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Emulsion Liquid Membrane in the Selective Extraction of Dy

Article in Chemical Engineering Research and Design · September 2022

DOI: 10.1016/j.cherd.2022.09.001

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 Chemical Engineering Research and Design 187 (2022) 497–506

Available online at www.sciencedirect.com

Chemical Engineering Research and Design

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

Emulsion liquid membrane in the selective

extraction of Dy
]]
]]]]]]
]]

⁎
Rajib Karmakar a, Pritam Singh a, Aparna Datta b, Kamalika Sen a,
a
Department of Chemistry, University of Calcutta, 92, A. P. C. Road, Kolkata 700009, India
b
UGC-DAE Consortium for Scientific Research, Kolkata Centre, III/LB-8, Bidhannagar, Kolkata 700098, India

a r t i c l e i n f o a b s t r a c t

Article history: Due to comparable ionic radii, lanthanoids are known to have similar physical and che­
Received 27 June 2022 mical properties. Separation of lanthanoids from one another is therefore a challenging
Received in revised form 19 August task. Such crucial separation chemistry could be performed with the help of solvent ex­
2022 traction technique. In order to overcome the associated problems based on solvent ex­
Accepted 1 September 2022 tractions, the emulsion liquid membrane based method has been applied to do the
Available online 6 September 2022 selective and efficient extraction of the lanthanoid Dy. This work describes the role of
emulsion liquid membranes for the selective extraction of Dy(III) ion with the help of
Keywords: aniline yellow dye at pH 3 medium. The emulsion was prepared using different oils viz,
Emulsion liquid membrane mustard oil, coconut oil and palm oil as the organic phase. The complexation of the
Dy(III) lanthanoids (La(III), Ce(III), Ce(IV), Pr(III), Gd(III), Sm(III) and Dy(III)) with aniline yellow (AY)
Lanthanoids and benzene azo naphthylamine (BAN) dye was studied using UV-Vis spectrophotometer
Feed solution at three different pH (pH 1, pH 3 and pH 5) conditions. The complexation was observed at
Stripping solution pH 3 and 5 for only Pr(III) and Dy(III) with both the dyes having high association constant
values (∼106 M-1). The emulsion liquid membrane (ELM) prepared with mustard oil, co­
conut oil and palm oil at pH 3 showed zeta potential value − 30.60 mV, − 27.00 mV and
− 35.90 mV respectively. Selective extraction of the Dy-AY complex was obtained for the
ELM prepared with mustard oil at pH 3 medium (90%). After extraction of the Dy-AY
complex, the zeta potential decreased to − 41.80 mV for the ELM. The effect of stirring
time, pH of the medium and the concentrations of the feed solutions have positive cor­
relations towards the extraction process. After the extraction process, the oil reach phase
was demulsified using a mixture of organic solvents and the extracted metal ion was
back-extracted with the help of cation exchange resin. 88% of the extracted Dy could be
back extracted upon demulsification.
© 2022 Published by Elsevier Ltd on behalf of Institution of Chemical Engineers.

