International Journal of Mineral Processing 168 (2017) 87–94

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International Journal of Mineral Processing

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

Secondary yttrium from spent fluorescent lamps: Recovery by leaching

and solvent extraction
Valentina Innocenzi, Ida De Michelis, Francesco Ferella ⁎, Francesco Vegliò
Dipartimento di Ingegneria Industriale, dell'Informazione e di Economia, Università degli Studi dell'Aquila, 67100 Monteluco di Roio, L'Aquila, Italy

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

Article history: The separation of yttrium and calcium from acid leach liquor obtained from leaching of fluorescent lamp phos-
Received 1 March 2017 phors has been investigated by solvent extraction with D2EHPA and Cyanex 272 in kerosene. The preliminary
Received in revised form 6 September 2017 tests suggested that D2EHPA was more efficient than Cyanex 272 for separation of yttrium. The experimental
Accepted 26 September 2017
tests allowed to define the best process conditions, among those investigated, to separate and recover yttrium
Available online 29 September 2017
selectively. The best separation circuit included three-stage cross current extraction with 20%v/v D2EHPA in ker-
Keywords:
osene (O/A = 1/1, room temperature, 10 min of contact, pH 0.02) and stripping step in counter current with
Fluorescent lamp 1.5 M sulfuric acid (O/A = 1/1, room temperature, 30 min of contact). After stripping, yttrium was recovered
Yttrium as oxalate by the addition of oxalic acid. According to the experimental results, a hydrometallurgical process
Solvent extraction was developed. The final recovery from leach liquor was around 90% and the grade of the final product was
Rare earths 97.5% as hydrated yttrium oxalate. The main impurity was sulfur, 1.28% wt, in addition to traces of other elements
Hydrometallurgy such as Si (0.057% wt), Zn (0.015% wt), Eu (0.14% wt) and Fe (0.02% wt).
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Rare earth elements (REE) are widely used in many technological
devices such as fluorescent lamps, laser, TVs, screens, liquid crystal dis-
plays (LCDs), special magnets and many others. The extraction of these
elements is concentrated in few countries, particularly China, so that
recycling of REEs is crucial in western countries. After the publication
of a report where 14 elements, including rare earths, were defined as
critical to the economy of EU by the European Commission in 2010,
the interest in collection and recycling of waste containing such critical
elements is growing and many directives entered into force to support
these strategies in the EU-27 (European Commission, 2010).
The above reasons explain why recycling of waste electrical and
electronic equipment (WEEE) is getting growing attention: moreover,
the amount of such waste produced in western countries is huge and
grows year by year. WEEE represent a real secondary mine, known as
urban mine, from which base, precious and rare earth elements can be
reclaimed. Pyrometallurgical and hydrometallurgical processes are the
most used, often in combination thereof, depending on the specific
equipment and metals (Tunsu et al., 2015).
The main components of the fluorescent powder are represented by
red phosphors Y2O3:Eu3 + (YOX), green phosphors LaPO4:Ce3 +,Tb3+
(LAP), (Gd,Mg)B5O12:Ce3 +,Tb3 + (CBT), (Ce,Tb)MgAl11O19 (CAT) and
blue phosphors BaMgAl10O17:Eu2 + (BAM) (Binnemans et al., 2013).
⁎ Corresponding author.
E-mail address: francesco.ferella@univaq.it (F. Ferella).
There are many papers, in the scientific literature, relevant to the recov-
ery of phosphors from spent lamps (Binnemans et al., 2013; Innocenzi
et al., 2014). The red phosphors can easily be dissolved with diluted
acids (Tunsu et al., 2014a). Regarding other phosphors, mainly the
green ones that contain other rare earths such as terbium, the recovery
is more difficult: the structure of green phosphors is hard to break and
very strong acidic conditions are necessary to leach REEs. A good combi-
nation to obtain an effective acidic medium is represented by a mixture
of hydrochloric acid in presence of hydrogen peroxide (Zhang et al.,
2013).
Alternatively, mechanical activation by ball milling to destroy the
crystal structure of the green and blue phosphors (Van Loy et al.,
2017; Tan et al., 2017) or a preliminary alkaline fusion (Innocenzi
et al., 2016b; Ippolito et al., 2017) are the mostly used techniques to
convert phosphors into oxides, that are more easily dissolved in diluted
acid media.
Mechanical activation, carried out by an intense frictional action, is
able to enhance the leaching yields of rare-earth elements from 0.9%
to 81% at room temperature (Van Loy et al., 2017).
The fluorescent powders were mixed with zirconia balls (Ø = 1, 3 or
10 mm) with a ball-to-powder ratio of 50:1 by weight. The samples
were milled for various time periods (15–60 min) at different rotational
speeds (100–800 rpm) with intermediate cooling periods (10 min) for
each 15 min of milling time to avoid overheating. The results showed
that the rotation speed was the crucial parameter and leaching yield
of 81% was obtained with fluorescent powders ground with 1 mm
grinding balls and at a rotational speed of 600 rpm. This high leaching

