Hydrometallurgy 171 (2017) 128–141

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Hydrometallurgical processes for recovery of valuable and critical metals MARK

from spent car NiMH batteries optimized in a pilot plant scale
Martina Petranikovaa,⁎, Irena Herdzik-Konieckoa,b, Britt-Marie Steenaria, Christian Ekberga
a
Chalmers University of Technology, Department of Chemistry and Chemical Engineering, Nuclear Chemistry and Industrial Materials Recycling, Gothenburg, SE -412 96,
Sweden
b
Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: With the increasing use of hybrid and electrical cars comes an increasing demand for rare earth elements (RREs)
NiMH batteries needed for the production of car batteries. Currently NiMH batteries contain approximately 3 kg of REEs, 11 kg
HEVs of nickel and 1.5 kg of cobalt. Leaching with HCl and solvent extraction using Cyanex 923 have been applied to
Hydrometallurgy recover metals from this waste. Process has been developed for NiMH car batteries, which can be dismantled
Leaching
manually or mechanically. Depending on the way of dismantling, three different materials can be obtained
Solvent extraction
(cathode plates, anode plates or mixed material). Developed technologies have been designed to recover metals
Recovery
either from cathodic and anodic material or from mixed (cathodic and anodic) material. Hydrochloric acid (8 M)
is used as a leaching agent at a temperature of 30 °C. The extraction system consists of the solvating extractant
trialkylphosphine oxide mixture (Cyanex 923) and tributyl phosphate (TBP) diluted in kerosene. A pre-main
extraction (8% Cyanex 923, 10% TBP, 82% kerosene) is used to remove Fe and Zn from cathode and mixed
material leachates. Zn and Fe are extracted in four extraction stages followed by three scrubbing stages to
remove co-extracted metal ions and four stripping stages to remove extracted Zn and Fe (99.9%). Aluminium and
REEs are separated from Ni, K, and Mg in three main extraction stages (70% Cyanex 923, 10% TBP, 10%
kerosene, 10% 1-Decanol). High purity Ni (> 99.9%) in a raffinate is obtained after main extraction. Loaded
organic phase is stripped with mixture of 0.9 M NaNO3 and 0.1MHNO3 to remove co-extracted Co, Mn and Ni.
Aluminium and REEs are recovered by stripping step using 1 M HCl after previous scrubbing of organic phase
with 1 M NaNO3 to remove residual Co and Mn. To determine required parameters McCabe-Thiele diagrams
were constructed. Obtained parameters were tested in a counter-current system using pilot plant scale mixer-
settlers and all three processes were optimized.

1. Introduction especially at high voltages) (Pollet et al., 2012).

Many electronic products are powered by rechargeable batteries.
The main use of NiMH batteries is in rechargeable AA, AAA batteries,
power tools and hybrid electric vehicles (HEVs) (USEPA, 2012; Young
et al., 2013). The major advantage from a manufacturing point of view
is the safety of NiMH compared to Li-ion batteries. Furthermore, NiMH
batteries are preferred in industrial and consumer applications due to
their design flexibility (e.g. ranging from 30 mAh to 250 Ah), environ-
mental acceptability, low maintenance, high power and energy den-
sities, cost and most importantly safety (in charge and discharge modes,
In general 7% of a typical NiMH battery is made up of rare earth
elements (REEs); this equates to around 1 g of REEs per AAA battery,
60 g for a household power tool and 2 kg for a hybrid electric vehicle
battery (USEPA, 2012). In 2008, 12,100 t of REEs was used for battery
production, of which lanthanum oxide accounted for 50%, cerium
oxide 33%, neodymium oxide 10% and praseodymium and samarium
oxides 3.3% each (Goonan, 2011). REEs are used as the active material
in the negative electrode of the batteries and are present as AB5
(LaCePrNdNiCoMnAl), A2B7 (LaCePrNdNiCoMnAl plus Mg), or disor-
dered AB2 (VTiZr-NiCrCoMnAlSn) type, where the “ABx” designation

Abbreviations: wt%, percentage weight total; D2EHPA, di-(2-ethylhexyl)phosphoric acid; E (in the flow-sheets), extraction step; HEHEHP 2, ethylhexyl-2-ethylhexyl-phosphonic acid;
HEV, hybrid electric vehicle; nd, `not detected; MS, mixer settlers; NiMH, nickel metal hydride; O:A, organic to aqueous ratio; REE, rare earth element (mixture of Ln, Y and Sc); REM, rare
earth metal (mixture of Ln); S (in the flow-sheets), stripping step; S:L, solid to liquid (ratio); TOA, tri-n-octylamine; TBP, tributyl phosphate; v/v, volume/volume; W (in the flow-sheets),
scrubbing step; w/v, weight/volume; Cyanex 923, extractant, mixture of trialkylphosphine oxides; Cyanex 272, extractant with active component: bis(2,4,4-trimethylpentyl)phosphinic
acid
⁎
Corresponding author.
E-mail address: martina.petranikova@chalmers.se (M. Petranikova).

http://dx.doi.org/10.1016/j.hydromet.2017.05.006
Received 5 October 2016; Received in revised form 27 February 2017; Accepted 8 May 2017
Available online 09 May 2017
0304-386X/ © 2017 Elsevier B.V. All rights reserved.
M. Petranikova et al. Hydrometallurgy 171 (2017) 128–141