elements by applying various mechanical and chemical

1. Introduction
treatments. Rare earth elements (REEs) are widely used in
magnets, alloys, rechargeable batteries, phosphors, catalysts,
In this new era, industrialisation has become the basis of
defence technologies, electric vehicles, etc. (Gergoric
economic growth of a country and with progress of time,
et al., 2017).
lives have been surrounded by more and more manmade
For the modification of high-strength permanent magnets
waste materials. As a result of this, countries all over the
(like Nd-Fe-B), Nd and Dy are used as the raw materials.
world are encountering difficulties of ‘urban mines’. The
These types of magnets are widely used in electric motor,
urban mines become alternative resources of many rare
voice coil motor, wind turbines, hard disk drives and in many
more applications. The NdFeB magnets lose their coercivity
easily at high temperature (around 200 °C). But on use of Dy
⁎
Corresponding author.
as an additive, the coercivity of the magnet remains intact
E-mail address: kamalchem.roy@gmail.com (K. Sen).
https://doi.org/10.1016/j.cherd.2022.09.001
0263-8762/© 2022 Published by Elsevier Ltd on behalf of Institution of Chemical Engineers.
498 Chemical Engineering Research and Design 187 (2022) 497–506
Fig. 1 – Schematic representation for the preparation of emulsion liquid membrane.
due to its resistance to diamagnetism at high temperature
(Zepf, 2013; Sun et al., 2018). Additionally, bromide and iodide
salts of Dy are used in high intensity halide discharge lamps
(Curry et al., 2012) and as catalysts (Veits and de Alaniz,
2012). Dysprosium oxide-nickel cermet is used in nuclear
reactors to cool the control rods as it can readily absorb the
neutrons. Dysprosium compounds are used in laser diodes
and in photo-optic applications as semiconductors, etc.
(Bowman et al., 2012; Bacherikov et al., 2018). The adaptation
of advanced green technology, expansion of automotive in­
dustry is increasing the demand of Nd, Pr and especially Dy.
On the other hand, only few countries have economic REE
reserves, out of which, China alone exports more than 80% of
the global need. Each year China produces around 99% of
total global production of Dy (Kramer, 2010). Thus there is
always a risk of supply disruption of REEs, which may be
caused due to either COVID-19 like pandemic situations or
geopolitical tension or any other unforeseen issues. Coun­
tries are looking for secondary sources to avoid crisis in their
manufacturing and technology sectors. A report proposed in
2012 that the demand of Dy will rise 2600% by the year of
2035 (Alonso et al., 2012). The approach to recover the REEs
from their waste has been adopted to sustain a steady
supply. Besides, the urban mining has other advantages over
primary mining, e.g., it reduces environmental problems.
The REEs coexist in the mines and are later extracted and
separated from each other to get high degree of purity for
their use. It is well known that the separation of one REE
from the other is a difficult task as they possess similar kind
of physical as well as chemical properties. Various types of
scientific techniques were developed for the extraction and
separation process like solvent extraction, solid-liquid ex­
traction, aqueous biphasic extraction, adsorption, ion ex­
change, co-precipitation, etc. Among all, solvent extraction is
a most commonly used technique than the others. But it is
not considered very effective for extraction and separation of
REEs having low level of concentration in their respective
waste (Suren et al., 2012). Other than that, it also uses large
amounts of organic toxic solvents and is time consuming
(Karmakar and Sen, 2019a, 2019b).
Liquid membrane technique is another efficient method,
which has also got importance for selective extraction and
purification of metal ions from aqueous solutions. For the se­
paration of metal ions, various types of liquid membranes are
used, such as emulsion liquid membrane (ELM) (Malik et al.,
2012), bulk liquid membrane (BLM) (Chang, 2016) and sup­
ported liquid membrane (SLM) (de Gyves and Rodríguez de San
Miguel, 1999). An ELM extraction process contains feed and
stripping solutions, surfactants, carriers and diluents. Emul­
sion liquid membranes are double emulsions; they are either
water/oil/water (w/o/w) or oil/water/oil (o/w/o) systems
(Chakraborty et al., 2010). The external phase is called the feed
phase. The feed phase is an aqueous solution, which generally
contains the analyte molecules to be extracted. The mem­
brane phase, i.e., the organic phase is dispersed in the feed
solution by forming emulsion. Surfactants are frequently used
for stabilisation of the emulsions by the virtue of micellisation.
The internal phase, i.e., stripping phase remains inside the
membrane phase in the form of emulsion. Fig. 1 shows the
schematic representation of the ELM.
ELM has some advantages over the solvent extraction
technique, e.g., ease of operation, suitability for low to high
concentration of metal ions, simultaneous extraction and
stripping, low energy and low cost. Additionally, the liquid
membrane containing the carrier and the surfactant can be
reused at the end of the process (Davoodi-Nasab et al., 2018;
Kumbasar, 2009). ELM was first used for the extraction of
metal ions from waste water by Li (1968). The main difficulty
in ELM techniques is associated with handling the emulsion,
which has a fragile stability (Noah et al., 2018; Jusoh and
Othman, 2016). Like conventional solvent extraction, ELM
extraction technique is also associated with large amount of
hazardous and volatile organic solvents usually petroleum-
based diluents such as n-heptane, kerosene, dichloroethane,
etc. (Malik et al., 2012). So, this LM has to be modified to a
greener system by using materials, which are environment
friendly. For example, instead of organic solvent, use of ve­
getable oils (mustard, sunflower, coconut or palm oil) makes
this process cleaner. To the best of our knowledge, there is
one research article on extraction of Dy from acidic chloride
solution containing Nd and Dy using ELM process where
Cyanex 572 is used as carrier (Raji et al., 2018).
Due to the comparable physical and chemical properties
of the lanthanoids, the selective extraction of them is quite
 Chemical Engineering Research and Design 187 (2022) 497–506