https://doi.org/10.1016/j.minpro.2017.09.017
0301-7516/© 2017 Elsevier B.V. All rights reserved.
88 V. Innocenzi et al. / International Journal of Mineral Processing 168 (2017) 87–94
yield was obtained with 4 N nitric acid solution, at room temperature for
240 min.
As already stated, another effective pre-treatment for spent fluores-
cent lamp phosphors is calcination: alkaline fusion with barium hydrox-
ide at 950 °C for 1 h was applied before leaching with sulfuric acid,
followed by precipitation with oxalic acid and calcination at 600 °C.
The composition of the recovered material was 2.22% Y2O3, 8.38%
Eu2O3, 2.43% Ce2O3, 2.29% of Gd2O3, 1.77% of La2O3 and 1.52% Tb2O3
by weight (Ippolito et al., 2017). After leaching, dissolved rare earths
can be recovered by precipitation (Innocenzi et al., 2013a, 2013b; I. De
Michelis et al., 2011; Xing and Zhang, 2011; Eberhard et al., 2000) or
by solvent extraction (Tunsu et al., 2014a, 2014b, 2016a, 2016b; Yang
et al., 2013; Guangjiun et al., 2009; Rabah, 2008; Nakamura et al.,
2007; Shimizu et al., 2005).
Shimizu et al. (2005) investigated the extraction of REEs from fluo-
rescent lamps using supercritical carbon dioxide containing tri-n-butyl
phosphate (TBP) complexes in HNO3 and H2O. Quantitative extractions
for yttrium and europium were obtained after 120 min, 15 MPa and
60 °C.
Nakamura et al. (2007) studied solvent extraction of REEs from leach
liquors coming from the dissolution of fluorescent materials with nitric
acid. In their research, PC 88A, diluted in kerosene, was used as extract-
ant. The experimental data were used to describe a possible process that
includes two extraction stages, at pH 2 and 2.6, scrubbing steps and pre-
cipitation with oxalic acid. The total recoveries were 97.8% for Y, 58.1%
for Tb, 52.8% for Eu and the purity of the final products was 98.1%,
85.7% and 100% for Y, Tb and Eu, respectively.
The process proposed by Rabah (2008) included leaching with a
mixture of sulfuric/nitric acid to dissolve yttrium and europium that
are thus converted to thiocyanates. Solvent extraction was performed
using TBP as extractant, followed by stripping with nitric acid. Europium
nitrate was separated from yttrium by dissolution with ethyl alcohol.
The final step was a thermal reduction with hydrogen at 850 °C and
1575 °C for recovery of Y and Eu metals, respectively.
Guangjiun et al. (2009) proposed one process to separate red (Y2O3:
Eu3+), blue (BaMgAl10O17: Eu2+) and green (CeMgAl10O17: Tb3+) rare
earth fluorescent phosphors. The treatment included two steps: in the
first one, the blue phosphors were extracted using 1% of potassium so-
dium tartrate, at pH 10.3, 0.25% of 2-thenoyltrifluoroacetone, aqueous/
organic volume ratio (A/O) = 3/2, 0.05 mL of 1-pentanol. Afterwards,
extraction of red and green phosphors was carried out with chloroform
and PST 0.5%, solid/liquid 30 g/L, 1-pentanol/chloroform 1/4, A/O = 3/2.
The products' purities were 96.9%, 82.7%, 94.6% for red, blue and green
phosphors, respectively, and recoveries were 92.5%, 98.8%, 82.6% for
red, blue and green phosphors, respectively.
Yang et al. (2013) studied the efficiency of N,N-dioctyldiglycol amic
acid (DODGAA) as extractant to separate from leach liquors yttrium and
europium. This extractant showed a high affinity for REEs ions although
a conventional commercial phosphonic extractant did not.
Tunsu et al. (2014b, 2016a) recovered yttrium and europium from
fluorescent lamp powder. Leaching with nitric acid was performed to
dissolve rare earths, hence a solvent extraction circuit was necessary
to extract and refine Y and Eu. Three stages of extraction using 35%v/v
Cyanex 923 in kerosene were carried out, followed by four stages of
stripping and the final precipitation with oxalic acid. The composition
of the final oxide was 94.61% of Y, 5.09% of Eu and 0.26% of other REEs.
The same authors (Tunsu et al., 2016b) described in another paper the
solvent extraction of yttrium and europium using Cyanex 572 in Solvent
70 from a nitric acid pregnant solution obtained by leaching of fluores-
cent phosphors. The results showed that Y was extracted at pH = 0
while Eu was extracted in a second step at pH = 1. Yttrium and Europi-
um were separately recovered, as oxides, by precipitation with oxalic
acid.
An alternative and greener technology was recently proposed by
Dupont and Binnemans (2015). In their research, the efficiency of
ionic liquid betainium bis(trifluoromethylsulfonyl)imide, [Hbet][Tf2N]
was studied. This compound dissolved Y and Eu selectively, without
leaching of the other compounds contained in the fluorescent powder
(such as phosphors, glass and alumina). The dissolved REEs were recov-
ered by a stripping step with oxalic acid or hydrochloric acid. The rare
earths obtained after precipitation with oxalic acid were calcined in
order to obtain a mixture of Y and Eu oxides (purity N99.9 %wt). Both
methods regenerate the ionic liquid, but the stripping with oxalic acid
has the additional advantage that no loss of ionic liquid into the water
phase take place: in this way, the loop of the recycling process is effec-
tively closed.
In the present paper the recovery of yttrium from fluorescent lamp
powders was investigated by using acid leaching and liquid-liquid
extraction.
The present paper is an improvement of the work carried out in the
ambit of the HydroWEEE projects (De Michelis et al., 2011; Innocenzi
et al., 2013a, 2013b; Innocenzi et al., 2016a). In those studies, the
main stages of the process were dissolution with sulfuric acid and pre-
cipitation with oxalic acid. In the present manuscript, a new series of ex-
periments, including selective solvent extraction of yttrium, were
described in order to increase the grade of the final oxide and thus min-
imize calcium contamination, that is the main impurity that affects the
grade of the REE oxalate. The primary goal was to investigate the selec-
tive separation of yttrium from calcium contained in the leach liquor, in
order to enhance the grade of yttrium. In the scientific literature, to the
knowledge of the authors, no reports on the extraction of metals with
D2EHPA from real leach liquors were found.
In the experiments described in the present manuscript, the influ-
ence of several factors (%v/v D2EHPA, mixing time, concentration) on
the extraction efficiency was investigated. Counter current stripping
tests were also conducted to recover yttrium from pregnant solutions.
The results of the tests were used to design a hydrometallurgical process
to reclaim yttrium from fluorescent phosphors, including leaching with
sulfuric acid, solvent extraction with D2EHPA in kerosene, stripping
with sulfuric acid and final recovery of yttrium by precipitation with
oxalic acid.
2. Materials and methods
2.1. Characterization of fluorescent phosphors
Original powder from dismantling of fluorescent lamps was ana-
lyzed by atomic absorption spectrometry (AAS) after acid digestion.
The grain size of the fluorescent powder, supplied by Relight srl (Rho,
Italy) and used in the leaching tests, was − 500 μm. Phosphors were
leached with sulfuric acid according to the best process conditions
found in previous tests. Details of the experimental procedures for dis-
solution of the fluorescent phosphors were described in our previous
works (De Michelis et al., 2011; Innocenzi et al., 2013a, 2013b). The
composition of the leachate is listed in Table 1.
Calcium is the main impurity; nonetheless, europium has a compa-
rable concentration but is another rare earth element that increases
the economic value of the final RE oxide concentrate. The other REEs
were determined in the final oxide in order to understand the actual
Table 1
Composition of the leach liquor.
Element Concentration (mg/L)
Ca 620
Y 14,900
Eu 610
Gd 139
Ce 51
Tb 36
La 33
Fe 275
Mn 98
 V. Innocenzi et al. / International Journal of Mineral Processing 168 (2017) 87–94 89

