Research Article

ChemSusChem doi.org/10.1002/cssc.202301418

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Green Deep Eutectic Solvents (DESs) for Sustainable Metal

Recovery from Thermally Treated PCBs: A Greener
Alternative to Conventional Methods
Snigdha Mishra,[a, b] T. N. Hunter,[b] K. K. Pant,*[a, c] and David Harbottle*[b]

Waste PCBs the core of e-waste is rich in copper, tin, zinc, iron, solubility. Oxalic acid has high selectivity for Sn. FA ChCl
and nickel. Leaching base metals from PCB used to be done in extracted Cu and Fe best at 16 h, 100 °C, and 1/30 g/mL.
toxic, corrosive acidic/alkali mediums. In this work, an environ- Urea ChCl extracted Zn (90.4 � 2.9 %) from TPCBs at 100 °C,
mentally friendly method for leaching metals from thermally 21 h, 1/20 g/mL, and 400 rpm. Oxalic acid (1 M) removed 92.3 �
treated PCBs (TPCBs) of mobile phones was proposed using 2.1 % Sn from TPCBs in 1 h at 80 °C and 1/20 g/mL. The
choline chloride based deep eutectic solvents (DES). DES shrinking core model-based kinetic investigation of FA ChCl for
selectivity and solubility of metals from metal oxides were the Cu extraction showed a diffusion-controlled process. The
main screening criteria. FA ChCl had the maximum solubility of proposed method is greener than mineral acids utilized for
Cu, Fe, and Ni, while Urea ChCl had high Zn selectivity and metal extraction.

1. Introduction generated 16 years ago.[2] Nevertheless, the recycling rate of e-

waste is quite low and mostly concentrated in unregulated
Electronic waste (e-waste) is a vastly underutilized resource that informal sectors, often involving open dumping or burning.[4]
offers a plethora of economic opportunities. E-waste contains a Metal extraction from e-waste presents opportunities in the
wealth of precious metals (platinum, gold, silver), base metals context of a circular economy driven by the need to recycle
(aluminum, iron, copper), heavy (zinc, mercury, chromium, valuable metals from discarded electronics and reduce environ-
lead), and rare earth metals (tantalum, platinum groups).[1] In mental impacts from traditional virgin mining. Printed circuit
2019, the estimated value of treasured metals in e-waste such boards (PCBs) are one of the vital components of any electronic
as gold, copper, iron, etc., inclusive of plastics obtained from e- gadget, constituting 3 % of the total collected electrical and
waste, is assessed to be equivalent to USD 57 billion.[2] electronic waste globally.[5] Recycling PCBs is necessary for
According to the UN World Economic Forum in 2019, the gold economic and environmental reasons, as they are rich in
present in a tonne of e-waste is 100 times more valuable than 1 valuable metals such as copper, iron, gold, silver, and hazardous
tonne of gold ores.[2] Likewise, a metric ton of printed circuit metals such as lead, chromium, etc. PCBs are often referred to
board (PCB) contains 30 to 40 times higher copper than one as an “Urban Mineral Source” due to their metal concentration
metric ton of natural copper ore.[3] The use of e-waste as a rich being 10 times richer than that of ores.[6]
secondary source of metals can significantly bridge the huge The development of a metal recycling process from PCBs is
gap between demand and supply of several scarce metals, e. g., necessary for the electronics industry to thrive sustainably.
tin, silver, gold, platinum, lithium, etc. The Global E-waste Conventional methods, such as electrostatic separation,[7] froth
Monitor Report 2020 revealed that ca. 53.5 million metric tons floatation,[8] and vibration gas-solid fluidized bed,[9] have been
(MMT) of e-waste was generated globally in 2019.[2] The report used to separate distinct non-metallic and metallic fractions.
also predicts that an astounding 74 MMT of e-waste will be Furthermore, to recover metals from e-waste, pyrometallurgy,
generated by the year 2030, nearly double the amount hydrometallurgy, and biohydrometallurgy have been
employed.[3] Pyrometallurgy operates at very high temperatures
and produces hazardous gases like dioxins due to the presence
[a] S. Mishra, K. K. Pant of brominated flame retardants, (hydro)chlorofluorocarbons,
Green and Sustainable Engineering Lab, Department of Chemical Engineer-
and mercury in PCBs.[10] Hydrometallurgy, a flexible alternative
ing, IIT Delhi, Hauz Khaz, Delhi, 110016, India
E-mail: [email protected] approach for recovering metals, uses alkaline,[11] cyanide,[12]
[email protected] thiosulphate,[13] mineral acid,[14] etc., as leaching agents to
[b] S. Mishra, T. N. Hunter, D. Harbottle extract metals such as copper, zinc and gold. However, poor
School of Chemical and Process Engineering, University of Leeds, Leeds, selectivity, toxicity,[15] and severe environmental threats have
LS29JT, United Kingdom
led to an exploration of greener alternatives to conventional
E-mail: [email protected]
metal extraction techniques.[16]
[c] K. K. Pant
Department of Chemical Engineering, IIT Roorkee, Roorkee, 247667, India The replacement of toxic reagents with green solvents, such
Supporting information for this article is available on the WWW under as ionic liquids and supercritical fluids, has been proposed by
https://doi.org/10.1002/cssc.202301418 several researchers.[17] Xiu et al. used supercritical water with