difficult and challenging. The task could be easy if we first try
to make complexation of these lathanoides with some dyes,
specially which have free amino groups, then few of the
lanthanoids may get eliminated due to the lack of com­
plexing ability or affinity towards that kind of dye. These
lanthanoid-dye complexes can then be extracted with the
help of ELM, provided the medium of the ELM is suitable for
the complex. The background for the choice of such com­
plexing agents, having free amino groups is that the lan­
thanoids have an affinity towards such groups (Kaboudin
et al., 2011, Chen et al., 2019). This lanthanoid-dye complexes
are present in the feed solution, may be selectively extracted
into the internal phase depending upon the pH, affinity,
stability of the emulsion upon interacting with the feed so­
lution. In the present study, our focus is to selectively sepa­
rate Dy(III) from other lanthanoid ions such as La(III), Ce(III),
Ce(IV), Pr(III), Sm(III) and Gd(III). For the selective extraction
of Dy(III), mustard, coconut and palm oils were used as the
membrane phase and aniline yellow (AY) and benzene azo
naphthylamine (BAN) were used as the complexing agent.
Triton-X-100 was used as the surfactant. It is a non-ionic
surfactant with the presence of both hydrophilic and hy­
drophobic moieties. This biodegradable surfactant could be
adsorbed at the interface of the emulsions and acts as elec­
trostatic or steric barriers against droplet coalescence and
increase the stability of the emulsions (Church et al., 2017,
Issaka et al., 2013). Different parameters, viz., pH, con­
centration of metal ions and stirring time were optimised.
The extracted Dy(III) was then back extracted upon de­
mulsification with ethyl acetate, ethanol and pet ether sol­
vent combination.
2. Experiment
2.1. Reagents
Dysprosium nitrate (Dy(NO3)3) (≥99.99%), samarium nitrate
hexahydrate (Sm(NO3)3·6H2O) (99.9%), lanthanum nitrate
hexahydrate (La(NO3)3·6H2O) (99.999%), praseodymium ni­
trate hexahydrate (Pr(NO3)3·6H2O) (99.9%), cerium chloride
(CeCl3) (99.9%), ammonium cerium nitrate ((NH4)2Ce(NO3)6)
(≥99.99%) and gadolinium nitrate hexahydrate (Gd
(NO3)3·6H2O) were procured from Sigma Aldrich (USA). HCl
(37%) and NaOH (≥97.0%) were purchased from Merck Life
Science Private Limited (India). Aniline yellow (AY) (IUPAC
name: 4-aminoazobenzene) (C6H5N = NC6H4NH2), benzene
azo naphthylamine (BAN) (IUPAC name: 4-phenylazo-1-
naphthylamine) (C16H13N3) were brought from Sigma-Aldrich
(USA). Triton-X-100 surfactant was purchased from
Spectrochem Pvt. Ltd. (India) and mustard oil (Scientific
name- Brassia nigra Koch), coconut oil (Scientific name-
Cocosnukifera) and palm oil (Scientific name- Elaeisguneesis
Jacq) were purchased from local market. Ethyl acetate (99.8%),
ethanol and pet ether were brought from Merck Life Science
Private Limited (India). All the reagents were of analytical
grade and used as received without any further purification.
Triple distilled water was used during the experiment for the
preparation of aqueous solutions.
2.2. Preparation of solution
0.1 and 0.05 mM solutions of La(III), Ce(III), Ce(IV), Pr(III), Gd(III),
Sm(III) and Dy(III) were prepared by dissolving La(NO3)3, CeCl3,
(NH4)2Ce(NO3)6, Pr(NO3)3, Gd(NO3)3, Sm(NO3)3 and Dy(NO3)3 in
499
apposite volume of triple-distilled water (TDW), respectively.
The pH of the solutions (1, 3 and 5) was adjusted using suitable
amounts of HCl. The solutions of AY and BAN were prepared
by dissolving them in TDW and ethanol, respectively.
2.3. Apparatus
The weight of the reagents was measured using a Mettler
Toledo digital balance with accuracy up to fourth decimal.
The pH of the aqueous solutions was measured and adjusted
to 1, 3 and 5 using a digital Mettler Toledo seven compact pH/
ion metre. A digital ultrasonic cleaner having wattage of 50 W
and 40 ± 3 kHz frequency was used to sonicate solutions.
The centrifugation was done with the help of Remi
Elektrotechnik Ltd. R-4C centrifuge machine. UV-Vis spec­
troscopic data were obtained from Agilent 8453 diode array
spectrophotometer. Malvern Instrument Nano- ZS was used
for performing the dynamic light scattering (DLS) of the
emulsions and analysing their zeta potentials.
2.4. Determination of stability constants of metal–dye
complexes
Before the study of the extraction of the metal ions, we
performed a detailed investigation about the interaction be­
tween the metal ions (La(III), Ce(III), Ce(IV), Pr(III), Sm(III), Gd
(III) and Dy(III), and the dyes (AY and BAN) at three different
pH (1, 3 and 5) using UV-Vis spectrophotometer. Among the
studied metal ions and dye solutions, we observed that the
two metal ions, viz., Pr(III) and Dy(III) can interact with two
dyes AY and BAN at pH 3 and 5 (Figs. S1–S8). 2 mL aqueous
solutions of different pH (viz., pH 1, pH 3 and pH 5) were
taken in quartz cuvettes and then treated with 0.005 mL of
10 mM dye solutions. The resulting mixtures were then
treated gradually with small aliquots of 1 mM of the metal
solutions and studied under UV-Vis spectrophotometer.
2.5. Preparation of emulsion liquid membranes (ELM)
We have prepared water/oil/water type emulsion liquid
membrane. The feed solution was the metal-dye complex
solution prepared at pH 3 or 5. We have chosen mustard oil,
coconut oil and palm oil as the organic phase or the mem­
brane phase. A non-ionic surfactant, Triton X-100 is used for
stabilising the emulsion. Only aqueous HCl solution of pH 3
or 5 was used as the stripping solution. In our experiment we
first prepared a water-in-oil emulsion. Then this emulsion
was stirred with the feed solution to obtain the required ELM.
2.5.1. Preparation of water-in-oil emulsion
For the extraction process, the emulsion was prepared as
follows.
1 mL Triton-X-100, 9 mL oil (mustard oil, coconut oil or
palm oil) and 1 mL aqueous solution of different pH (3 or 5)
were taken in a 100 mL conical flask. The mixture was then
sonicated for 10 min to prepare the emulsion.
Table 1 tabulates the sample ID of the prepared water-in-
oil emulsions by using different conditions of oils, and
stripping solutions.
2.5.2. Preparation of feed solution
After the preparation of emulsion, the next job is to add the
feed solution to the emulsion to study the extraction process.
The feed solution contains metal-dye complex prepared at
500 Chemical Engineering Research and Design 187 (2022) 497–506