refers to the ratio of the A type elements (LaCePrNd or TiZr) to that of Table 1
the B type elements (VNiCrCoMnAlSn). Starting from the LaNi5 type, La Optimal leaching conditions for black mass of NiMH batteries (Tunsu et al., 2015).
has been substituted by mischmetal. Mishmetal is a mixture of REEs
Reference Leaching conditions
such as Ce (50–55%), La (18–28%), Nd (12–18%), Pr (4–6%) and other
REEs in small quantities, as well as impurities (Ruetschi et al., 1995). Leaching agent Temperature (°C) Time (h) S:L ratio
The positive electrode of the battery is nickel oxyhydroxide
(Pietrelli et al., 2002) 2 M H2SO4 20 2 1:10
(NiOOH) powder coated on a porous nickel substrate. The cathode
(Nan et al., 2006)a 3 M H2SO4, 70 5 1:15
and anode are separated by an inert separator made of nylon (poly- H2O2
amide) or polypropylene while the electrolyte is made of potassium (Rodrigues and 8% H2SO4b 30 1 1:10
hydroxide or sodium hydroxide solution. Mansur, 2010) 8% H2SO4c 30 1 1:10
With the increasing use of HEVs follows a higher demand for more (Innocenzi and 2 M H2SO4b 80 3 1:6.66
Vegliò, 2012) 1 M H2SO4c 25 1 1:6.66
effective recycling methods. Spent portable NiMH batteries have been
(Zhang et al., 1998) 3 M HCl 95 3 1:9
pyrometallurgically recycled for the Ni and Co content. REEs have not (Yang et al., 2014) 20% HCl 70 1.66 1:10
been recovered from the slag, where their concentration is much lower
a
than in the starting material (Binnemans et al., 2013). In 2010 the Mixed black mass from NiMH and Li-ion batteries.
European Commission declared the REEs to have the highest supply risk
b
Two-step leaching process; first leaching step.
c
Two-step leaching process; second leaching step.
among 41 different raw materials, thus the possibility to develop
methods for recovery of metal ions from different secondary sources
Table 2
of REEs became a high interested for the research activities. Umicore
Conditions applied for metal ion separation.
and Rhodia have developed a hydrometallurgical process for the
recovery of REEs slag after pyrometallurgical treatment of spent NiMH Reference From Mean of Reagent pH Separated
batteries (Binnemans et al., 2013). Because the hydrometallurgy is media separation metal ions
considered more suitable for the recovery of high purity products from
(Mantuano H2SO4 Solvent 0.3 M pH 3 Zn, Al
complex streams than pyrometallurgy, the search has shifted towards et al., extraction Cyanex pH 5 Co, Mn
the development of such hydrometallurgical methods to recover metals 2006) 272 in the raffinate Ni
directly from the battery waste. There are only a few studies, in which (Provazi H2SO4 Solvent 0.6 M pH 1 Zn, Ti
the developed technologies were tested in a counter-current extraction, et al., extraction Cyanex pH 3 Ni, Cd, La
2011) 272 pH 6 Fe, Ce
even though, for the industrial applications it is necessary to test and pH 7 Mn, Cu, Co,
optimize the proposed steps in the same or similar equipment as the one Cr, Pb
used in the industry. One of the main differences between pyrometal- (Nan et al., H2SO4 Precipitation NaOH, pH 1.6 REEs
lurgy and hydrometallurgy is, that there are many streams involved, 2006) Na2CO3
Solvent 10 wt% pH 1.5–1.7 Cu
which can be re-use within the process (e.g. organic solvents can be
extraction Acorga
regenerated and used again), but all those possibilities have to be tested M5640
and optimized before building a scaling up such technologies. In this 1M pH 5.1 Co
article, one such process was optimized and tested in larger equipment. Cyanex pH 6.3 Ni
Some streams were re-used again and the effects of such steps were 272
(Zhang HCl Solvent 25% pH 2 REEs Al,
observed and included into the optimization.
et al., extraction D2EHPA Fe, Zn
1998) in the raffinate Co, Ni
2. Background (Granata H2SO4 Solvent 2M pH 4 Mn
et al., extraction D2EHPA
2012) Cyanex pH 5.5 Co
Several hydrometallurgical processes have been developed to
272
recycle metal ions from spent portable NiMH batteries in a laboratory
scale. Inorganic acids such as hydrochloric (Zhang et al., 1998)
sulphuric (Pietrelli et al., 2005; Pietrelli et al., 2002) or sulphuric with was carried out to determine effectiveness of the selective precipitation
addition of hydrogen peroxide (Mantuano et al., 2006; Nan et al., 2006) and solvent extraction. It was concluded that precipitation was not
were used for the leaching of the black mass from the batteries. The sufficient to obtain high purity products due to metal co-precipitation.
addition of citric acid as a reducing agent at 80 °C was used in the In another work the combination of precipitation and solvent extraction
leaching step with sulphuric acid (Innocenzi and Veglio, 2012; was also used (Nan et al., 2006). REEs were precipitated adjusting pH to
Innocenzi and Vegliò, 2012). It was concluded that the addition of 1.6. Extracted Cu was recovered by 10 wt% Acorga M5640 diluted in
hydrogen peroxide or citric acid to sulphuric acid did not have a kerosene. Subsequently Co and Ni were recovered by 1 M Cyanex 272.
significant effect on the leaching of REEs (Innocenzi and Vegliò, 2012; The REEs, Al, Fe and Zn were separated from Co and Ni in a HCl
Rodrigues and Mansur, 2010). The low solubility of REE sulphates at leachate at pH 2 using 25% D2EHPA in kerosene (Zhang et al., 1998).
higher temperatures (80–95 °C) was utilized to recover REEs as The loaded organic phase was scrubbed with 0.3 M HCl to remove the
precipitates (Li et al., 2009; Wu et al., 2009). There are optimal co-extracted Co, prior to stripping the REEs with 2 M HCl and their
leaching conditions obtained by different research groups shown in subsequent precipitation with oxalic acid and calcination. Mixed REE
Table 1. oxide containing 53.3% La2O3, 3.4% CeO2, 10.5% Pr6O11, 32.1%
Depending on the general composition of batteries, the presence of Nd2O3 and 0.8% Sm2O3 was obtained. The total recovery of REEs
the metals such as Al, Fe, Ni, Co, REEs (Ce, La, Nd, Pr), Mn, Zn etc., can reached around 98%.
be expected in the leachates. To recover and separate those metal ions, Only a few processes have been tested in the counter-current way. In
solvent extraction and precipitation were applied in several studies a study by Wu and co-workers, (Wu et al., 2009) REEs were first
(Table 2). recovered as precipitate during the leaching with sulphuric acid. To
Mostly acidic extractants such as Cyanex 272, D2EHPA, PC-88A, separate residual REEs from other metal ions, 20% PC-88A was applied
Acorga M5640 but also solvating extractants such as Cyanex 923 and and mixer-settlers equipment was used. In the counter current process,
TBP were used. Precipitation was applied in the metal ion separation, REEs were recovered at pH 3.5 using 8 extraction stages. Co and Ni
but solvent extraction was preferred due to possibilities to obtain were scrubbed out using 0.2 M H2SO4. Zn and Mn were removed by
products with higher purity. A comparison study (Provazi et al., 2011)

