less than 0.4% for
zinc. The separation factors increased with an increase in the pH value
of the aqueous phase. For example, the copper/iron separation factor
βCu / Fe increased to 465.53 at pH 2.00 while the copper/zinc separation
(a) microchannel reactor
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Minerals Engineering 127 (2018) 296–304
factor βCu / Zn increased to 1089.71 at the same pH value of 2.00. Thus,
the aqueous phase pH value of 2.00 was selected as the preferred op-
erational condition for the microfluidic solvent extraction of copper
from sulfate solution.
3.2.3. Extractant concentration
The copper extraction experiments were carried out with varied
DZ988N concentrations from 5% (v/v) to 25% (v/v) at an aqueous
phase pH of 2.00. The results are shown in Fig. 8(a) and (b).
Fig. 8(a) shows that the extraction of copper and iron increased
from 69.05% and 0.83%, respectively, to 86.02% and 1.5% with an
increase of DZ988N concentration from 5% (v/v) to 25% (v/v). The
extraction of less than 0.5% zinc was negligible in the DZ988N con-
centration range tested. As shown in Fig. 8(b), the copper/zinc se-
paration factor obviously increased with an increase of DZ988N con-
centration and increased to 1249.70 at the DZ988N concentration of
25%. However, the copper/iron separation factor decreased when the
DZ988N concentration was above 10%. As is commonly known, the
higher the separation factor, the better the separation effect. βCu / Fe
values of above 200 and βCu / Zn values of above 1000 show that copper
has been separated well from the mixed solution. Therefore, the effect
of the DZ988N concentration range tested on the separation factors may
be ignored. Ensuring high extraction efficiencies and separation factors,
while reducing the consumption of the extractant is a better choice.
Therefore, based on the above discussion, it can be seen that 15% (V/V)
of DZ988N concentration is appropriate to extract copper from the
solution containing copper, iron and zinc ions.
3.3. Stripping of copper
From the extraction experiments, it was shown that the DZ988N
Fig. 6. Overall volumetric mass transfer coeffi-
cient (KL α ) variation with residence time.
(b) batch
F. Jiang et al.
Fig. 7. Effect of pH on (a) extraction of copper and (b) separation of copper from iron, zinc (conditions: [Fe3+] = 2.0 g/L, [Zn2+] = 1.0 g/L, [Cu2+] = 3.0 g/L,
[DZ988] = 10%, flow rate = 0.05 mL/min, residence time: 0.783 s).
could extract Cu selectively from the Cu-Fe-Zn mixed solution. In this
section the application of the Y-Y type of microchannel for Cu stripping
from the organic phase, which is an important step to prepare the Cu
solution for electrowinning, was also evaluated. The procedures of the
Cu stripping experiment are similar to the experiments of extraction.
Effects of Cu2+ concentration in the loaded organic phase, the con-
centration of sulfuric acid, and the phase ratio on the stripping effi-
ciency were studied.
3.3.1. Copper concentration in the loaded organic phase
The effect of Cu2+ concentration in the loaded organic phase on
stripping efficiency was investigated at varied flow rates. Cu2+ con-
centrations in the loaded organic phase of 1.396 g/L and 3.002 g/L
were selected to investigate the influence of Cu2+ concentration in the
loaded organic phase on stripping. The results are shown in Fig. 9(a)
and (b).
From Fig. 9(a) and (b), the stripping efficiency decreased with an
increase of flow rate for both concentrations. In other words, the
stripping efficiency increased with an increase of residence time. The
stripping efficiency reached maximums of 88.63% and 59.20%, re-
spectively, for the Cu2+ concentrations of 3.002 g/L and 1.396 g/L at
the residence time of 3.915 s. The residence time (3.915 s) for stripping
of copper using microfluidic technology was less than that (about
10 min) using conventional solvent extraction equipment (Alguacil
et al., 2002). The stripping efficiency increased with an increase in
Cu2+ concentration in the tested range of the loaded organic phase.
This is because the copper concentration in the stripping phase was
much less than the equilibrium concentration. This stage was con-
sidered the initial stage of stripping. The Cu2+ concentration in the
Fig. 8. Effect of extractant concentration on (a) extraction of copper and (b) separation of copper from iron, zinc (conditions: [Fe3+] = 2.0 g/L, [Zn2+] = 1.0 g/L,
[Cu2+] = 3.0 g/L, flow rate = 0.05 mL/min, residence time = 0.783 s, pH = 2.00).
302
Minerals Engineering 127 (2018) 296–304
stripping phase didn’t reach the equilibrium concentration. Therefore,
the stripping efficiency increased with an increase of Cu2+ concentra-
tion in the loaded organic phase.
3.3.2. Concentration of H2SO4
To study the influence of H2SO4 concentration on the stripping of
copper, the sulfuric acid and the loaded organic phase (Cu2+ con-
centration of 3.002 g/L) were mixed at a 1:1 phase ratio in the Y-Y
microchannel. H2SO4 concentrations of 140, 200, 250 g/L were selected
to investigate the influence of H2SO4 concentration on the stripping of
copper at varying flow rates (0.01, 0.03, 0.05, 0.07 mL/min). The re-
sults are shown in Fig. 10.
As shown in Fig. 10(a), with an increase in flow rate, the stripping
efficiency rapidly decreased from 99.99% to 42.03% for the various
H2SO4 concentrations. In other words, the stripping efficiency increased
with an increase in residence time, as shown in Fig. 10(b). The stripping
efficiency increased to 99.99%, 98.78%, and 98.94%, respectively, with
an increase in residence time for the H2SO4 concentrations of 140, 200,
250 g/L at a residence time of 3.915 s. The stripping efficiency in-
creased with an increase in H2SO4 concentration at the same residence
time. An increase in H2SO4 concentration results in an increase of H+.
This will lead to an increase in the instability of the Cu2+ and the ex-
tractant chelate. Reaction (1) will shift to the left and the driving force
of the Cu2+ entering the aqueous phase will increase at the interface.
Therefore, the stripping efficiency will increase with an increase in
H2SO4 concentration. However, a high H2SO4 concentration will cause
corrosion of the equipment, therefore, the H2SO4 concentration should
be less than 200 g/L.
F. Jiang et al. Minerals Engineering 127 (2018) 296–304