part at the bottom of the test tube and taken for spectro­
Table 1 – Sample identity of the prepared water-in-oil
photometric study.
emulsion.
A suitable blank was also prepared using this technique
Sample ID of ELM Oil used pH of stripping solution
wherein only pH adjusted aqueous solution was used instead
ELM 1 Mustard oil 3 of the metal-dye complex as the feed solution. The re­
ELM 2 Mustard oil 5 maining procedure was same as that of the earlier one. The
ELM 3 Coconut oil 3 lower part of the emulsion was treated in the same way as
ELM 4 Coconut oil 5
with the mixed solvent system in the previous case. This
ELM 5 Palm oil 3
ELM 6 Palm oil 5
blank solution was used as a solvent to obtain a suitable
calibration of the metal-dye complex.

2.7. Dynamic light scattering (DLS) study

Table 2 – Feed composition table.
Sample ID for feed pH Metal solution Dye solution
solution
F1 3 5 mL 0.1 mM 5 mL 0.1 mM
F2 5 5 mL 0.1 mM 5 mL 0.1 mM
either pH 3 or pH 5. Table 2 describes the details of the feed
solutions that were used for the process. In brief, the metal-
dye complex of definite composition prepared at a particular
pH, was used as the feed solution. 5 mL of 0.1 mM metal so­
lution maintained at pH 3 or 5 was treated with 5 mL of
0.1 mM dye solution (AY/BAN) maintained at the same pH to
prepare 10 mL of 0.05 mM metal-dye complex solution at
that pH.
2.5.3. Preparation of ELM and determination of the amount of
metal ion extracted
After the preparation of water-in-oil emulsion and feed so­
lution, emulsion liquid membrane was prepared and studied
for the extraction of the metal-dye complex from the feed
solution. The emulsion prepared at pH 3 or pH 5 must be
treated with feed solution prepared at pH 3 or pH 5 respec­
tively. After addition of the proper feed solution to the cor­
responding emulsion, the mixture was stirred for 10 min to
get the desired ELM. This ELM was then centrifuged at
4500 rpm for 15 min. As a result of that, a bi-phasic system
was observed. The lower part is water rich phase, in which
the feed solution is predominated. Whereas, the upper part is
oil rich phase, in which the extracted metal-dye complex is
present. The upper oil rich phase is carefully pipetted out
and preserved for back extraction. The lower water rich
phase is taken for spectroscopic studies.
As the oil rich phase was too incoherent to study under
the UV-Vis spectrophotometer, the lower part, i.e., the water
rich phase was used for the spectrophotometric studies for
metal quantitation after suitable treatment as described
below.
2.6. Treatment of the water rich phase for UV-Vis
spectrophotometric study
Although this water rich phase looked simple and clear but
the real situation was quite different. A part of the emulsion
still remained in the aqueous layer and made it unsuitable
for spectrophotometric study. Therefore, we opted to de­
mulsify this water rich phase using different individual or
combined solvents. Demulsification was best observed with
the solvent combination of ethyl acetate, ethanol and pet
ether. 1 mL each of these three solvents were treated with
1 mL of the water rich phase. With this solvent system, a bi-
phasic system was further obtained with a clear aqueous
DLS analysis was performed in order to get the information
about the size of the emulsion. The synthesis process of the
emulsion was same as that discussed previously. In brief,
9 mL of oil (coconut, mustard or palm oil) was treated with
1 mL of Triton X-100 and 1 mL of either pH 3 or pH 5 solution.
Then this mixture was sonicated for 10 min to get the water-
in-oil emulsion. As our aim was to estimate the size of the
emulsion in ELM in presence of the feed solution, so after
formation of emulsion we added 10 mL of solution having
same pH as that of the stripping solution. The mixture was
then stirred for 10 min. This ELM mixture was then finally
diluted 1000 times with water and then taken in a plastic
cuvette to perform the DLS analysis.
2.8. Effect of solution’s pH
The interaction between metal and dye as well as the ex­
traction phenomena are highly pH dependent (Karmakar and
Sen, 2019a, 2019b). As discussed earlier, the interaction and
the complexation between the metal and dye were studied
with variation of pH. On the basis of that, the extraction
phenomenon was also pH dependent and hence, the strip­
ping solutions and the feed solutions were maintained at a
requisite pH to achieve the maximum extraction efficiency.
As the metal and dye complexation was not observed at pH 1,
so conditions of lower pH were avoided for the preparation of
emulsions or ELMs. The complexation between the metal
and dye was mostly observed at either pH 3 or pH 5, therefore
the ELM was also prepared with the stripping solution as well
as the feed solutions having these pH conditions.
2.9. Effect of stirring time
Stirring time is another very important parameter in the
synthesis of ELM as well as the extraction study. The effect of
stirring time for the extraction of Dy using AY dye was ex­
amined. The stirring time after addition of the feed solution
into the prepared emulsion to get the ELM was varied from
5 min to 30 min. As the maximum and selective extraction of
Dy was obtained for the ELM prepared with mustard oil as
organic phase at pH 3 medium (discussed in Section 3.3), so
the variation of stirring time was only examined for the
emulsions prepared using these conditions. The percentage
of extraction of metal was calculated to observe the effect of
stirring time.
2.10. Effect of concentration of metal-dye complex in the
feed solution
To observe the effect of concentration of the metal-dye
complex in the feed solution on the extraction percentage of
 Chemical Engineering Research and Design 187 (2022) 497–506 501