129
M. Petranikova et al.
Fig. 1. Flow-chart of proposed technology by Larsson et al., 2012.
stripping the loaded organic phase with 2 M HCl, but 17 stripping
stages were needed to remove those impurities. REEs were stripped out
using 4 M HCl in 6 stages.
Another process developed in our research group, used mixture of
solvating extractant Cyanex 923 and TBP to recover and separate metal
(Al, Ce, Co, Fe, K, La, Mg, Mn, Nd, Ni, Pr, Y, Zn) from the hydrochloric
media (Larsson et al., 2012; Larsson et al., 2013a). Process was partially
tested in the mixer-settler equipment. Research studied Toyota Prius
battery. The battery was manually dismantled. The preliminary process
developed by Larsson, involved leaching of battery cathodes, anodes
and mixed electrodes (cathodes and anodes) with 8 M HCl at 30 °C and
pH 1 (the process flow chart is shown in the Fig. 1). Metal ions recovery
consisted of a pre-main extraction for Fe and Zn removal and a main
extraction for the separation of metal ions into three groups: I. Ni, K,
Mg; II. Co and Mn; III. Al and REEs. The main extraction was based on
the extraction using 70% Cyanex 923, 10% TBP, 10% 1-Decanol and
10% kerosene to extract all metals except Ni, K, Na and Mg. The loaded
organic phase was then washed with water to remove co-extracted Ni. A
stripping solution containing 0.1 M HNO3 and 0.9 M NaNO3 was used
to strip out Co and Mn. Additional scrubbing by 1 M NaNO3 was used to
remove the rest of Co and Mn from the organic phase. REEs and Al were
stripped out by 1 M HCl.
The present paper describes the optimization of the process
proposed by Larsson and co-workers (Larsson et al., 2013b) and its
testing in a larger pilot scale plant. This was needed since the
parameters of all steps were not determined in the original work. In
addition some of the proposed steps were not performed in a counter-
current process and the technology was only tested in a small mixer-
settler equipment (120 ml/unit). Some of the suggested parameters
130
Hydrometallurgy 171 (2017) 128–141
determined by bench scale testing, were not suitable for performance in
mixer-settlers equipment (e.g. very high O:A ratio such as 100:1, etc.).
Hence this study was focused on determining the missing parameters,
optimizing particular steps in semi-large mixer-settlers (120 ml/unit)
and scaling up complete technologies in larger mixer-settlers (500 ml/
unit).
The technology was tested and further developed in the mixer-
settlers equipment for the counter-current process. Parameters pro-
posed by Larsson et al. are given in Table 3.
As it is shown in the Table 3, the parameters for a stripping with 5 M
HNO3 were not set for the cathodic and mixed material in the pre-main
extraction process. Parameters of the water scrubbing step are not
applicable in the counter current process and this step had to be
evaluated. Parameters for two steps (scrubbing with 1 M NaNO3 and
stripping with HCl), were not optimized by previous research, and those
steps were tested only in the batch cross-flow way. To fully optimize all
three processes further investigation was performed.
The main goals of the optimization were:
I. To determine the parameters for the particular steps (stripping of Fe
and Zn from the loaded organic phase in the pre-main extraction,
scrubbing of Co and Mn from the loaded organic phase by 1 M
NaNO3 in the main extraction and stripping of Al and REEs with 1 M
HCl from the loaded organic phase also in the main extraction),
which were not defined by Larsson et al.
II. To test the optimized steps in the larger mixer-settler equipment.
To fulfill the first goal, McCabe-Thiele diagrams were constructed
and mixer-settlers with the volume 120/unit were used. Mixer-settlers
M. Petranikova et al.
Table 3
Parameters proposed by Larsson et al. (Larsson et al., 2013b).
Process Steps
Pre-main extraction Extraction
Scrubbing with 3 M HCl
Stripping with 5 M HNO3
Main extraction Extraction
Water scrubbing
Stripping with mixture 0.1 M HNO3 and 0.9 M NaNO3
Scrubbing with 1 M NaNO3
Stripping with 1MHCl
with volume 500 ml/unit were used to achieve the second goal of this
study. Mixer-settlers with volume 120 ml/unit were the same as used
by Larsson. Mixer-settlers with volume 500 ml/unit are the same type,
but with larger capacity. The outcome of the result is linear in
comparisons to smaller mixer-settlers.
3. Experimental
3.1. Dismantling of the battery and pre-treatment
A discharged Panasonic battery (the 1st generation) for Toyota Prius
HEV was manually dismantled. After dismantling, battery modules
were opened and electrode material was removed. Anodes and cathodes
were manually separated. For the mixed sample (cathodes and anodes)
no separation was needed. The electrodes were washed with ultra-pure
water (MilliQ Millipore, > 18 MΩ/cm) to remove the electrolyte at
solid to liquid ratio 1:1. Anode active material is not bounded to the
steel grids and can be easily separated. Hence the steel grids were
removed from the material after the washing with water. The washed
material (black mass) was filtered and used for the leaching experi-
ments. The cathodic material was leached directly after the disman-
tling, i.e. the active material was leached together with the nickel grid.
Mixed material and anodic material were leached without the steel
grids.
3.2. Material characterization
Metal content of the cathodic and anodic material was determined
by dissolution of the samples of cathodic and anodic active material
(0.2 g) in aqua regia (50 ml) prepared by mixing of HCl (37%, puriss,
Merck) and HNO3 (66%, puriss, Merck) in ratio 3:1. Dissolution was
performed at 80 °C. Stirring with magnetic stirrer was used. Triplicate
leaching experiments were made for both types of electrode material
(cathodic and anodic). After the dissolution samples were diluted by
0.5 M nitric acid solution and the metal content was determined using
Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES)
(iCAP 6500, Thermo Fisher). The phase composition of cathodic and
anodic active material was determined by powder X-ray diffraction
analysis (XRD) using D2 Phaser Bruker instrument using Cu Kα
radiation. The conditions for data collection were continuous scanning
using a detector covering over a 2Θ angular range from 10° to 90° with
a step size of 0.04 and a wavelength of 1.541874 Å (Cu characteristic
radiation).
3.3. Leaching process
Leaching experiments were performed in a glass reactors (Lasilaite).
Thermostat (Julabo F12) was used to sustain the required temperature.
Leaching temperature was 30 ± 0.02 °C. Solid to liqiud ratio was used
based on previous research (Larsson et al., 2013a). 8 M HCl (37%,
Hydrometallurgy 171 (2017) 128–141
Cathodic material Mixed material Anodic material
O:A ratio Number of stages O:A ratio Number of stages O:A ratio Number of stages
1:2 4 1:2 4
2:1 3 2:1 3
Not defined.
2:1 3 2.5:1 3 3:1 3
25:1 1 25:1 1 25:1 1
50:1 1 50:1 1 50:1 1
100:1 1 100:1 1 100:1 1
1:1 5 1:1 5 1:1 5
Not defined.
Merck) was used as a leaching agent. Depending on the type of the
material, the amount of acid needed was 3750 ± 15 ml for 1 kg of
anodic material, 1960 ± 5 ml for 1 kg of cathodic material and
2700 ± 10 ml for 1 kg of mixed material. Solid sample was added
into the leaching media in smaller amounts at the time (2 g per minute).
The volume of the leaching media was 95% of the calculated volume
needed for the reaction. A programmable titration device (718 Titrino,
Metrohm) was used to control and adjust pH.
In the previous research (Larsson et al., 2013b) leaching was
performed in an inert atmosphere of N2.To simplify the leaching
process and to improve the recovery of the Fe in the pre-main
extraction leaching batch experiments were here carried out at the
present of oxygen in the atmosphere in which Fe should oxidize from
Fe2 + to Fe3 + (Cyanex 923 extracts preferably Fe3 +). The oxidizing
conditions could lead to dissolution of the nickel grid from cathodic
material. Hence the batch leaching experiments of cathodic material
were carried out in the presence of the air to determine the effect of the
oxidizing conditions on a nickel grid dissolution. Leaching experiments
were carried out using solid to liquid ratio 1:1.96 at temperature 30 °C.
To not affect the solid to liquid ratio, separate experiments for each
time interval were performed using the same conditions. The experi-
ments were stopped after particular time and samples were taken. The
leaching time was 0.5, 1, 2, 3, 4, 5, 10, 20, 30 and 60 min. All
experiments were done in triplicates. After leaching, solid to liquid
separation was performed to separate leachate from the solid residue
using a vacuum filtration system (Lafil 400-LF30/SMI-LabHut Ltd).
3.4. Solvent extraction process
A mixture of trialkyl-phosphine oxides: 14% trioctylphosphine
oxide, 42% dioctylmonohexylphosphine oxide, 31% dihexylmonooctyl-
phosphine oxide and 8% trihexylphosphine oxide commercially known
as Cyanex 923 (Cytec Inc.) with purity 93% and Tributyl phosphate
(Sigma Aldrich) with a purity 96% were used. A counter-current
process was tested using mixer-settler equipment described in the
Section 3.5.
Batch experiments were carried out to get data for the construction
of McCabe-Thiele diagrams for the optimization of the scrubbing and
stripping steps. The experiments were performed by varying O:A ratio,
which was 0.05, 0.1, 0.25, 0.5, 0.75, 1, 2, 3, 5 and 10. Organic
respectively aqueous samples were mixed in glass tubes using a shaking
machine (IKA - Vibrax). The contacting time was 5 min. Aqueous
samples were diluted and analyzed by ICP-OES and the extraction
yields were calculated by mass balance.
3.5. Pilot plant equipment characterization and capacity
Leaching experiments were performed in 2 and 5 L glass reactors
(Lasilaite) with double walls to sustain the required temperature. Water
circulation in the walls and water heating was provided by using
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M. Petranikova et al.
thermostat (Julabo F12). For the counter-current process of solvent
extraction, mixer-settlers units were used. The mixer-settler unit
consists of: (I) mixing camber, where organic phase and aqueous phase
are mixed using a motor stirrer, (II) settling chamber, where the phases
are separated by density difference and (III) aqueous outlet compart-
ment, from which the aqueous phase exits the unit (Liljenzin et al.,
1981). The aqueous and organic phases were pumped into the mixer-
settlers using electromagnetic pumps (Iwaki). Organic to aqueous ratio
was controlled mechanically by adjusting the level of the outcoming
aqueous phase using a screw. Flow rates of the organic and aqueous
phase were controlled by the setting of the income volumes pumped by
pumps. Mixer-settlers were connected to each other in a parallel way.
One unit per one stage. Particular steps (extraction, scrubbing and
stripping) were divided by separation unit. Mixer-settlers units, separa-
tion units and connection parts are all made of polymer - polyvinyli-
dene fluoride.
For the study, two sets of mixer-settlers with volume 120 ml/unit
(small pilot size) and 500 ml/unit (large pilot size) were used.
Equipment with smaller volume were used for the optimization, the
mixer-settlers with larger volume (500 ml/unit) were used for the
testing of the optimized process. The mixing speed was approximately
1000 rpm ensured by electric motors with a control system for rpm
(Mymeko).
4. Results and discussion
4.1. Material characterization
4.1.1. Material balance of the battery
The battery contained 38 battery modules. Each battery module
consisted of 6 battery cells. One battery cell contained 12 cathode plates
(+ separators) and 13 anode plates. The material balance of the battery
was following: 74.6 wt% battery modules, 19.8 wt% steel parts, 1.4 wt
% cables (and copper), 1.7 wt% plastic parts, 0.6 wt% printed circuit
boards, 0.5 wt% aluminium and 1.4 wt% other. The weight of the
battery was approximately 53 kg.
The weight of one battery module was 1040 g. The battery case is
made of on PPE (Poly Phenylene Ether)/PP (Polypropylene)/HSBBC
(Hydrogenated Styrene Butadiene Block Copolymer)/HSIBC
(Hydrogenated Styrene Isoprene Block Copolymer) Blend. The separa-
tor is made of Polypropylene-Polyolefine mixed sheet (Panasonic EV
Energy Co., 2003). The material balance of one battery module was as
follow: 26.8 wt% anodes, 21.2 wt% cathodes, 19.9 wt% steel compo-
nents, 4.1 wt% separator, 14 wt% casing, and 14 wt% electrolyte. Each
anode (3.79 ± 0.074 g) consisted of steel grid (0.88 ± 0.01 g) and
active material (2.90 ± 0.03 g). the cathodes (4.53 ± 0.02 g) con-
sisted of nickel mesh (1 ± 0.04 g) and active material
(3.52 ± 0.02 g). The separators (0.73 ± 0.03) are attached to each
cathode.
4.1.2. Characterization of the electrode materials
4.1.2.1. Phase composition of anodic and cathodic material. In general
mixtures of rare-earth element (REE) alloys, the so-called mischmetals,
designated as AB5 alloys, where A = La, Nd, Ce, or Pr and B = Ni, Co, Mn,
or Al are used as active material for anodes. (Santos et al., 2012). The XRD
analysis of the anode electrode material confirmed the active material is
based on AB5 alloy type La0.5Ce0.3Pr0.1Nd0.1Mn0.4Co0.75Ni3.55Al0.3
(Fig. 2a). The positive electrode (cathode) generally consists of a porous
nickel substrate that is impregnated with nickel hydroxide as the main
active material. The substrate acts as a mechanical support for the active
material as well as a current collector. The addition of small amounts of
Co, Ca, and Zn improves the capacity of the electrode (Santos et al., 2012).
The cathode material also contains Y. Addition of Y2O3 decreases the
storage corrosion rate. Yttrium is added as oxide either to the electrode or
to the electrolyte (Arnaud et al., 2005). XRD analysis of the cathode
material confirmed the presence of Ni(OH)2 and metallic Ni (Fig. 2b).
132
Hydrometallurgy 171 (2017) 128–141
4.1.2.2. Metal composition of anodic and cathodic material. The chemical
analysis confirmed that the majority of the cathodic sample is based on
Ni, Co and Mn. There are also Fe, Al, Mg, Y, and Zn present in a lower
concentration. Anodic material contains, except previously mentioned
metals, REEs originating from the misch-metal. The metal content of
cathodic and anodic material is given in the Table 4.
4.2. Leaching
4.2.1. Kinetic study of the cathodic material leaching
The leaching method in the previous research done by Larsson et al.
(Larsson et al., 2013a) was based on leaching of cathodic and mixed
material in the protective atmosphere of N2 to prevent the leaching of
the nickel grid. In this research, batch leaching experiments were
carried out in the presence of oxygen to test its effect on nickel grid
dissolution.
The kinetic study showed that the leaching efficiency of Ni
increased very slowly (Fig. 3). In the first 5 min approximately 22%
of Ni is leached. It can be explained by dissolution of the active material
based on Ni(OH)2. The further slow increase in the leaching efficiency
is due to nickel grid dissolution. The leaching kinetic of other present
metals is quick and equilibrium is reached for most of them in less than
30 min. Based on these results it can be concluded that the kinetic of the
nickel grid leaching is comparatively slow and thus the presence of
oxygen has no significant effect on the nickel grid dissolution from
cathodic and mixed material.
4.2.2. Large scale leaching
Based on the results presented above, large scale leaching of all
three materials was performed in the presence of air. Metal concentra-
tions in the leachates are shown in the Table 5.
The resulting solution from leaching of the cathodic material does
contain some traces of rare earth elements due to cross-contamination
during the dismantling and mechanical separation process.
4.3. Solvent extraction (optimization part)
Parameters for several steps of the technologies were not deter-
mined in the work of Larsson et al. (Larsson et al., 2013b). Stripping of
Fe and Zn in the pre-main extraction, scrubbing of Co and Mn with 1 M
NaNO3, and stripping of REEs and Al with 1 M HCl in the main
extraction were steps lacking the parameters required for the scaling
up. Hence in the following section results of bench scale tests performed
to obtain missing parameters are shown below and discussed. Para-
meters were determined using McCabe-Thiele plots. Extraction and
stripping isotherms for McCabe-Thiele diagrams were obtained per-
forming bench scale experiments described in Section 3.4. Acquired
results were tested in a semi large mixer-settler equipment (120 ml/
unit). Based on the results of counter-current tests, particular steps were
optimized.
4.3.1. Pre-main extraction: Stripping of Fe and Zn
Pre-main extraction developed to extract Fe and Zn from the
leachates. Parameters for a stripping were not determined in the
proposed technology. Loaded organic phase was prepared by the
preforming the extraction and scrubbing steps according to the original
technology (Larsson et al., 2013b) in mixer-settlers equipment with
volume 120 ml/unit. From the preceding studies, the extraction of Fe
(III) with Cyanex 923 (TRPO) when extracted from hydrochloric acid
solutions can be represented as (Saji et al., 1998):
Fe3+aq + 4CI−aq + 2TRPOorg < = > FeCI 4 ·2TRPOorg (1)
Zn2+ + 4Cl− + 2TRPO < = > ZnCl 4 . 2TRPOorg
aq aq (2)
Sample of loaded organic phase was then stripped at different O:A
ratio with 5 M HNO3 as it is described in the experimental part.
M. Petranikova et al. Hydrometallurgy 171 (2017) 128–141