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HCl leaching for 100 % Cu recovery and iodine-iodine leaching stage by dissolving various metal oxides.[25b,34] Further, based on
to recover silver, gold, and palladium from PCBs.[18] Golazary the solubility of metals in respective DESs, each selective
et al. combined the supercritical water process as pre-treatment solvent was chosen for optimizing parameters in metal
followed by supercritical CO2 to recover 97 % copper from PCBs extraction. FA ChCl showed the highest solubility of Cu, Fe, and
at 60 °C and 200 bar.[17a] However, high pressure to attain the Ni, while Urea ChCl exhibited selective solubility of Zn. For Sn
supercritical state is a concern in these technologies. Ionic extraction, 1 M oxalic acid demonstrated the highest efficiency.
liquids are promising and environmentally sound alternatives to TPCBs of mobile phones with high metal concentrations have
organic solvents. Huang et al. used [bmim]HSO4 ionic liquid been used as feed materials for metal leaching experiments in
with hydrogen peroxide to extract copper from PCBs.[19] the screened solvents. The influence of several leaching
Barrueto et al. observed that acidic ionic liquid ([Bmim]HSO4 parameters such as time, temperature, and S/L ratio, in base
and [Hmim]HSO4) extracted 86.2 % and 76.6 % copper, respec- metal leaching in DESs has been discussed in detail. Since
tively, while basic ionic liquid ([Bmim]Cl) extracted 47.3 % silver copper has the highest contribution to the metallic composition
and 19.1 % gold.[20] Nevertheless, the exploration of safer, of PCBs, the shrinking core model leaching kinetics of the highly
cheaper, and tunable solvents for sustainable chemicals has extracted copper using FA ChCl DES, and the activation energy
received much attention in recent years. of copper were assessed. A plausible mechanism was proposed
Deep eutectic solvents, composed of naturally occurring based on literature, DFT and Pourbaix diagram.
compounds, have high extraction efficiency for metals and low
toxicity with a cutting edge over ionic liquids in terms of easy
preparation method, less corrosive, and relatively easy biode- 2. Materials and Methods
gradation. The advantage of DESs lies in the difference in the
coordination ability of components and metals, providing a 2.1. Chemicals and Reagents
low-cost green strategy with the potential to selectively extract
metals on a large scale from complex ores or waste material. Waste PCBs of miscellaneous brands used in this study were
Malonic acid-choline chloride (MA ChCl), Oxalic acid-choline provided by Exigo Recycling Pvt. Ltd, Haryana, India. The PCBs
chloride (OA ChCl), and Ethylene glycol-choline chloride were crushed and ground to a size below 1.0 mm for the
(EG ChCl) DESs were checked by Abbott et al. for transition experiment. For the digestion of solid samples, nitric acid (86 %,
metal oxide dissolution.[24] Selective dissolution of metals was HNO3) and hydrochloric acid (37 %, HCl) from Fisher Scientific
observed in choline chloride (ChCl) DES. Since then, the were used to prepare the aqua regia solution.
development of DES synthesis has taken precedence in the For DES synthesis, choline chloride (> 98 %) was purchased
sector as a means of effective metal extraction from compli- from Alfa Aesar, formic acid (99 %), urea (> 98 %), ethylene
cated compounds under benign conditions.[25] Choline chloride- glycol (> 95 %), malonic acid (99 %), and oxalic acid (99.5 %)
based DESs were reported to have highly efficient metal were obtained from Fisher Scientific. Metal oxides, including
leaching from Li-ion batteries[26,27], NdFeB magnets,[26] ores,[27] copper oxide (> 99 %, CuO), iron oxide (> 96 %, Fe2O3), zinc
minerals,[28] and electric arc furnace dust.[29] oxide (> 97 %, ZnO), and nickel oxide (> 99 %, NiO) were
Recoveries of metals from spent lithium-ion batteries are purchased from Sigma Aldrich. For dilution, double-distilled
extensively studied.[30] Li et al. found DESs to be a greener water with a conductivity of less than 1 μS/cm was employed.
alternative to inorganic acids with metal leaching efficiency (> All the reagents used in this experiment are of analytical grade
99 %) but with slower leaching kinetics.[30c] Wang et al. con- and were used as received.
cluded that the high reducing power of Urea ChCl DES makes
it the best DESs for cathode recycling of Li-ion batteries.[31] Tran
et al. observed that ethylene glycol ChCl DESs recover 99.3 % 2.2. Experimental
of cobalt and lithium from lithium cobalt oxide, and metal
leaching efficiency increases with time and temperature.[30e] The Waste PCB samples were comminuted and screened to obtain a
use of green solvents for metal extraction from e-waste is a powder with a particle size of less than 1 mm. Particles smaller
promising area of research with the potential to reduce the than 1 mm in size were separated using an ASTM E11 #
environmental impacts of traditional mining processes. Lactic 18 mesh screen (American Society for Testing and Materials).
acid ChCl,[32] malonic acid ChCl,[32] and ethylene glycol ChCl[33] The organic content was removed from the PCBs using thermal
have been used to extract metals from WPCBs, covering limited pre-treatment, which involved pyrolyzing them in an inert
aspects. However, no detailed study of formic acid-choline environment. Pyrolysis was conducted in a fixed bed reactor at
chloride and urea-choline chloride in metal extraction from 500 °C for 30 min in a nitrogen atmosphere, as these conditions
WPCBs has been done in the past to the best of our knowledge. are sufficient for the cracking of the plastic part of PCBs, as
Considering this research gap and the Choline chloride DES discussed by Marco et al..[35] The extraction efficiencies of Cu,
advantage of selective metal extraction, the present study is Zn, and Sn from TPCBs were calculated using the following
proposed. formula (1).
The present study uses green deep eutectic solvents and
organic acid for the selective recovery of Cu, Fe, Ni, Zn and Sn
from PCBs. Screening of green solvents was done in the first

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Cl � V l varied from (20–140 °C), stirring speed (100–800 rpm), time (1-
Extraction efficiency ðE %Þ ¼ � 100 (1) 24 h), and S/L ratio (1/10–1/50 g/mL). The extraction of tin in
WmTPCB
oxalic acid time was evaluated at process conditions with time
(1–5 h); temperature (50–80 °C) and oxalic acid concentration 0–
Where Cl is the metal content in leached solution (g/L); Vl is 3 g/L. High temperatures (> 100 °C) were avoided considering
the leach volume (L), and WmTPCB is the weight of the metal in the economical and energy point of view.[36] Glass bottles were
TPCBs (g). closed to prevent the loss of vapors.

2.2.1. Synthesis of Deep Eutectic Solvents 2.2.3. Individual recovery of copper

The DESs were prepared via the heating method. Hydrogen The metal-leached solution obtained under optimized condi-
bond acceptor (HBA), ChCl, was combined with hydrogen bond tions was utilized for copper recovery from FA ChCl through
donors (HBD), i. e., FA, urea, ethylene glycol, malonic acid, and the cementation process. The metallic zinc powder was
oxalic acid in a (2 : 1) molar ratio in sealed 50 mL glass vials introduced into the leached solution to facilitate the recovery of
while being continuously stirred at 200 rpm at 50 °C to create a metallic copper. The process began by transferring 200 mL
eutectic mixture. However, mole ratios of individual compo- metal leached solution into a beaker followed by the gradual
nents in OA ChCl and MA ChCl DES were 1 : 1.[25a] The solvents addition of Zn powder. The appropriate stoichiometric amount
were then stored at room temperature in a desiccator to avoid of Zn was used to ensure effective copper cementation. Once
moisture absorption. the cementation was completed, the precipitated copper was
recovered, dried, and subjected to analysis. The concentration
of metal ions in the solution is determined by ICP-MS and
2.2.2. Metal leaching cementation efficiency (q) was calculated by equation (3):