the metal, we prepared three different concentrations (viz.,

Table 3 – Association constant for the interaction
0.01 mM, 0.05 mM and 0.1 mM) of the metal-dye complex
between different metal ions and dye.
solution. As the maximum and selective extraction of Dy was
Metal Dye pH K (M-1)
obtained for mustard oil as membrane phase, AY as com­
plexing agent, at pH 3 medium (discussed in Section 3.3), so Pr(III) AY 3 1.4 × 106
these two reagents (Dy metal and AY dye) were used in the Pr(III) BAN 3 8.2 × 105
feed solution of emulsion. 5 mL metal solution having con­ Dy(III) AY 3 1.5 × 106
Dy(III) BAN 3 4.4 × 105
centrations of 0.02 mM, 0.1 mM and 0.2 mM of pH 3 were
Pr(III) AY 5 3.8 × 106
treated with 5 mL of equal concentrations of AY of same pH Pr(III) BAN 5 4.3 × 106
solution to be used as feed solution. Dy(III) AY 5 3.6 × 106
Dy(III) BAN 5 4.6 × 106

2.11. Zeta potential measurement

The Benesi–Hildebrand (B-H) equation is as follow (Ghatak

To get an idea about the surface charge and the stability of
et al. 2013):
emulsion droplets, the zeta potential of emulsions formed by
mustard oil, coconut oil and palm oil were measured. The 1 1 1
= + (1)
preparation of the ELMs has already been discussed pre­ A A0 A1 A0 (A1 A0 ) K [M]
viously. The ELM thus obtained was then finally diluted 1000
Where, A = observed absorbance of the experimental solu­
times with water and then introduced into a disposable
tion containing metal ion and dye.
folded capillary cell with the help of a 1 mL syringe for
A0 = absorbance of dye in water.
measurement of zeta potential.
A1 = absorbance when metal ion is completely bound with
the dye.
2.12. Back extraction of Dy from the organic phase [M] = Concentration of the lanthanoid ion.
K = binding/association constant.
To recover the extracted Dy(III) ions from the organic phase, On plotting 1 vs 1 , a straight line was obtained (inset
A A0 [M]
back extraction study was performed. For that purpose, we 1 1
of Fig S1–S8) with a slope = and intercept = .
followed the extraction steps with mustard oil as organic (A1 A0 ) K A1 A0