Fig. 2. Anode (a) and cathode (b) powder XRD diffractogram.

Table 4 FeCI 4·2TRPOorg + H+aq + NO−3 < = > Fe3+aq + 4CI−aq + H+aq + NO−3 + 2TRPOorg
Metal content of cathodic and anodic material. (3)
Element Content [mg/g of material] / Element Content [mg/g of ZnCl 4 . 2TRPOorg + H+aq + NO−3 < = > Zn2+aq + 4Cl−aq + H+aq + NO−3 + 2TRPOorg (4)
type of material material] / type of material
The concentration of Fe in the loaded organic phases was 0.57 g/l
Cathode Anode Cathode Anode
material material material material
(mixed material) and 0.78 g/l (cathodic material). Concentration of Zn
was 1.2 g/l (mixed material) and 1.6 g/l (cathodic material).
Al 4.5 ± 0.3 19.0 ± 0.5 Mn 45.0 ± 0.7 6.0 ± 0.1 The construction of McCabe-Thiele diagrams for the stripping of Fe
Ce nd 54.0 ± 0.9 Na 0.5 ± 0.05 0.3 ± 0.01 and Zn from the loaded organic phase (Fig. 4 and Fig. 5) has shown that
Co 84.0 ± 0.3 53.0 ± 0.4 Nd nd 24.0 ± 0.6
Fe 29.0 ± 0.4 1.3 ± 0.02 Ni 638.0 ± 0.7 554.0 ± 2
six stripping stages are needed to strip out Fe from the loaded organic
K 184.0 ± 0.5 1.5 ± 0.04 Pr nd 24.0 ± 0.6 phase when using O:A ratio 3:1 and three stripping stages are needed to
La nd 197.0 ± 0.2 Y 12.0 ± 0.7 8.0 ± 0.3 remove Zn from the organic phase.
Mg 8.0 ± 0.1 0.2 ± 0.01 Zn 8.8 ± 0.6 0.8 ± 0.01 Obtained data were tested in a counter current way. Loaded organic
phase was stripped with 5 M HNO3 using six stripping stages at O:A
nd – not detected
ratio 3:1 in mixer settlers with volume 120 ml/unit. By those tests, it
was confirmed that six stripping stages were sufficient to remove Fe
from the organic phase. Also Zn was removed after three stripping
stages at it was determined by McCabe-Thiele diagrams using 3:1 O:A
ratio.
Pre—main extraction for cathodic and mixed material was tested in
mixer-settlers (120 ml/unit) including optimized stripping step for Fe
and Zn. Flow-rates of the liquids were determined based on the
behavior of the system and in order to obtain required purities of the
streams. Data obtained by those test were utilized for scaling-up
described in the Section 4.4.