All leaching/extraction experiments were carried out in 50 mL C

q ¼ ð1 Þ � 100 % (3)
Borosil glass on a hot magnetic stirrer (Cole-Parmer Stuart) with C0
an oil bath. Primarily, for screening DESs, 0.1 g of respective
metal oxides: CuO, Fe2O3, ZnO, and NiO were dissolved in 10 mL Here, q is metal precipitation efficiency (%), C0 is initial metal
EG ChCl, Urea ChCl, FA ChCl, OA ChCl, and MA ChCl for 24 h concentration in optimized leaching solution, mg/L; and C is
at 80 °C. The temperature of 80 °C is selected as Abbott et al.[34] metal concentration in a solution after cementation, mg/L.
observed high solubility of zinc in urea ChCl at a temperature
greater than 60 °C. Respective DES were selected for individual
metal extraction. 1 M oxalic acid was also tested to check the 2.3. Instrumentation and analysis
solubility of copper, iron, zinc, and nickel from oxides.
A parameter selectivity (Sm) was defined to evaluate the A Nicolet iS50 FTIR spectrophotometer with an ATR crystal
effectiveness of different leaching solutions. It is calculated by detector was used to record infrared spectra. Samples were
dividing the concentration of the metal of interest (m) by the scanned 32 times with a resolution of 4 cm 1 in the range of
sum of concentrations of all leached metals in the solution by 400–4000 cm 1. Background reference spectra were obtained
equation (2). before sample measurement to avoid interferences. All samples
were measured under atmospheric conditions.
X
Sm ¼ Cm = Ci � 100 % The distribution of metal phases was investigated using X-
(2) ray diffraction (XRD) by Rigaku Mini Flex 600 instrument from
i

Japan. Cu K radiations were utilized, with graphite serving as a

Here, C m is the concentration of metal of interest in leaching monochromator. The XRD measurements were conducted at
solution and Ci is the concentration of any metals in a leached 40 kV and 15 mA, employing an X’Celerator detector. The
solution. scanning process involved a ramp rate of 5°/min, spanning an
A series of leaching optimization experiments were con- angle range of 5–80°.
ducted to find the maximum copper, zinc, and tin leaching Netzsch STA449 Thermo Gravimetric Analyzer (TGA) was
efficiency in their respective highest soluble solvents. Filter used to assess the thermal degradation of DES. 10–20 mg of
paper with a 0.22 μm pore size was used to separate the solid DES was placed in a nitrogen environment throughout a
residue from the leach liquor. The residue was washed with temperature range of 25–800 °C.
ultrapure water and dried for 24 h at 100 °C. For metal The density of solvents was measured by Mettler Tolardo
extraction from e-waste, 1g of TPCB sample was taken in a DE45 Delta Range Density meter. The viscosity of DESs was
given volume of FA ChCl, Urea ChCl, and 1 M oxalic acid measured by Anton Paar MCR302 rotational and oscillatory
solution. The effect of time (1–32 h), temperature (20–100 °C), rheometer equipped with cone and plate geometry (CP 50,
and S/L ratio (1/10–1/40 mg/L) were evaluated for Cu, Fe, Zn, diameter 50 mm, and angle 1°) at 303.15, 323.15 and 343.15 K
Ni, and Sn in FA ChCl. In Urea ChCl, the temperature was temperatures at constant shear rate of 1000 s 1.

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Metal extraction in DESs was determined by Elan DRCe transition metals in the PCBs are comparable to those
(Perkin Elmer) ICP-MS, diluting the samples 1000 times with previously reported.[38]
doubly distilled water. The solubility experiments and measure- Figure 1 compares the FTIR spectra and XRD patterns of the
ments were done in triplicate. PCB and TPCB. The FTIR spectra (Figure 1a) of the PCB show the
presence of CH3 methyl aromatics at 2967 cm 1, C=O at
1738 cm 1, benzene ring at 1610 cm 1 and 1506 cm 1. C Cl and
2.4. Computational Method C Br functional groups in the range of 500–750 cm 1. In the
case of TPCB, several characteristic peaks of PCB (C=O,
A theoretical study of DES was done by optimizing ChCl, FA, halogens, C=C trans) disappeared, signifying the loss of the
urea, and oxalic acid. Geometrical optimization of structures organic functional group after pyrolysis at 500 °C.
was done using Gaussian with B3LYP 631 g + (d,p) basis set.[37] Figure 1b compares XRD patterns for PCB and TPCB
The dispersion effect was avoided by adding the keyword showing peaks at 44°, 51° and 74°, which correspond to
“empirical dispersion = D3” in the command section. Hydrogen metallic copper with Miller Indices (111), (002) and (022),
bond distances and angles of DESs have been calculated and respectively (JCPDS 00–004-0836). As such, the pyrolysis process
quantified for H-bonds. The spatial distribution of electrostatic does not affect the metal phase or its oxidation state. Figure 1c
interactions in the solvent system was determined by Electro- depicts the models of HBD involved in this study.
static potential surface (ESP) calculation. The interaction energy
of copper with hydrogen bond donors of DES has been
assessed. 3.2. Screening of DES and strategies for metal extraction:

To determine the DES for maximum extraction of Cu, Ni, Fe, Zn

3. Results and Discussion and Sn, the respective metal oxides were tested for dissolution
in a range of DES: EG ChCl, Urea ChCl, FA ChCl, OA ChCl,
3.1. Characterization of PCB and TPCB MA ChCl, and 1 M oxalic acid, as shown in Table S1.
The solubility of Cu in FA ChCl was 1.60 � 0.06 (×105) ppm.
As a feedstock, PCBs are rich in critical metals such as Cu, Ag, However, this DES had the lowest solubility of Zn at 3.12 � 0.12
Au and Al. Table 1 summarizes the elemental composition of (×102) ppm, while OA ChCl and MA ChCl had much higher
the PCB used in the current study. Among these metals, Cu is solubilities for Zn at 9.65 � 0.09 (×104) ppm and 1.62 � 0.05
the most prevalent metal in the PCB constituting 29.6 wt%, (see (×104) ppm, respectively. For Cu, those DESs showed an
Table 1). After subjecting the PCB to the thermal treatment, the intermediate solubility, which affects its selectivity towards zinc.
Cu content increased to 58.8 wt% due to the removal of the The solubility of Zn in Urea ChCl was in the range of 105 ppm,
non-metallic fraction. The initial Fe and Zn contents in the PCB but for Cu, the solubility was very low at 10 ppm. Based on
were 9.6 wt% and 0.2 wt%, respectively, and were enriched to these findings, FA ChCl was selected to extract Cu from TPCB,
14.4 wt% and 0.5 wt% in the TPCBs. Additionally, the contents and Urea ChCl for Zn extraction.
of Al, Ni and Sn ranged from 0.4–2 wt%, in the PCBs, and As for Sn, SnO2 solubility in dicarboxylic acid DES was higher
enriched to 0.6–8 wt% in the TPCBs.[38] The concentrations of as compared to other types of DES. OA ChCl DES also leached
Cu and Zn in the solution due to the presence of Cl . Oxalic

Table 1. Elemental composition of PCB and TPCB (w/w%).