membrane phase and pH of the aqueous solutions was kept
at 3. After extraction procedure, 2 mL of the upper phase i.e.,
oil rich phase was taken out. Then 2 mL of each of ethyl
acetate, ethanol and pet ether were added and shaken to
break the ELM. 1 g of cation exchange resin was then added
to the resulting solution and shaken for 1 h. Then the su­
pernatant solution was removed and the resin was washed
for 4–5 times with the mixed solvent of ethyl acetate, ethanol
and pet ether. Next, the resin was treated with 4 mL 4 (M) HCl
solution and shaken for 1 h. After 1 h of shaking, the super­
natant solution was collected. The resin was washed for
2–3 times with water and the washings were collected in the
same container. The volume of solution was finally reduced
to 1 mL by evaporating under IR lamp. The amount of Dy(III)
present in the sample was then analysed spectroscopically
using our previously reported methodology (Singh et al.,
2020). In brief, 2 mL of 0.01 M HCl solution was treated with
0.02 mL of ruthenium-morin nanocomposite solution
(gamma irradiated with ∼38 kGy) and then a particular
amount of the sample solution containing Dy(III) was added
to this nanocomposite solution. The UV-Vis adsorption value
was recorded at 287 nm and compared with a suitable cali­
bration plot, to obtain the amount of unknown Dy(III).
3. Result and discussion
3.1. Spectrophotometric study of interaction between the
metal ion and dye
The complexation of different lanthanoids (La(III), Ce(III), Ce
(IV), Pr(III), Gd(III), Sm(III) and Dy(III)) with the two dyes AY
and BAN were studied using UV–vis absorption spectrometry
at different pH conditions (Fig S1 to S8). The stoichiometry
and the corresponding association constant (K) value of the
complexation were obtained using the Benesi-Hildebrand (B-
H) equation [Eq. 1] and are tabulated in Table 3.
From the values of these two parameters, the association
constant (K) can be calculated as K = Intercept .
Slope
At pH 1 of aqueous solution, no interaction was observed
between any lanthanoid ion and either of the two dyes. At pH
3 and 5 the absorption spectra indicated interactions of Pr(III)
and Dy(III) ions with AY and BAN. Interaction between other
lanthanoid ions and dyes were not observed at these two pH
conditions (3 and 5). The B-H plot also indicates that all the
lanthanoid ions form complexes with AY and BAN in 1:1
stoichiometric ratio.
3.2. DLS study
The DLS data reveals that the average diameter of the pre­
pared emulsions lies in the range 50–200 nm. The data also
suggests that the average diameter of the emulsion prepared
with mustard oil and coconut oil were of comparable size at
both pH 3 and 5. That is ∼120 nm and ∼110 nm at pH 3 and 5
respectively with mustard oil and ∼116 nm and 105 nm at pH
3 and 5 respectively with coconut oil. Those of the palm oil
were slightly lower i.e., ∼83 nm and ∼53 nm at pH 3 and 5
respectively (Table S1). The emulsion properties such as
emulsion size, stability, viscosity, etc., depend on the nature
of the oil i.e., their chain length, solid lipid content, etc.
(Zheng et al., 2020) as well as on the type and amount of
surfactant used (Ahmad et al., 1996). The lower emulsion
diameter in case of palm oil is probably due to higher con­
centration of emulsifier present in this particular system,
which comes from the natural origin of palm oil. It is worth
mentioning that palm oil contains phospholipids as natural
surfactants, which increases the overall emulsifier content
and hence decreases the resultant emulsion size (Ahmad
et al., 1996). Additionally, we also observed that, the diameter
of the emulsion was increased in higher acidic media than
that of the lower one. This is mainly because of higher hy­
drophobic-hydrophilic interactions in higher acidic medium
502 Chemical Engineering Research and Design 187 (2022) 497–506
Fig. 2 – Percentage extraction of metal ions using mustard
oil as membrane phase in presence of AY and BAN dye.
that results due to the presence of free ions in the higher
acidic solution. As a result, the hydrophobic microsystem
tends to separate out from the matrix and aggregate in the
emulsion phase to form spheres of larger diameter (Onsaard
et al., 2005). Measurements of the average diameter of the
emulsion indicated that increased aggregation of droplet
occurred at pH 3 as compared to pH 5.
3.3. Emulsion liquid extraction of metal ions at pH 3 and
5 with the help of AY and BAN
For the selective separation of Dy(III) ions from different
lanthanoids, first the complex formation ability of the metal
ions with the dyes AY and BAN at pH 3 and 5 were in­
vestigated (Table 3) and discussed above. Out of a set of the
metal ions La(III), Ce(III), Ce(IV), Pr(III), Gd(III) and Dy(III), only
Pr(III) and Dy(III) were found to exhibit interactions with the
two dyes. Therefore, their extraction behaviour was ex­
amined using mustard oil, coconut oil, and palm oil as or­
ganic liquid membrane phases. The percentage of
extractions in presence of mustard oil, coconut oil, and palm
oil are represented in Figs. 2–4. Fig. 2 represents the extrac­
tion efficiencies of Pr(III) and Dy(III) using mustard oil as or­
ganic phase in presence of AY and BAN dye. Fig. 3 represents
their percentage of extraction using coconut oil while Fig. 4
represents that using palm oil and AY and BAN as com­
plexing agent.
The results so obtained suggest that, the extraction effi­
ciencies of the two metal ions were altered with the variation
of dye and pH of the stripping as well as feed solutions. With
mustard oil as the membrane phase (Fig. 2), selective ex­
traction of Dy(III) was observed as 83% Dy(III) is extracted
with no contamination from the Pr(III) in presence of AY dye
in pH 3 medium. This means that when the Dy-AY complex
is prepared in the feed solution, it gets entrapped in the
micellar stripping medium and is thus separated from its Pr
counterpart at pH 3. ∼36% of Dy(III) and 54% of Pr(III) could be
extracted at pH 5 medium using AY as complexing agent. In
presence of BAN as complexing agent and mustard oil as
membrane phase, at pH 3 showed ∼80–100% extraction of
both Pr(III) and Dy(III) (Fig. 2), but the extraction percentage
deceases in presence of pH 5 medium. However, selectivity in
the extraction behaviour was not observed at any of the
conditions with BAN. This is quite an expected behaviour
since the lanthanoids have remarkable similarities in their
chemical properties that make their separation quite difficult
when present in combined form. The only condition of dif­
ference in the extraction of the two metal-dye complexes
therefore occurs at pH 3 with AY which is the possible
Fig. 3 – Percentage extraction of metal ions using coconut
oil as membrane phase in presence of AY and BAN dye.
outcome of the final stabilisation attained by the micelles
after internalisation of the complex (described further in
Section 3.6).
When coconut oil was used as the membrane phase, ex­
traction of Pr(III) in presence of AY as complexing agent was
observed in the range 41–46% in both the pH conditions.
Under similar conditions, 58% of Dy(III) was extracted at pH 3
while that at pH 5 medium was almost negligible (Fig. 3).
Thus, a selective extraction of Dy(III) was not possible using
coconut oil as membrane phase. A high extraction percen­
tage of Pr(III) (94–96%) could be achieved using BAN as a
complexing agent at both the pH media. However, there is
also a significant extraction of Dy(III) in both the cases and