4.3.2. Main extraction: Scrubbing of Ni by water

Fig. 3. Leaching behavior of metals from the cathodic material at the presence of the air.
McCabe-Thiele diagrams were constructed for the stripping of Fe and
Zn originated from cathodic and mixed material. The mechanism of the
stripping step can be expressed according following equations:
Raffinate after pre-main extraction was used as a feed for main
extraction, where Al, Co, Mn and REEs are separated from Ni, Mg and
K. Approximately 97–99% of Ni is not extracted in the main extraction.
To remove entrapped Ni (Larsson et al., 2013b), a water washing step
was suggested. To consider this step, two issues had to be taken into
consideration. The first issue was that the proposed O:A ratio for this
step was 100:1, 50:1 and 25:1, but the mixer-settlers equipment does
not allow the use such a high O:A ratio due to its construction. The
second issue was that Cyanex 923 as a solvating extractants extracts
free mineral acids from the aqueous solutions (Alguacil and López,

Table 5
Metal concentrations in the leachates.

Element Content [mg/g of material] / type of material Element Content [mg/g of material] / type of material

Mixed Cathodic material Anodic material Mixed material Cathodic material Anodic material
material

Al 1.9 ± 0.2 0.3 ± 0.01 3.0 ± 0.1 Mn 6.0 ± 0.1 0.2 ± 0.02 6.0 ± 0.2
Ce 8.2 ± 0.1 0.03 ± 0.01 13.0 ± 0.1 Nd 3.0 ± 0.1 0.2 ± 0.02 4.0 ± 0.1
Co 12.0 ± 0.1 19.0 ± 0.2 10.0 ± 0.2 Ni 69.0 ± 0.3 89.0 ± 0.5 75.0 ± 0.4
Fe 0.3 ± 0.01 0.4 ± 0.01 0.05 ± 0.01 Pr 3.0 ± 0.1 0.2 ± 0.01 5.0 ± 0.1
La 21.0 ± 0.2 0.2 ± 0.01 35.0 ± 0.5 Y 2.0 ± 0.2 2.0 ± 0.2 2.0 ± 0.1
Mg 0.07 ± 0.01 0.09 ± 0.01 0.02 ± 0.01 Zn 0.5 ± 0.02 1.0 ± 0.03 0.2 ± 0.01

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M. Petranikova et al.
Fig. 4. McCabe-Thiele plot for Fe (III) stripping [Fe3 +]org = 0.57 g/l (mixed material)
and [Fe3 +]org = 0.78 g/l (cathodic material). Operating line represents O:A 3:1.
Fig. 5. McCabe-Thiele plot for Zn (II) stripping [Zn2 +]org = 1.2 g/l (mixed material) and
[Zn2 +]org = 1.6 g/l (cathodic material). Operating line represents O:A 3:1.
1996; Martínez et al., 1996). The extraction of the HCl can be expressed
by in the simplified form by general formula:
HClaq + TRPOorg = HCl. TROPOorg
When water washing was introduced in the system, the extracted
acid was stripped from the loaded organic phase and caused partial
stripping of REEs. In the case of anodic material 34% of extracted REEs
was stripped out. To eliminate decreases of REEs concentration in the
loaded organic phase, washing step was excluded from the process. Ni
was completely stripped out in the following step – stripping with a
solution containing 0.9 M NaNO3 and 0.1 M HNO3.
4.3.3. Main extraction: Scrubbing of Co and Mn with 1 M NaNO3
Another step, which has been not optimized in the method proposed
by Larsson was the scrubbing of residual Co and Mn from the loaded
organic phase, after previously stripping Co, Mn, and Ni with the
solution containing 0.9 M NaNO3 and 0.1 M HNO3 (so called nitrate
stripping). The loaded organic phase was prepared by performing the
extraction and the “nitrate” stripping step in the mixer-settler equip-
ment using cathodic material and mixed (after pre-main extraction) and
anodic material. The resulting samples organic phase from the nitrate
stripping were used for the experiments to construct the McCabe-Thiele
diagrams. There are McCabe-Thiele diagrams of Co and Mn stripping
shown in the Fig. 6 and Fig. 7. The concentration of Mn in the loaded
organic phase was 0.9 g/l (mixed material) and 1.1 g/l (anodic
material) respectively. The concentration of Co in the loaded organic
phase was 1.8 g/l (mixed material), 0.9 g/l (anodic material) and 2.2 g/
Hydrometallurgy 171 (2017) 128–141
Fig. 6. McCabe-Thiele plot for Mn scrubbing [Mn2 +]org = 0.9 g/l (mixed material) and
[Mn2 +]org = 1.1 g/l (anodic material). Operating line represents O:A 1:1.
Fig. 7. McCabe-Thiele plot for Co scrubbing [Co2 +]org = 1.8 g/l (mixed material),
(5) [Co2 +]org = 0.9 g/l (anodic material) and [Co2 +]org = 2.2 g/l (cathodic material).
Operating line represents O:A 1:1.
l (cathodic material). Concentration of metal ions in the organic phase
was determined using stripping. Stripping products were analyzed
using ICP-OES and concentration of metals in the organic phase was
calculated by mass balance.
The McCabe-Thiele diagrams indicate that two scrubbing stages are
required to scrub out Mn from the loaded organic phase from mixed and
anodic material. The concentration of Mn in the loaded organic phase
of cathodic material was very low (0.2 g/l), so they are omitted from
the results shown in the figure.
The results have indicated that four scrubbing stages are enough to
scrub out Co and Mn at O:A ratio 3:1. However the experimental
performance has shown that the phase separation is faster at lower O:A
ratios while the same time less REEs are scrubbed out from the loaded
organic phase. Cyanex 923 as a solvating extractants extracts free
mineral acids from the aqueous solutions (Alguacil and López, 1996;
Martínez et al., 1996). When higher O:A ratio were used extracted HCl
was scrubbed out from the organic phase. Due to high O:A ratio the
concentration of HCl was high enough to scrub out REEs as well (10%
of REEs were scrubbed out from mixed material and 25% of REEs were
removed from anodic material).
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M. Petranikova et al. Hydrometallurgy 171 (2017) 128–141

Fig. 8. McCabe-Thiele plot for Al stripping [Al3 +]org = 1.5 g/l (mixed material) and Fig. 10. McCabe-Thiele plot for Ce stripping [Ce3 +]org = 3.3 g/l (mixed material) and
[Al3 +]org = 2.5 g/l (anodic material). Operating line represents O:A 1:1. [Ce3 +]org = 5.2 g/l (anodic material). Operating line represents O:A 1:1.