Cu Fe Al Zn Ni Sn

PCB 29.63 � 1.25 9.66 � 0.20 0.43 � 0.02 0.15 � 0.01 1.26 � 0.12 1.90 � 0.14
TPCB 58.76 � 2.01 14.45 � 1.20 0.62 � 0.03 0.52 � 0.02 2.53 � 0.13 7.88 � 0.17

Figure 1. FTIR of PCB and TPCB (a); XRD of PCB and TPCB with clear peaks (*) at 44°, 51° and 74°. (b); models of HBDs used in the DES (c).

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Figure 2. Selectivity of leached metals into different DESs and oxalic acid.

Table 2. Viscosity (mPa.s) of the synthesized DES as a function of temper-

acid is a good reducing agent, consequently having a high
ature.
selectivity for Sn over Zn and with a high leaching efficiency (>
DES 30 °C 50 °C 70 °C
95 %).[39] This high selectivity results from the interaction of 2
carbon atoms of oxalic acid, preferentially interacting with FA ChCl (2 : 1) 1.04 � 0.001 0.54 � 0.002 0.46 � 0.001
Urea ChCl (2 : 1) 725 � 13.100 160 � 2.100 99 � 4.280
stannous salt (Sn salt) to form a Sn-dicarboxylate complex.[39 40]
Furthermore, TPCB is taken as the feed material to identify
trends in selectivity and explore the leaching behavior of
solvents under the same experimental conditions as the metal across the temperature range, which was significantly lower
oxides at 80 °C, as shown in Figure 2 and elaborated in Table S1. than the viscosity of Urea ChCl, which was several hundred
mPa.s. Consequently, FA ChCl DES exhibits little mass transfer
resistance compared to Urea ChCl. The high viscosity of
3.3. Characterization of DES Urea ChCl can be attributed to factors such as the presence of
a prevalent hydrogen bond network, large ion size, and small
The physicochemical properties of DES are obligatory for its void volumes. For both DES the fluid viscosity decreased with
industrial applications. The synthesized DES, including FA ChCl, increasing temperature, see Table 2.[22] Higher temperatures
EG ChCl, MA ChCl, and OA ChCl, were characterized to also enhance the leaching efficiency by enhancing the mass
estimate their physical properties, including the density, transfer of the dissolved species.[43] In the context of extracting
viscosity, and conductivity of DES. These properties have metal ions from electronic waste, it is often observed that a
significant implications for understanding fluid behavior, heat reduced viscosity of the leaching agent, such as DES, is
transfer, mass transport, and designing chemical processes.[21] advantageous for facilitating the dynamic conditions of the
Density and viscosity were evaluated at different temperatures liquid-solid reaction and the subsequent separation process.
to comprehend the behavior of the liquid under various Figure 3a shows the IR spectra of FA, ChCl and 2FA ChCl.
thermal conditions. Vibrations of FA ChCl account for OH stretching at 3359 cm 1,
Choline chloride DES typically has a density of 1–1.3 g/ C H stretching at 1474 cm 1, sp2 C O stretching at 1710 cm 1,
cm3..[41] In our last study, the densities of FA ChCl, MA ChCl, and sp3 C O stretching at 1078 cm 1.[44] The C H vibration
and OA ChCl were reported to be 1.16, 1.23 and 1.15, g/cm3, shifted from 1482 cm 1 in ChCl to 1474 cm 1 in FA ChCl.
respectively.[41] The density of ethylene glycol-choline chloride FA ChCl exhibits significant peaks of neat FA and ChCl peaks
was 1.08 g/cm3.[42] The shear viscosities of all the synthesized with some shifts indicating an H-bond in between FA and ChCl.
DES were measured at 30, 50 and 70 °C, to understand the Figure 3b represents the IR spectra of ChCl, urea and
behavior of solvent viscosity with temperature according to Urea ChCl. The IR spectra of urea show symmetric stretching
Table 2. The viscosity of FA ChCl ranged from 0.4 to 1 mPa.s C=O at 1675 cm 1, which was also observed in DES with a shift

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Figure 3. FTIR of FA, ChCl and 2FA ChCl (a); Urea, ChCl and 2Urea ChCl (b).