hence a selective extraction condition was not obtained
(Fig. 3). The possibility of extraction of each metal dye com­
plex in the membrane phase therefore seem to depend on
several interrelated factors (i) size and surface charge of the
emulsion (ii) size and overall charge of the metal-dye com­
plex (iii) resultant hydrophobic and hydrophilic interactions
between the components of the membrane phase with that
of the components of the feed solution (iv) type of oil that
resides on the hydrophobic part of the micelles and decides
its overall nature (v) dipole-dipole interactions between the
surfactant and those of the metal-dye complex which again
depends on the pH of the medium. However, the final ob­
servation after the extraction is the resultant stability at­
tained by the whole system (as explained with zeta potential
studies described further).
In case of palm oil as membrane phase, the extraction of
both the lanthanoids was poor by using AY dye in both of the
pH media (Fig. 4). In presence of BAN as complexing agent,
the extraction percentage of Pr(III) was increased for both the
pH conditions and of Dy(III) at only pH 3. However, a selective
Fig. 4 – Percentage extraction of metal ions using palm oil
as membrane phase in presence of AY and BAN dye.
 Chemical Engineering Research and Design 187 (2022) 497–506
Fig. 5 – Variation of extraction percentage upon variation of
stirring time.
extraction condition was not obtained for this method
also (Fig. 4).
On analysis of these results with variation of membrane
phase, complexing agent and pH, the only selective extrac­
tion of Dy(III) was obtained for mustard oil as membrane
phase, AY as complexing agent, at pH 3 medium. The me­
chanism behind the extractions and the selectivity for Dy(III)
at a particular condition is explained on the basis of zeta
potentials in the upcoming section (Section 3.6). This tech­
nique was further utilised for the variation of stirring time
and concentration of the feed solution to get an optimised
extraction condition.
3.4. Effect of stirring time on the extraction of Dy(III)
using mustard oil
Effect of stirring time was studied as it has a significant role
on extraction efficiency. The result shows the effect of in­
creasing stirring time on the extraction of Dy(III) at pH 3
medium from 5 min (80% extraction) to 30 min (78% extrac­
tion) in presence of AY dye, taking mustard oil as organic
phase (Fig. 5). The results suggest that the extraction per­
centage first increased gradually to 88% upto 20 min and then
decreased on increasing stirring time beyond 20 min. This
may be due to the rupture of some membrane droplets
during the stirring process for a long period. Thus 20 min
stirring time was chosen for the selective extraction study.
For this particular study emulsion was prepared in pH 3
medium, AY dye was used as the complexing agent, mustard
oil as organic membrane phase and concentration of Dy(III)-
dye complex was kept at 0.05 mM.
3.5. Effect of concentration of Dy(III)-dye complex in feed
solution on the percentage extraction
After standardisation of the stirring time, the effective con­
centration of Dy-AY complex was varied to get the maximum
extraction efficiency. The Dy(III)-AY concentration was
varied from 0.01 mM to 0.1 mM. For this study also, emulsion
was prepared in pH 3 medium, mustard oil as organic
membrane phase and stirring time was kept at 20 min. The
results suggested that, the optimum concentration for the
maximum extraction efficiency (90%) was observed for
0.01 mM of the metal dye complex. On further increasing the
concentration, there was a gradual decrease in extraction
efficiency, which may be due to the saturation of the strip­
ping solution by the complex molecules (Kumar et al., 2018,
Malik et al., 2012). The internal phase saturates rapidly in
presence of a very high concentration of the feed solution.
503
Increase of the metal concentration in the feed solution de­
velops an osmotic imbalance and a difference in ionic
strength between the internal and the external phase of the
ELM. This results in swelling of the emulsions and hinders
the passage for the transformation of the solute. At a very
low concentration of the extractant in the feed solution, the
diffusion coefficient is low but the distribution coefficient
gradually increases with the increase in the concentration of
the extractant thereby increasing the extraction efficacy.
However, with a very high concentration of the extractant in
the feed solution, although the diffusion coefficient is high
but due to the poor distribution coefficient value, the ex­
traction efficiency decreases (Malik et al., 2012). There may
also be steric repulsive interactions between the complex
molecules at higher concentrations when they try to fit in­
side the small water droplets inside the emulsion that pre­
vent them to get further extracted.
3.6. Zeta potential measurement: mechanism behind the
extractions
Emulsions attain their stability through developing charge at
their surface when present in the dispersion medium. This is
why emulsions prepared in slightly acidic medium are much
more stable than those in neutral medium (Strassner, 1968,
Benderrag et al., 2016). When two emulsions approach close
to each other, electrostatic repulsion is generated due to the
surface charge. This electrostatic repulsion force prevents
them to coalesce with each other. The zeta potential mea­
surement gives an idea about the surface charge density on
emulsion particles. Greater the value of zeta potential, more
is the surface charge density of emulsions, which will cause
more electrostatic repulsion, hence the emulsion droplets
find it more difficult to coalesce. Therefore, greater the zeta
potential value, greater is the stability of emulsion droplets
(Bhatt et al., 2010; Huang et al., 2020). The measured zeta
potential values for 18 different emulsions are shown in
Table 4. These emulsions were prepared with metal-AY dye.
The zeta values of the emulsions prepared with metal-BAN
complex are tabulated in Table 5.
From the data presented in Table 4 we have obtained the
difference in zeta potential of each lanthanoid-dye complex
encapsulated in the respective emulsion from that of the
pristine emulsion. Fig. 6 shows this change in zeta potential
for each lanthanoid dye complex upon emulsification. It can
be seen that the highest change in zeta potential (−11.2 mV)
was observed for Dy-AY complex in mustard oil and that too
with a large negative value indicating maximum stabilisa­
tion. This indicates that the extraction of the metal dye
complex in the emulsion is associated with an attainment of
extra stabilisation, which is reflected in the increased nega­
tive zeta potential value. The decrease in effective zeta po­
tential with enhanced surface charge upon internalisation of
the metal-dye complex in the emulsion becomes the driving
force of the process. All other Δzeta values are either less in
magnitude or have a positive value indicating lesser stabili­
sation. This observation has been found to recur for all the
extractions at all pH conditions.
Fig. S9 shows the variation of zeta values of the ELMs
prepared with metal-AY complex compared to that of pure
ELMs prepared at pH 5. It can be seen that extractions cor­
responding to low values like 2–5% have positive or very low
negative Δzeta values. On the other hand, 40–50% extractions
were observed when Δzeta values lie in the range − 2.7 to
504 Chemical Engineering Research and Design 187 (2022) 497–506