4.3.4. Main extraction: Stripping of REEs and Al with 1 M HCl

This step was originally designed using an O:A ratio of 10:1,
however, the construction of the mixer-settlers does not allow for such
high ratios. The McCabe-Thiele diagrams were designed to determine
the proper O:A ratio for stripping of REEs and Al by 1 M HCl. The
mechanism of the stripping step of REEs can be expressed according to
the following equations:
REE(Cl)3 TRPO3org + H+aq + Cl− < = > REE3+aq + CI−aq + H+aq + 3TRPOorg
(6)
The organic phase samples for McCabe-Thiele diagram construction
were obtained after the stripping and scrubbing steps. There are
McCabe –Thiele diagrams for Al and La shown in Fig. 8 and Fig. 9.
McCabe-Thiele diagrams are shown for the mixed and anodic material, Fig. 11. McCabe-Thiele plot for Pr stripping [Pr3 +]org = 2.3 g/l (mixed material) and
where REEs are present. [Pr3 +]org = 3.8 g/l (anodic material). Operating line represents O:A 1:1.
The McCabe-Thiele diagrams for Al and La stripping has shown that
five stripping stages are needed to strip out Al and seven stripping
stages are required to strip out La. At higher O:A ratios 5:1 and 10:1 La
was extracted back to the organic phase due to extraction of hydro-
chloric acid and a substencial increase in pH of the aqueous phase was
also observed in a similar study (Tunsu et al., 2016). The same
phenomena can be observed in the stripping of Ce, Pr, Nd and Y
(Fig. 10–13).
The McCabe-Thiele diagrams for REEs stripping show that to strip
out Ce, Pr, Y and Nd, 4, 3 and 2 stages are needed respectively. Due to
back-extraction of REEs and slow phase separation an O:A ratio 1:1 was
selected for testing the process in the mixer-settlers equipment. This
O:A ratio was also selected to decrease the possibility of extraction of
acid into the organic phase. If a higher O:A ratio were selected for the
testing hydrochloric acid with higher concentration should be used for
Fig. 12. McCabe-Thiele plot for Nd stripping [Nd3 +]org = 1.5 g/l (mixed material) and
stripping (e.g. 2 M and higher). Further separation of REEs will be
[Nd3 +]org = 2.6 g/l (anodic material). Operating line represents O:A 1:1.
performed using acidic extractants since, it is preferable to use 1 M HCl

Fig. 9. McCabe-Thiele plot for La stripping [La3 +]org = 17.5 g/l (mixed material) and Fig. 13. McCabe-Thiele plot for Y stripping [Y3 +]org = 1.5 g/l (mixed material) and
[La3 +]org = 28.1 g/l (anodic material). Operating line represents O:A 1:1. [Y3 +]org = 2.5 g/l (anodic material). Operating line represents O:A 1:1.

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M. Petranikova et al.
and a lower O:A ratio, in order to keep the pH of the raffinate at higher
values. Flow-rates of the organic phase and stripping agent were
determined based on previous batch experiment, in which the phase
separation time was investigated at different O:A ratios.
4.4. Solvent extraction (scaling up part)
Optimized processes were scaled up using mixer-settlers with
volumes of 500 ml/unit. Factor of 4 was chosen for re-calculation of
flow rates for incoming liquids in large mixer-settlers considering the
linearity of the equipment. Processes for all three leachates were scaled
up. Leaching processes of all three materials were performed using
parameters previously tested for each type of the material. The amount
of acid needed was 3750 ± 15 ml for 1 kg of anodic material,
1960 ± 5 ml for 1 kg of cathodic material and 2700 ± 10 ml for
1 kg of mixed material. The metal concentrations in all three leachates
were identical to the values mentioned in Table 5. Firstly, Zn and Fe
present in cathodic and mixed leachate were removed in the pre-main
extraction. The raffinates were then used in the main extraction. The
leachate from anodic material was processed directly in main extrac-
tion, because anodic material does not contain neither Zn nor Fe.
4.4.1. Process for recovery of metal ions from cathodic material
Approximately 99.9% Zn and 99.9% Fe were extracted in the pre-
main extraction at O:A ratio 1:2 after four stages. Co-extracted
impurities (9% Co, 6% Y, and 2% Mn) were scrubbed out using 3 M
HCl at O:A ratio 3:1 after three stages. Approximately 4% of Zn was
scrubbed out in this step and < 0.01% of Mn and Co remained in the
organic phase. Subsequently Zn and Fe were stripped out using 5 M
HNO3 at O:A ratio 3:1. As it was determined by McCabe-Thiele
diagram, six stripping stages were sufficient to strip out Zn and Fe.
There is an aqueous phase concentration of stripped metal ions after
each stripping stage shown in Fig. 14.
To sustain the required O:A ratio and considering the time needed
for separation of organic and aqueous phase, by testing the system in
mixer-settler equipment, flow-rates were determined as following:
1200 ml/h for aqueous phase, 600 ml/h for organic phase, 200 ml/h
of scrubbing solution (3 M HCl) and 200 ml/h for stripping solution
(5 M HNO3). There is flow chart of pre-main extraction shown in
Fig. 15. Scrubbing product based on 3 M HCl and containing Co, Y, Zn,
and Mn was utilized in the leaching process.
Ni, K and Mg in the Raffinate I·C (aqueous product after extraction
step) were subsequently separated from Al, Co, Mn and Y in the main
extraction process using a mixture of 70% Cyanex 923 10%TBP, 10% 1-
Decanol and 10% kerosene at O:A ratio 2:1 and three extraction stages.
In the main extraction process, around 97% Ni, 99% K and 99.4% Mg
was not extracted (Raffinate II·C). Only 3% of Ni was co-extracted in the
extraction step. Subsequently the majority of extracted Co (83%) and
Mn (91%) was stripped out by 0.1 M HNO3, 0.9 M NaNO3 at O:A ratio
1:1 using five stripping stages. Residual Co and Mn were then scrubbed
by 1 M NaNO3 at O:A ratio 1:1. Previous tests in mixer-settler
Fig. 14. Logarithm of Zn and Fe concentration in the loaded organic stripped by 5 M
HNO3 (cathodic material) using 6 stripping stages and O:A ratio 3:1.
136
Hydrometallurgy 171 (2017) 128–141
confirmed the indications obtained from the McCabe-Thiele diagrams,
namely that two scrubbing stages are sufficient to remove Co and Mn
from loaded organic phase. Even though three stages were tested in
smaller mixer-settler, only two stages were selected when scaling up the
process. Process behavior during testing is shown in Fig. 16.
Residual Ni, which was not completely stripped out in the previous
nitrate stripping, was scrubbed out in this step. Washing product based
on 1 M NaNO3 containing mostly Co and Mn was used as a stripping
medium together with HNO3 in the previous stripping step. Tests
showed that re-use of scrubbing products didn't have a negative effect
on the stripping efficiency. Al and Y were then stripped by 1MCl at O:A
ratio 1:1 after five stripping stages. To maintain O:A ratio and
separation time of organic phase and aqueous phase, the following
flow-rates were used: 400 ml/h for Raffinate I·C, 800 ml/h for organic
phase, 800 ml/h of stripping solution (by 0.1 M HNO3, 0.9 M NaNO3),
800 ml/h for scrubbing solution (1 M NaNO3) and 800 ml/h of strip-
ping solution (1 M HCl). There is flow chart of main extraction show in
Fig. 17.
Pre-main extraction process and main extraction process for recov-
ery of metal ions from cathodic material resulted in four main product
solutions. Stripping solution containing Fe and Zn. The concentration of
Zn and Fe in the solution is too low to be efficiently utilized as a
product. Pre-concentration step is thus required not only to increase the
concentration of metals but also to regenerate HNO3 in order to re-use it
for a stripping step. The metal concentrations in aqueous products are
shown in Table 6.
Raffinate II. C is a high purity nickel solution (99.9%) and Ni can be
recovered directly by applying precipitation or electrowinning pro-
cesses. Co, Mn, and Ni present in the stripping product have to be
separated and recovered using solvent extraction process. Y can be
recovered from a stripping product after the final step. HCl can then be
re-used in either leaching or in the stripping step.
4.4.2. Process for recovery of metal ions from mixed material
From the leachate obtained after leaching mixed material, 99.9% Zn
and 99.9% Fe were extracted in the pre-main extraction process at O:A
ratio 1:2 after four stages. Approximately 8% Co, 5% Y, 1% Mn and 2%
of REEs was co-extracted. Impurities were removed from the loaded
organic phase using 3 M HCl at O:A ratio 3:1 and three stages. In the
scrubbing step, 5% of Zn was removed from the organic phase. The
resulting organic phase contained less than 0.01% of Mn and Co after
the scrubbing step. Six stages of stripping with 5 M HNO3 were applied
to strip out Zn and Fe at O:A ratio 3:1. As determined in the McCabe-
Thiele diagram six stripping stages were sufficient to strip out Zn and
Fe. There is an aqueous phase concentration of stripped metal ions after
each stripping stage shown in Fig. 18. Scrubbing product containing Co,
Y, Zn, Mn and REEs was utilized in the leaching process.
Raffinate I.M (aqueous product after extraction step) was subse-
quently treated in the main extraction to separate Ni, K and Mg from Al,
Co, Mn, and REEs using mixture of 70% Cyanex 923 10%TBP, 10% 1-
Decanol and 10% kerosene at O:A ratio 2.5:1 and three extraction
stages. Approximately 98% Ni, 99.8% K, and 99.5% Mg stayed in the
aqueous phase (Raffinate II.M). Co-extracted Co and Mn was stripped
out by 0.1 M HNO3, 0.9 M NaNO3 at O:A ratio 1:1 using five stripping
stages. 90% Co, 89% Mn, and 1.9% Ni was removed from the loaded
organic phase in this step. Residual Co, Mn and Ni were then scrubbed
by 1 M NaNO3 at O:A ratio 1:1 using two stages. Scrubbing product 1 M
NaNO3 containing scrubbed Co, Mn and low amount of REES was
employed in the previous stripping step after addition of HNO3 to
sustain ratio 0.9 M NaNO3: 0.1 M HNO3. Al and REEs were subse-
quently stripped out using 1 M HCl at O:A ratio 1:1. Results obtained
from McCabe-Thiele diagrams were used for scaling up. The results
from the stripping step for Al, Ce, La, Nd and Y tested in mixer-settlers
at O:A ratio 1:1 shown in Fig. 19.
It was confirmed that seven stages were sufficient to strip out Al and
REEs. Based on the results obtained after batch testing and mixer-settler
M. Petranikova et al. Hydrometallurgy 171 (2017) 128–141