Fig. 9. Effect of concentration of copper in the loaded organic phase on the stripping of copper. (conditions: [H2SO4] = 180 g/L, flow rate = 0.01, 0.03, 0.05,
0.07 mL/min, flow rate ratio = 1:1).

3.3.3. Phase ratio Table 3

The volume ratio of organic to aqueous phases will be adjusted by Flow rate of two phases.
the flow rate ratio in the Y-Y microchannel. Two phase volume ratios of Volume ratio 1/3 1/2 1/1 2/1
1/3, 1/2, 1/1, and 2/1 were selected to investigate the influence of
volume ratio on stripping. The flow rates of the two phases are shown in Flow rate of organic phase (mL/min) 0.03 0.03 0.03 0.06
Table 3. The results are shown in Fig. 11. Flow rate of aqueous phase (mL/min) 0.09 0.06 0.03 0.03

From Fig. 11, it can be seen that the stripping efficiency increased
linearly with an increase in the volume ratio (organic/aqueous). The
stripping of copper reached 89.10% at the volume ratio of 2/1. During
the experiments, the organic/aqueous volume phase ratio was adjusted
by changing the organic and aqueous flow rates. An increase in the ratio 90
reflects an increase in the Cu2+ loaded organic phase volume. Cu2+
80
Stripping Efficiency (%)

stripped to the aqueous phase would increase. Therefore, the stripping

efficiency increased with an increase of volume ratio. 70

60
4. Conclusions
50
The solvent extraction and stripping of copper has been performed
in a Y-Y type microchannel reactor. Effects of residence time, aqueous 40
phase pH, and concentration of extractant on the extent of extraction
were investigated and the overall volumetric mass transfer coefficients
30
(KL α ) were calculated to evaluate mass transfer characteristics. Effects 20
of Cu2+ concentration in the loaded organic phase, H2SO4 concentra-
tion, and phase ratio on stripping were studied. 1/3 1/2 1/1 2/1
The extents of extraction and the separation factors in Y-Y type Volume Ratio
microchannel reactors are higher than those in batch extraction. The
Fig. 11. Effect of volume ratio on the stripping of copper (conditions:
optimal residence time of 0.783 s in a microchannel reactor is much less
[Cu2+]org = 3.002 g/L, [H2SO4]aq = 180 g/L).
than that in batch extraction (at least 60 s). The maximum extraction
and stripping of copper reached 86.02% and 98.94%, respectively. The

Fig. 10. Effect of H2SO4 on the stripping of copper (conditions: [Cu2+]org = 3.002 g/L, flow rate = 0.01, 0.03, 0.05, 0.07 mL/min, flow rate ratio = 1:1).

303
F. Jiang et al.
maximum separation factors, βCu / Fe and βCu / Zn , were up to 465.53 and
1249.70, respectively. Much higher KL α values for Cu
(0.4937–3.3969 s−1) and lower KL α values for Fe (0.0477–0.3173 s−1)
and Zn (0.0395–0.2130 s−1) demonstrated an effective separation be-
tween Cu and Fe, Zn. Cu KL α values (0.4937–3.3969 s−1) within 5 s in a
microchannel reactor were orders higher than those in batch extraction
(0.006–0.073 s−1). The aqueous phase and organic phase formed stable
parallel flow patterns in both experiments and simulation. The Cu
stripping experiments showed that the Y-Y type of microchannel reactor
not only can be used for Cu extraction, but also can be used for Cu
stripping processing. In summary, microfluidic extraction and stripping
is a potential technique for the enhancement of liquid-liquid mass
transfer.
Many researchers have indicated that the microreactor could be
scaled up easily by the numbering-up approach to avoid pilot scale
testing. For example, a microreactor has been successfully used for
producing nitroglycerine at Xi’an North Huian Chemical Industry Co.,
in Xi’an, China (Wirth, 2013). A capacity of 15 kg/h production was
achieved at a total liquid flow of about 100 L/h. Therefore, this type of
technology has promising industrial application for the extraction and
stripping of metal ions.
Conflict of interest
None.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant number: 51504116) and the China
Scholarship Council (Grant number: 201608740004).
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