Table 4 – Zeta potential values of the prepared ELMs.

Sample identity Organic phase Feed solution pH of the medium Zeta potential value (mV)

S1 Mustard oil Water 3 -30.60

S2 Dy-AY complex -41.80
S3 Pr-AY complex -29.93
S4 Coconut oil Water -27.00
S5 Dy-AY complex -30.50
S6 Pr-AY complex -30.32
S7 Palm oil Water -35.90
S8 Dy-AY complex -36.10
S9 Pr-AY complex -36.00
S10 Mustard oil Water 5 -33.53
S11 Dy-AY complex -36.24
S12 Pr-AY complex -37.21
S13 Coconut oil Water -28.1
S14 Dy-AY complex -27.23
S15 Pr-AY complex -31.20
S16 Palm oil Water -27.57
S17 Dy-AY complex -30.77
S18 Pr-AY complex -30.57

Table 5 – Zeta potential values of the prepared ELMs with BAN dye at pH 3 and pH 5.
Sample identity Organic phase Feed solution pH of the medium Zeta potential value (mV)

S19 Mustard oil Water 3 -30.60

S20 Dy-BAN complex -42.80
S21 Pr-BAN complex -41.60
S22 Coconut oil Water -27.00
S23 Dy-BAN complex -27.60
S24 Pr-BAN complex -39.50
S25 Palm oil Water -35.90
S26 Dy-BAN complex -47.90
S27 Pr-BAN complex -47.00
S28 Mustard oil Water 5 -33.53
S29 Dy-BAN complex -36.63
S30 Pr-BAN complex -33.99
S31 Coconut oil Water -28.10
S32 Dy-BAN complex -31.30
S33 Pr-BAN complex -40.20
S34 Palm oil Water -27.57
S35 Dy-BAN complex -27.90
S36 Pr-BAN complex -39.15

− 12 mV, which resulted due to higher stabilisation of the

emulsions upon uptake of the respective metal-dye complex.

3.7. Back extraction of Dy from the organic phase

Back extraction of extracted elements is very essential for the

Fig. 6 – Variation of zeta values of the ELMs prepared with
metal-AY complex compared to that of pure ELMs prepared
at pH 3.
− 3.5 mV. Similar were the results with metal-BAN complexes
at pH 3 and 5 (Fig. S10 and S11 respectively). High extraction
percentage (∼80–90%) showed a large Δzeta value of − 11 to
purpose of its reuse. Thus in this experiment cation ex­
change resin was used to remove Dy(III) from the emulsion
phase. It was observed that around 88% of Dy(III) could be
back extracted into aqueous solution after the series of
treatment of the ELM as described in the experimental sec­
tion. After breaking of the ELM with the mixed solvent (ethyl
acetate, ethanol and pet ether), the Dy(III) (whether in com­
plex form or free ionic form) prefers to bind with the cation
exchange resin. During shaking with resin, the H+ ions of the
resin were replaced by Dy(III) and on washing the resin with
4 M HCl solution, the Dy(III) ions are regenerated into the
aqueous phase.
 Chemical Engineering Research and Design 187 (2022) 497–506
Fig. 7 – Statistical representation of the overall extraction results.
4. Conclusion
The present work describes the generation of water in oil in
water emulsion for the selective extraction of Dy(III) ion with
the help of AY as a complexing agent from a mixture of La
(III), Ce(III), Ce(IV), Pr(III), Gd(III) and Dy(III) ions. We have
chosen three different oil media, viz., mustard oil, coconut oil
and palm oil as the organic phase. The emulsion was pre­
pared at two different pH media to study the extraction ef­
ficacy of different lanthanoids in presence of two different
complexing agents AY and BAN. The size of the prepared
emulsions was estimated with the help of DLS analysis. The
extraction efficacy was found to be dependent on the selec­
tion of oil as well as the complexing agent and the pH of the
medium. Apart from Pr(III) and Dy(III) all other lanthanoids
did not show complexation with AY and BAN at the chosen
pH conditions. The selectivity towards extraction of metal
ion was achieved for Dy(III) ion in presence of AY as a com­
plexing agent with mustard oil as the organic phase at pH 3.
Fig. 7 shows the overall results in statistical form. The me­
chanism behind the selectivity is the stabilisation of the
emulsion formed after Dy(III) extraction, which is reflected in
the decrease in zeta potential upon extraction of the ion. The
highest extraction efficacy was observed for 20 min of stir­
ring in presence of 0.01 mM concentration of the feed solu­
tion. Back extraction study showed ∼ 88% of the metal could
be back extracted from the ELM. Thus a clean selective ex­
traction method of Dy(III) from different lanthanoids has
been developed, which is considered to be highly challenging
in separation chemistry.
Declaration of Competing Interest
Authors declare no conflict of interest.
Acknowledgements
R. K. gratefully acknowledges the University Grants
Commission (UGC), New Delhi, India (Ref No. of R. K. 19/06/
2016(i)EU-V dated 14/06/2017) for providing necessary fel­
lowship. P. S. expresses sincere thanks to the University
Grants Commission (UGC) (Ref. No. of P. S. 20/12/2015(ii)EU-V
dated 24.08.2016) for providing necessary fellowship. The
authors are thankful to UGC-DAE-CSR, Kolkata Centre, India,
for providing DLS and Zeta potential measurement facility.
505
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.cherd.2022.09.001.
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