to 1665 cm 1. The frequency of 1590 cm 1 in urea represents desirable in applications. Hence, the mild oxidizing agent
symmetric bending NH and NH2, which was observed at hydrogen peroxide was selected for further experiments.
1599 cm 1 in Urea ChCl. NH stretch peak of urea at 3433 and Different molar concentrations of H2O2, ranging from 0.5 M
3342 cm 1 has a lower shift to 3322 cm 1 and 3186 cm 1 in – 2 M, have been investigated to examine the impact on metal
Urea ChCl, which is attributed to the N H stretch. It should be extraction while keeping other parameters constant (400 rpm,
noticed that the Urea ChCl characteristic spectrum nearly 24 h, 1/20 g/mL, 100 °C). After adding H2O2, metal extraction in
overlaps that of urea and ChCl. CH3 at 1482 cm 1, CH2 at FA ChCl increases to 94.3 � 2 % Cu, 81.2 � 2.4 % Fe and 91.6
1084 cm 1, and CCO at 950 cm 1 appeared in the DES spectrum, � 1.1 % Sn as depicted in Figure 4. There was no significant
revealing that the structure of ChCl was retained in DES. change in metal extraction beyond 1 M H2O2 in FA ChCl DESs.
The thermal stabilities of FA ChCl and Urea ChCl were Thus, 1 M is chosen as the optimum H2O2 concentration.
evaluated using TGA. FA ChCl degrades from 388 K, while the Hydrogen peroxide has a similar effect as the presence of
degradation temperature is much higher for Urea ChCl at oxygen; the extra oxygen is known as “active oxygen,” which
440 K. Therefore, the maximum operating temperature of interacts with metals and changes their oxidation states. Moffett
FA ChCl should be less than 388 K, whereas, for Urea ChCl, et al. discussed the mechanism of oxidation or reduction
440 K is the maximum operating temperature, as depicted in reaction of H2O2 with Cu(II) and Fe(III).[46] Colcleu et al. illustrated
Figure S1. the interaction of H2O2 with metallic copper in the presence of
sulphuric acid.[47] Equation (4–6) discusses the credible mecha-
nism of metal oxidation.
3.4. Parameter study on metal extraction
M ðsÞ ! M2þ þ 2e (4)
3.4.1. Effect of oxidizing agent
H2 O2 ðaqÞ þ 2 Hþ ðaqÞ þ 2e ! 2 H2 O (5)
[45]
DES have no oxidizing power of their own. However, they
could be used to dissolve metals either using oxidizing agents M þ H2 O2 ðaqÞ þ 2 Hþ! M2þ þ 2 H2 O (6)
or as an electrolyte for the electro-oxidation of metals.[45]
Without the addition of oxidizing agents, there is a slight Furthermore, the oxidized metal forms complexes either
elemental metal breakdown from e-waste into the solution, with Cl or with COOH of DESs, which enhances the efficiency
specifically in DES. A further oxidation phase with an oxidizing of metal extraction. There have been almost negligible studies
agent is therefore required for the dissolution of metals. on the extraction of metals from electronic waste using DESs
Potassium permanganate (KMnO4) and hydrogen peroxide with H2O2. However, carboxylic acids were used as a leaching
(H2O2) are commonly used oxidizing agents for the oxidation of agent along with hydrogen peroxide to extract metals from
metals in the leaching system. In this system, both KMnO4 and electronic wastes.[48] For zinc extraction in Urea ChCl, H2O2 was
H2O2 were tested in combination with DES to extract metals. observed to have maximum extraction efficiency at 1 M H2O2.
The addition of KMnO4 in DES showed higher dissolution of The molar concentration of oxalic acid was varied from (0.5–
copper and iron as compared to H2O2, as shown in Table S2. 2 M) to check the extraction of tin according to Figure 7a. It was
However, potassium permanganate can be relatively expensive observed that at 1 M, there is the maximum extraction of tin,
and generate significant amounts of waste, making it less and it remained the same on further increasing molar

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Figure 4. Effect of H2O2 concentration on metal extraction from PCB using FA ChCl (400 rpm, 24 h, 1/20 g/mL and 100 °C).

concentration. However, no oxidizing agent was used to leach 3.4.3. Effect of time
tin from PCB using optimized 1 M oxalic acid.
The effect of metal extraction efficiency in individual DESs was
studied by varying time from 1–32 h at 100 °C constant temper-
3.4.2. Effect of temperature ature and 1/20 g/mL in FA ChCl. It was observed that copper,
nickel, and iron extraction reached 93.5 � 3.47 %, 90 � 1.73 %,
Based on the thermal stability of solvents by TGA, the maximum and 93.5 � 2.52 % extraction at 21 h and are almost at
operating temperatures were selected. The efficiency of metal equilibrium after 21 h. After 24 h, the extraction efficiency of
extraction by changing reaction temperature was studied in the these three metals in FA ChCl was above 93 %, as demon-
individual solvent system by ranging temperature from 20– strated in Figure 5a. However, low soluble metals zinc and tin
100 °C for FA ChCl, 20–100 °C for 1 M Oxalic acid, and varying reach 34.3 � 2.34 % and 51.8 � 2.27 % metal extraction till 32 h,
20–130 °C for Urea ChCl. For FA ChCl, all the other parameters respectively, in FA ChCl.
were kept constant, time at 21 h, solid-liquid ratio of 1/20 g/mL, The effect of time on metal extraction in Urea ChCl was
and stirring speed of 300 rpm. Figure 5b depicts that an studied by varying it from 1–24 h at (100 °C; 1/20 g/mL;
increase in temperature had a remarkable effect on metal 400 rpm). It was observed that after 16 h, zinc extraction was
extraction efficiency from ~40–42 % of copper, nickel, and iron 90.1 � 4.1 % and did not have significant changes in metal
to greater than 90 % of metal extraction in FA ChCl at 100 °C. extraction, as shown in Figure 6b. Hence, 16 h is the optimum
An increase in reaction temperature enhances the collisions time for maximum Zn extraction.
between reactants, thereby enhancing metal extraction.[49] The The time effect on metal extraction from PCBs with oxalic
optimum temperature of 100 °C was selected for FA ChCl. acid was studied from 30 min to 2 h, as shown in figure 7b.
Low-moderate reaction temperatures (20–140 °C) were Temperature of 100 °C, S/L ratio of 1/20 g/mL, and 300 rpm
selected for Urea ChCl to evaluate temperature effect on metal were fixed. It was observed that in 1 h, extraction of tin was
extraction efficiency, keeping other parameters viz, time (21 h), 91.3 � 2.1 % which varies barely on increasing time till 5 h.
solid-liquid ratio (1/20 g/mL), stirring speed (300 rpm) constant. Therefore, 1 h is chosen as the optimum time for maximum tin
In Urea ChCl, zinc extraction drastically increased to 90.37 � extraction.
1.97 % on increasing temperature to 80 °C, as shown in
Figure 6a. In the temperature range between 80–120 °C,
selective extraction of Zn was also observed. Therefore, 80 °C is 3.4.4. Effect of S/L ratio and stirring speed
preferred as the optimum temperature for Urea ChCl.
1 M oxalic acid was examined from 20–50 °C to evaluate the Metal extraction efficiency in DES is highly dependent on the
extraction of tin from TPCBs, as shown in Figure 7c. It was available area per unit volume of the solution. The solid-liquid
observed that extraction of tin at 20 °C was 75.32 � 1.06 % while ratio was examined in FA ChCl for metal extraction, ranging
it raised to 91.28 � 2.32 % at 80 °C in 1 h, 1/20 g/mL, 300 rpm. from 1/20 to 1/40 g/mL while keeping other process parameters
constant: time (16 h), temperature (80 °C) and stirring speed
(300 rpm). It must be noted that along with DESs, 1 M H2O2 has