Fig. 15. Flow chart of pre-main extraction process for cathodic material (using multistages mixer-settler system). Values in red relate to metal in the organic feed after last stage of each
step. Values in black relate to metal in the aqueous feed. All the values are reported in regard to the metal concentration in the initial aqueous feed. Symbols E, W and S represent
extraction, scrubbing and stripping steps respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 16. Logarithm of Mn and Co concentration in the loaded organic phase during
stripping by 1 M NaNO3 (cathodic material) using 3 stages. LO – concentration of the
metal in the organic phase before scrubbing.
testing (120 ml/unit), following flow-rates were used: 400 ml/h for
Raffinate I.M 1000 ml/h for organic phase, 1000 ml/h of stripping
solution (by 0.1 M HNO3, 0.9 M NaNO3), 1000 ml/h for scrubbing
solution (1 M NaNO3), and 1000 ml/h of stripping solution (1 M HCl).
There is flow-chart of main extraction process show in Fig. 20.
Four main products result out of the processes. The procedure of
possible metal recovery is same as described in the end of the Section
3.4.1. The final stripping product contains concentrated REEs which
can be recovered either as a mixture after separation of Al or selectively
separated. Metal concentration of aqueous products is shown in
Table 7.
Raffinate II. M contains only Ni (99.9%) and low amount of Mg.
Such solution is suitable for Ni recovery directly without any further
purification steps. Stripping product (after nitrate stripping) contains
Co, Mn, and Ni but also low amounts of REEs. This stripping product
has to be treated with additional purification steps to separate present
metals. Final stripping product (after stripping with 1 M HCl) needs also
further separation of Al from REEs.

Fig. 17. Flow chart of main extraction process for cathodic material (using multistages mixer-settler system). Values in red relate to metal in the organic feed after last stage of each step.
Values in black relate to metal in the aqueous feed. All the values are reported in regard to the metal concentration in Raffinate I·C. Symbols E, W and S represent extraction, scrubbing
and stripping steps respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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M. Petranikova et al. Hydrometallurgy 171 (2017) 128–141

Table 6
Metal concentration in aqueous products after leaching, pre-main extraction and main extraction of the cathodic material [g/l] and metal yields in the aqueous products [%].

Metal Metal concentration in aqueous products [g/l] Metal yields [%]

Cathodic leachate Raf. Raf. Nitrate stripping Stripping in the in the stripping in the raffinate in the nitrate in the stripping
I·C II.C product product (HCl) leachate product II.M stripping product product (HCl)
(5 M HNO3)
Al 0.3 0.3 nd nd 0.15 100 – – – 99.9
Co 19 17.3 nd 7.8 0.008 98 – – 97.9 0.1
Fe 0.4 0.001 nd nd nd 97 96.9 – – –
Mg 0.09 0.09 0.089 0.001 nd 100 – 100 – –
Mn 0.2 0.16 nd 0.45 0.008 100 – – 99.9 0.1
Ni 89 89 86.3 1.3 nd 22 – 19.1 2.9 –
Y 2 1.88 nd 0.009 1.87 99 – – 1 98
Zn 1 0.0001 nd nd nd 90 89.9 – – –

nd – not detected.

4.4.3. Process for recovery of metal ions from anodic material
Leachate after leaching of anodic material was treated in the main
extraction directly. Anodic material does not contain Fe or Zn so pre-
main extraction is not needed. Main extraction was performed at O:A
ratio 3:1 using three extraction stages. Approximately 97% Ni, 99.9% K
and 99.5% Mg stayed in the aqueous phase (Raffinate A). Subsequently
Co, Mn, and Ni was stripped out from loaded organic phase by 0.1 M
HNO3, 0.9 M NaNO3 at O:A ratio 1:1 using five stripping stages. 89%
Co, 88% Mn and 2.9% Ni was stripped out from the loaded organic
phase. Remaining Co, Mn, and Ni were removed in following scrubbing
step using 1 M NaNO3 at O:A ratio 1:1 after two stages. 1 M HCl was
then used to strip out Al and REEs at O:A ratio 1:1. The results from the
scrubbing step for Co and Mn and stripping step for Al, Ce, La, Nd, and
Y tested in mixer-settlers at O:A ratio 1:1 are shown in Fig. 21.
Seven stages were adequate to strip out Al and REEs. To sustain the
required O:A ratio flow-rates were set to: 400 ml/h for Raffinate I.M,
1200 ml/h for organic phase, 1200 ml/h of stripping solution (by 0.1 M
HNO3, 0.9 M NaNO3), 1200 ml/h for scrubbing solution (1 M NaNO3)
and 1200 ml/h of stripping solution (1 M HCl). A flow-chart of main
extraction is shown in Fig. 22.
Metal concentration of aqueous products resulting from the pro-
cesses is shown in Table 8. Raffinate after main extraction containing
preferable Ni can be mixed with a raffinate coming from a main
extraction of cathodic leachate. Both solution do not contain other
impurities than Mg.
Raffinate A is a product containing only Ni (99.9%) and low amount
of Mg. Stripping products after nitrate stripping and stripping with 1 M
HCl require further steps for metal ion separation.
5. Summary of the optimization process
There are the parameters determined by the optimization of three
processes summarized in the Table 9. In the pre-main extraction
parameters for the stripping with 5 M HNO3 were set for cathodic
and mixed material. Those parameters were not optimized in the
previous research (Larsson et al., 2013b).
In the main extraction, the parameters for the extraction step and
stripping with mixture 0.1 M HNO3 and 0.9 M NaNO3 were not
changed. But the optimization excluded the water scrubbing step, due
to co-stripping of REEs as it is explained in the Section 4.3.2 (Main
extraction: Scrubbing of Ni by water). Parameters for two steps
(scrubbing with 1 M NaNO3 and stripping with HCl), which were not
optimized by previous research. Those parameters were set by the
optimization based on counter-current test.
The optimization also provided several data usable for the evalua-
tion of the feasibility of the recycling process. Due to battery construc-
tion it is possible to assume, that the dismantling can be automatized.
Such dismantling could enable selective mechanical separation of the
cathodes and the anodes. Due to lack of the binder between active
anode material and steel grids, those can be completely separated by
the washing with a water. Steel grids can be recovered before the
leaching. This will increase material recovery rate, simplified the
leaching process and decrease the risk of the potential contamination
of the feed with iron from steel. Active anode material is completely