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Figure 5. Effect of Time (100 °C; 1/20 g/mL; 300 rpm) (a); Temperature (21 h; 1/20 g/mL; 300 rpm) (b); S/L ratio (100 °C; 21 h; 300 rpm (c); in metal extraction
from TPCB to FA ChCl.

been used for metal leaching experiments in DES systems. It should be a trade-off between metal extraction efficiency and
was observed that 1/30 g/mL is the optimum solid-liquid ratio process yield. Thus, a 1/20 g/mL and a 1/30 g/mL ratio are the
for 94.5 � 2 % copper, 95.1 � 1.2 % iron, and 95.6 � 1.8 % nickel optimum solid-liquid ratios for maximum tin extraction in oxalic
extraction in FA ChCl as shown in Figure 5c. At a higher S/L acid and base metals extraction in FA ChCl, respectively.
ratio (1/10 g/mL) there is a reduction in metal extraction due to In order to reduce the impact of external mass transfer, the
the diminution of available surface area per volume of solution effect of stirring speed was visualized by changing the stirring
resulting in low interaction of PCB powder and FA ChCl speed in extremely viscous Urea ChCl DESs from 100 to
solution. Furthermore, at a low S/L ratio, there is an increase in 800 rpm, as shown in figure 6d. It was observed that 400 rpm is
solution viscosity due to the agglomeration of PCB powder the optimum stirring speed for maximum zinc recovery. An
particles, which is unfavorable for mass transfer and diffusion increase in stirring speed leads to efficient mass transfer
resulting in low metal extraction.[43] On further decreasing the without agglomeration, thereby decreasing mass transfer
S/L ratio, there is an excessive solvent that does not have a resistance and increasing metal extraction. However, 300 rpm is
significant effect on metal extraction efficiency.[50] selected for FA ChCl and oxalic acid as in literature, 300 rpm
In Urea ChCl, zinc extraction reaches 90.1 � 1.1 % at a was found to be the optimum stirring speed.[52]
1/30 g/mL ratio, with conditions of 100 °C, 21 h and 400 rpm
stirring speed. Further, increasing the volume of solution only
yields a marginal difference in extraction efficiency. Thus, a 1/30 3.5. Kinetic study
solid-liquid ratio is considered the optimum condition for
achieving maximum zinc extraction in Urea ChCl, as shown in The dissolution of metals from PCBs to organic acid-choline
figure 6c. In the case of oxalic acid, after a 1/20 g/mL ratio, there chloride DES is a solid-liquid reaction. Liquid goes through the
was no significant difference in tin extraction as depicted in solid with an effective diffusivity while solid was supposed to
figure 7d; Wang et al. conducted selective extraction of tin from homogeneously diffuse all over the material. In the present
zinc leaching residue using oxalic acid-sulfuric acid mixture and work, the reaction for metal extraction begins at the particle‘s
concluded that a lower S/L ratio is beneficial for efficient mass outer surface, which causes the reaction zone to contract as the
diffusion from solid to liquid.[51] reaction time increases. Due to this, the reaction zone moves
A high S/L ratio is required to increase process yield; inward, and the extracted metals stay in the aqueous solution.
however, it reduces metal extraction efficiency. Hence, there There are two major assumptions of the shrinking core model.

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Figure 6. Effect of Temperature (21 h; 1/20 g/mL; 400 rpm) (a); Time (100 °C; 1/20 g/mL; 400 rpm) (b); S/L Ratio (100 °C; 21 h; 400 rpm) (c); and stirring speed
(d) in metal extraction from TPCB in Urea ChCl.

The first assumption is that the reacting solid particle has a Organic acids form complexes with the metal ions, and the
spherical shape. This simplifies the mathematical description of resulting complexes are soluble in water, which facilitates their
the reaction because it allows for a uniform reaction rate at the separation from the solid material and leaves an inert solid
particle‘s surface. Particles can have more complex shapes, but residue without metals. The leaching process was analyzed
the spherical symmetry assumption is often used as an using a kinetics model based on the shrinking core concept.
approximation.[53] The second assumption is that the rate of the This model was employed due to the observation that the solid
chemical reaction at the surface of the solid particle is surface underwent shrinkage during the reaction, resulting in
uniform.[53] As copper is a bulk metal, copper dissolution kinetics the inward movement of the reaction zone and the manifes-
in FA ChCl DESs are discussed in detail in this study. Metal tation of a shrinking core phenomenon. Within the leaching
leaching has three vital steps, which involve (1) Diffusion of system, the step that exhibits the lowest rate is referred to as
reactants: molecules/ions (H +, FA, Urea, Cl , etc.) into the solid the rate-determining phase. The extraction process is diffusion
surface of PCBs (Cu, Fe, Zn, Ni, Sn) and adsorbed (2) Interfacial controlled or chemical reaction controlled is denoted by
surface chemical reaction by complexation reaction. (3) Diffu- equations (7–8)
sion of products: dissociation of the metal complex (Zn Urea,
Cu Choline chloride, etc.) and diffusion in DES solution. As 1-ð2=3Þ c ð1 cÞ2=3 ¼ kt ðdiffusion controlledÞ (7)
copper content in TPCBs is maximum, hence kinetics of copper
extraction in FA ChCl is discussed in detail. The process of 1-ð1 cÞ1=3 ¼ kt ðinterfacial chemical reaction controlledÞ (8)
metal extraction in organic acids involves the principle of
complexation, where the organic acid forms a complex with the Here, χ is the leaching efficiency of metals (Cu), %; k is the
metal ions, which makes them more soluble in the aqueous rate constant, h 1; t is time in h. Figure 8 (a–d) represents the
solution. It can be implied from the abovementioned discussion experimental data fitting in the equations (7–8). It is evident
that extraction of metals depends on mass transfer and from Figure 8 (b and c) that the extraction of copper in FA ChCl
chemical reaction on the surface. fits well with equation 7 and is a diffusion-controlled phenom-

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Figure 7. Effect of Molar concentration of oxalic acid (100 °C; 1 h; 1/30 g/mL) (a); Reaction time (100 °C, 1/20 g/mL) (b); Reaction temperature (1 h; 1/20 g/mL)
(c); S/L Ratio (100 °C; 1 h) (d). stirring speed is constant = 300 rpm in oxalic acid.

Ea
enon. The rate constants are determined in the temperature ln k ¼ ln A (9)
RT
range of 20–100 °C using linear regression. The k value and R2
are represented in Table 3, through which it can be concluded
that R2 of diffusion-controlled model 1 2=3c ð1 cÞ2=3 is Here, k is the reaction rate constant (h 1), A is the frequency
near to 1. Hence, in the extraction of Cu from PCBs to FA ChCl, factor, Ea is apparent activation energy (kJ/mol), R is gas
diffusion is a rate-determining step. The activation energy (Ea) constant 8.3145 (J/K-mol), and T is reaction temperature in K.
for Cu extraction was regulated by a linearised form of the The Ea value of Cu extraction in FA ChCl comes to 16.21 kJ/mol
Arrhenius equation (9) and portrayed in Figure 8d. in the diffusion-controlled model. It has been thoroughly
reported in the literature that Ea less than 25 kJ/mol suggests a
diffusion-controlled region, while greater than 30 kJ/mol sug-
gests a chemical reaction-controlled process.[54] The shrinking
core model was used by Huang et al. to fit the copper leaching
Table 3. Kinetic parameters of interfacial chemical reaction controlled and
diffusion-controlled models at different reaction temperatures. data (in ionic liquids), the reaction was diffusion-controlled and
Temperature 1-(1-χ)1/3 1 2=3c ð1 cÞ2=3
the apparent activation energy calculated was 25.36 kJ/mol.[19]
(°C) Topcu et al. evaluated activation energy for the dissolution of
k(h 1) R2 k(h 1) R2 copper, 8.86 kJ/mol and zinc, 14.48 kJ/mol from copper con-
20 0.01159 0.870 0.0029 0.958 verter slag to urea ChCl DESs.[54a] The activation energy of the
40 0.01209 0.916 0.00404 0.975 dissolution of copper in conventional acids is in the range of
60 0.01917 0.913 0.00848 0.988
11–55 kJ/mol quite higher than the activation energy of copper
extraction in DES.[55]
80 0.01840 0.951 0.00851 0.972
100 0.02481 0.922 0.01169 0.977

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Figure 8. Plots of extraction of Cu with respect to time and temperature (a); [1-(1-χ)1/3] vs. time at different temperatures and time (b); [1–2/3χ-(1-χ)2/3] s time at
different temperatures and time (c); Arrhenius plot for extraction of Cu in both models (d).

3.6. Mechanism of metal leaching supply protons and ligands to dissolve metals by acidification
and complexation reactions. Organic acid dissociates to protons
DESs have an interaction of hydrogen bond donors and (H +) and promotes dissolution. Interactions of metal with
acceptors and form hydrogen bonds, hence conferring high organic acids have been discussed in the literature.[58] Never-
dissolution properties. Abbott et al. discussed the chemistry of theless, there is still a lack of literature and understanding of
metal complexes with carboxylic acid-choline chloride DESs.[34] metal dissolution in organic acid based DESs.
There was a correlation between the solubility of metal oxide in
malonic acid-choline chloride and HCl. It was concluded that RCOOH þ H2 O Ð RCOO þ H3 Oþ (10)
the proton acts as an oxygen acceptor, forming metal
complexes. Detailed analysis of metal complexes revealed the Proton reduction leads to hydrogen and oxidizes metal.
formation of MClx in most choline chloride DESs.[34] Figure S3
reveals the map of the electrostatic potential calculation of 2H3 Oþ þ 2e ! H2 þ 2H2 O (11)
choline chloride, which reveals that chloride ions have the most
negative electrostatic potential values at an iso value of 0.02. Complexation reaction occurs alike formate in formic acid
The electrostatic potential is an important descriptor to under- and acetate in acetic acid to form stable complex as denoted
stand the reactive behaviour of molecules such as to determine by equation (12)
nucleophilic and electrophilic sites in molecules. In choline
chloride surface analysis chloride has the most negative HCOO þ MðH3 Oþ Þ ! RCOOM þ H2 O (12)
potential, hence more prone to electrophilic attack.[56] Hartley
et al. investigated the metal solubility in diols-based DESs Another reason for an increase in metal extraction with the
where metal speciation has proven to be a controlling factor addition of H2O2 is the formation of peroxy carboxylic acid; in
with the dominance of anion of the solvent.[57] Organic acids

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the case of formic acid, performic acid is formed as shown in 3.7. Separation of metals from leached solution
(13):[59]
Cementation is an electrochemical phenomenon characterized
HCOOH þ H2 O2 ! HCOOOH þ H2 O (13) by the displacement of a metal ion from solution by more
reactive metals (sacrificial). Cementation has the advantage of
Performic acid has high oxidizing power; hence it oxidizes easy operation, cost and high metal recovery and is a common
metal (14). technique used in metallurgy and hydrometallurgy for metal
recovery from leached solution. The cementation process is
HCOOOH þ M þ 2H ! HCOOH þ H2 O þ M2þ (14) classified as a galvanic process due to its lack of dependence on
an external current source. The phenomenon of metal ion
Urea ChCl DES form metal complex anion [MxClO(urea) ] reduction in a solution to its metallic form is attributed to the
from its metallic oxides or sulphate forms. Urea act as a ligand disparity in standard electrode potential between the two
and forms metal complexes anions. metals involved. The equation of the typical cementation
process is:
Zn2þ þ HOC2 NðCH3 Þ3Cl þ NH2 CONH2 !
(15)
ZnOClðNH2 CONH2 Þ2 aMbþ þ bN0 ! bNaþ þ aM0 (16)