Fig. 18. Flow chart of pre-main extraction process for mixed material (using multistages mixer-settler system). Values in red relate to metal in the organic feed after last stage of each step.
Values in black relate to metal in the aqueous feed. All the values are reported in regard to the metal concentration in the leachate. Symbols E, W and S represent extraction, scrubbing and
stripping steps respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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M. Petranikova et al. Hydrometallurgy 171 (2017) 128–141

Fig. 19. Logarithm of Mn and Co concentration in the organic phase during stripping by 1 M NaNO3 (on the left) and Logarithm of Al, Ce, La, Nd, Pr and Y concentration in the organic
phase during stripping by 1 M HCl (on the right). LO – logarithm of concentration of the metal ions in the organic phase before each step.

Fig. 20. Flow chart of main extraction process for mixed material (using multistages mixer-settler system). Values in red relate to metal in the organic feed after last stage of each step.
Values in black relate to metal in the aqueous feed. All the values are reported in regard to the metal concentration in Raffinate I.M. Symbols E, W and S represent extraction, scrubbing
and stripping steps respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Table 7
Metal concentration in aqueous products after leaching, pre-main extraction and main extraction of the mixed material [g/l] and metal yields in the aqueous products [%].

Metal Metal concentration in aqueous products [g/l] Metal yields [%]

Leachate Raf. Raf. Nitrate stripping Stripping product in the in the stripping in the raffinate in the nitrate in the stripping
I.M II.M product (HCl) leachate product II.M stripping product product (HCl)
(5 M HNO3)

Al 1.9 1.9 nd nd 0.76 100 – – – 99.9

Ce 8.2 8.2 nd 0.13 3.3 100 – – 0.8 99.2
Co 12 11.1 nd 4 0.04 98 – – 97.9 0.1
Fe 0.3 nd nd nd nd 98 99.9 – – –
La 21 20.6 nd 0.3 8.12 100 – – 1.7 98.3
Mg 0.07 0.07 0.07 nd nd 100 – 99.5 – –
Mn 6 5.95 nd 2.1 0.02 98 – – 97.9 0.1
Nd 3 2.95 nd 0.05 1.2 100 – – 0.4 99.6
Ni 69 69 67.6 0.5 nd 75 – 98 2 –
Pr 3 2.95 nd 0.05 1.2 100 – – 0.4 99.7
Y 2 1.9 nd 0.03 0.7 100 – – 0.7 99.5
Zn 0.5 nd nd nd nd 90 99.9 – – –

nd – not detected.

dissolved in the leaching process and thus the filtration step is not
needed. Separated processing of cathodic and anodic materials can be
considered to be more economically feasible due to use of lower amount
of chemical reagents and obtaining final products with higher metal
concentration.
This optimization improved the technical feasibility of metal
recovery from such material, but further investigation involving
economic feasibility study is needed to fully evaluate developed
processes for the industrial scaling up.

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M. Petranikova et al. Hydrometallurgy 171 (2017) 128–141

Fig. 21. Logarithm of Mn and Co concentration in the organic phase during stripping by 1 M NaNO3 (on the left) and Logarithm of Al, Ce, La, Nd, Pr and Y concentration in the organic
phase during stripping by 1 M HCl (on the right). LO – logarithm of concentration of the metal ions in the organic phase before each step.

Fig. 22. Flow chart of main extraction process for anodic material (using multistages mixer-settler system). Values in red relate to metal in the organic feed after last stage of each step.
Values in black relate to metal in the aqueous feed. All the values are reported in regard to the metal concentration in Leachate A. Symbols E, W and S represent extraction, scrubbing and
stripping steps respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Table 8
Metal concentration in aqueous products after leaching, pre-main extraction and main extraction of the anodic material [g/l] and metal yields in the aqueous products [%].

Metal concentration in aqueous products [g/l] Metal yield [%]

Metal Anodic Raffinate Stripping product Stripping product (HCl in leachate in the in the stripping product in the stripping product
leachate (nitrate stripping) stripping) raffinate (nitrate stripping) (HCl stripping)
Al 3 nd nd 1.2 100 – – 99.9
Ce 13 nd 0.2 5.2 100 – 1.2 99.8
Co 10 nd 3.3 0.03 100 – 99.9 0.1
La 35 nd 0.5 13.5 100 – 2.3 97.7
Mg 0.02 0.019 0.003 nd 100 99.5 – –
Mn 6 nd 2.2 0.03 100 – 99.9 0.1
Nd 4 nd 0.06 1.6 100 – 0.8 99.2
Ni 75 74.6 0.5 nd 100 97 3 –
Pr 5 nd 0.08 2.1 100 – 0.7 99.3
Y 2 nd 0.04 0.8 100 – 1 99

nd – not detected.

6. Conclusions 1-Decanol). High purity Ni (> 99.9%) in a raffinate can be obtained

The proposed technologies allow for separation of metals present in
the leachates into four main groups. Pre-main extraction process (8%
Cyanex 923, 10% TBP, 82% kerosene) is used to remove Fe and Zn from
cathode and mixed material leachates. Approximately 99.9% of Zn and
99.9% of Fe are removed from the aqueous phase after pre-main
extraction. Rare earth elements are separated from Ni, K, and Mg in 3
main extraction stages (70% Cyanex 923, 10% TBP, 10% kerosene, 10%
after main extraction. Loaded organic phase is stripped with 0.9 M
NaNO3 and 0.1 M HNO3 to remove co-extracted Co, Ni, and Mn. Al, Ce,
La, Nd, Pr, and Y are recovered by using 1 M HCl from the organic
phase after previously stripping with 1 M NaNO3 used for removal of
residual Co and Mn. Proposed technologies have been tested in a
counter-current system using pilot plant scale mixer-settlers. For all
steps mixing speed and flow rates were tested as well. All parameter
which were not settled in the previous research, were determined by

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M. Petranikova et al.
Table 9
Parameters determined by the process optimization.
Process Steps Cathodic material
O:A ratio Number of stages
Pre-main extraction Stripping with 5 M HNO3 3:1 5 3:1
Main extraction Water scrubbing Excluded
Scrubbing with 1 M NaNO3 1:1 2 1:1
Stripping with 1MHCl 1:1 5 1:1
construction McCabe-Thiele diagrams. All those parameters were
optimized in semi-large mixer-settlers and then tested in large mixer
settlers with a volume of 500 ml/unit. Because mixer-settlers used for
those processes are linear a factor of 4 was chosen for re-calculation of
flow rates for incoming liquids in large mixer-settlers. All processes
with re-calculated flow-rates were tested in large mixer-settlers. Results
obtained after semi-large and large mixer-settlers were compared and
linearity of mixer-settlers was confirmed.
Acknowledgements
The authors would like to acknowledge the financial support of
VINNOVA (the Swedish government agency for innovation systems)
under Grants 2012-04047 and 2014-03460. This research was also
supported by Swedish Energy Agency – Battery fund (Grant No: 37714-
1).
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