The energy difference between the Highest Occupied Here, Mb + is the target metal, M0 is the cemented target
Molecular Orbitals (HOMO) and the Lowest Unoccupied Molec- metal in metallic form, N0 is a sacrificial metal used for
ular Orbital (LUMO) of a complex is a crucial factor that helps in cementation while Na + is a sacrificial metal used for cementa-
understanding the electron properties and reactivity. High and tion. Table S3. illustrates the standard electrode potential of
low energy difference has a significant implication for the metals. The disparity in standard reduction potentials between
complex’s behaviour. The energy difference of HOMO LUMO of copper (Cu) at 0.34 V and zinc (Zn) at 0.76 V instigates the
metal complexes is illustrated in Table S5. Formic acid inter- reduction of copper ions into their elemental form. The
action with copper has the lowest energy gap, which reveals its standard electrode potentials of copper and zinc are illustrated
higher reactivity with the complex as compared to other by
hydrogen bond donors. However, the low energy gap of oxalic
acid interaction with copper reveals its tendency to form Cu ðsÞ ! Cu2þ ðaqÞ þ 2e -0:34 (17)
copper oxalate. Figure S4 shows the interaction of the Cu4
cluster with different electron-deficient sites of components of Zn2þ ðaqÞ þ 2e ¼ Zn ðsÞ-0:76 (18)
DES.
Eh ph diagram, commonly known as the Pourbaix diagram, As discussed in our previous paper by Jadhao et al. (2023),
aids in understanding the behavior of individual metals in the cementation of copper is thermodynamically feasible.[52] An
aqueous solutions. Materials project an open-source platform, optimized metal leached solution of FA ChCl was used for this
was utilized to plot Eh ph diagram of Fe, Cu, Ni, Zn and Sn as process. At room temperature, metallic zinc powder was added
shown in Figure S2 (a–e).[60] Fe2 +, Cu2 +, Zn2 +, Ni2 + and Sn2 + are to the leached FA ChCl solution. The cementation efficiency of
the major metal species present in solution. Standard electrode copper was observed to be 99.8 � 0.8 %. However, XRD of
potential of (metals and H2O2) and pH of all DES are tabulated recovered powder reveals the presence of copper formate
in Tables S2 and S3, respectively. Electrode potential differences along metallic copper. Figure 9 depicts the XRD of recovered
of Fe, Cu, Zn, Ni, Sn and H2O2 are 1.336 V, 1.436 V, 2.536 V, powder after cementation along with FESEM and cementation
2.026 V and 1.63 V, respectively. Considering the Eh ph dia- efficiency.
gram of all metals, Fe2 +, Cu2 +, Zn2 +, Ni2 + and Sn2 + species exist
in the acidic pH range above 0.5 V, 0.4 V, 0.8 V, 0.2 V and
0.5 V, respectively. Metal species form metal complexes as 3.8. Proposed integrated process
denoted by equation (12–13) resulting in metal extraction. For
tin extraction in oxalic acid, it was presumed to form tin oxalate. The cumulative multistage leaching process was employed for
Wang et al. discussed the reduction of Sn (IV) to Sn (II) by E ph the selective extraction of metals from PCBs taking 5 g of TPCBs.
diagram.[51] Sn4 + has a stable region in the highly acidic Initially, 1 M Oxalic acid was used to leach Sn from the PCB for
environment; however, the required pH range for the stable 1 h, in 1/20 g/mL ratio at 80 °C, 300 rpm. ICP-MS analysis of
region of Sn2 + is below pH 3. Compared to sulphuric acid and leachate revealed that 93.5 � 0.4 % of Sn was leached in 1 M
hydrogen peroxide, E (CO2/H2C2O4) reduction potential is oxalic acid solution. Alongside, iron extraction was 34.7 � 1.2 %
0.59 V, while E(Sn4 + /Sn2 +) is 0.15; hence thermodynamically and 10–8 % of Cu in the solution. Further, the solid residue was
oxalic acid can reduce Sn (IV) to Sn (II), thereby has higher washed and treated with Urea ChCl for 16 h, 1/30 g/mL ratio,
extraction. 80 °C, 400 rpm to extract 90.3 � 1.3 % of zinc. The solid residue
was washed and dried and treated with FA ChCl DES to extract
90 � 0.9 % Cu, 89 � 0.2 % Fe, and 88 � 1.9 % Ni in a leachate
solution. Figure 10 depicts the proposed process flowsheet.

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Figure 9. XRD of recovered powder after cementation from FA ChCl leached solution (a). FESEM of recovered salt along with visual representation (b).
Cementation efficiency of copper from FA ChCl leached solution using zinc dust (c).

Figure 10. Flowsheet of proposed work for selective extraction of metals from PCBs.

There are various aspects in metal extraction from DES suggested by a shrinking core model-based kinetic investiga-
which is still not much explored. Exploration of electrowinning tion of copper extraction in FA ChCl. The apparent activation
integrated with DES metal extraction can be done. The energy of copper was 16.21 kJ/mol. Metal extraction mechanism
integrated process environmental impact could be evaluated in DES is a two-step process with a major complexation reaction
using LCA studies. Alongside, scaleup study to set up greener of metals with ligands of hydrogen bond donor or acceptor
technology alternative to conventional technology ought to be anion, which is explained by Eh ph diagram of metals. This
explored. study provided a detailed investigation of metal extraction in
green solvents, which paved a new approach for the selective
extraction of metals from PCBs. Further analysis of the
4. Conclusions mechanism of metal extraction in the green solvent must be
studied in detail, correlating theoretical calculations with
In this work, DESs (FA ChCl, Urea ChCl) and organic acid have experimental results to further understand at a molecular scale.
been tested as potential leaching agents for the selective Moreover, detailed research on metal speciation in DES systems
extraction of metals from PCBs. Leaching experiments states is required to fully comprehend the mechanism.
that FA ChCl showed high copper, iron, and nickel solubility in
the range of 105 ppm while negligible solubility of Zn. However,
Urea ChCl was observed to be selective in the solubility of Zn. Abbreviations
Metal leaching experiments in FA ChCl with H2O2 uncover that
extraction of Cu, Fe, Ni, and Zn is greater than 90 % at B3LYP Beck’s three parameter functional Lee Yang Parr
optimized conditions (100 °C, 1/30 g/mL, 16 h, 300 rpm). Zn ChCl Choline Chloride
extraction from TPCBs was observed to be 90.4 � 2.9 % at DESs Deep Eutectic Solvents
(100 °C, 1/20 g/mL, 21 h, 400 rpm). 1 M oxalic acid selectively DFT Density Functional Theory
extracted 92.3 � 2.09 % Sn from TPCBs under optimal conditions EG Ethylene Glycol
(1 h, 80 °C, 1/20 g/mL). The diffusion-controlled reaction is EG ChCl Ethylene Glycol-Choline chloride

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RESEARCH ARTICLE
S. Mishra, T. N. Hunter, K. K. Pant*, D.
Harbottle*
1 – 16
Green Deep Eutectic Solvents (DESs)
for Sustainable Metal Recovery from
Thermally Treated PCBs: A Greener
Alternative to Conventional Methods

Green choline chloride-based deep chloride, while ~90 % zinc extraction

eutectic solvents are potential in Urea-choline chloride. An inte-
leaching agents for selective transition grated multistage leaching process is
metal extraction from e-waste. ~90 % projected for the selective extraction
extraction of copper, iron, and nickel of metals from mobile printed circuit
is observed in Formic acid-choline boards.