economic value of the product. Gd, Tb, Ce and La have low concentration
in the leach liquor (extraction yields lower than 10%): in fact, they are
contained in green phosphors that require a thermal pre-treatment to
be extracted quantitatively (Innocenzi et al., 2016b).

2.2. Hydrometallurgical tests

Leach liquors from dissolution of lamps were used to perform sol-

vent extraction tests. The original leach liquor contained around
15 g/L of Y and 0.6 g/L of Ca, that is the main impurity (see Table 1). So-
dium hydroxide (Fluka, ≥97%) and sulfuric acid (Carlo Erba, 96%) were
used to adjust the pH during solvent extraction tests: The organic
phases were obtained by dilution of Cyanex 272 (Cytec Industries BV)
or D2EHPA (Sigma Aldrich) in kerosene (Carlo Erba, Pure). Oxalic acid
Fig. 1. Extraction efficiency of Y and Ca from leach liquors of lamps versus equilibrium pH
(Fluka, ≥97%) was used as precipitating agent in order to recover yttri- for 20%v/v D2EHPA in kerosene, A/O = 1/1.
um as oxalate from stripped solution.

2.3. Extraction procedure The extraction yield, for the metals of interest, was calculated by the fol-
lowing equation:
Solvent extraction studies were carried out using Cyanex 272 and
D2EHPA as organic extractant. Kerosene was used as diluent. In each Yi −Y f
Extraction yield ð%Þ ¼  100 ð1Þ
test, the pH was adjusted to the required values by the addition of con- Yi
centrated sulfuric acid or sodium hydroxide solutions. Several tests,
listed in Table 2, were carried out. where Yi and Yf are the masses of the metal in the aqueous phase before
According to the main results from extraction and stripping tests, the and after the extraction process, respectively. The stripping yield for the
overall process for recovery of yttrium was simulated. Such process in- metals of interest was calculated by Eq. (2):
cludes solvent extraction, stripping and precipitation of yttrium oxa-
lates. The aqueous solutions, after stripping, were used in precipitation Yfs
Stripping yield ð%Þ ¼ ∙100 ð2Þ
tests, in which a white salt was recovered, washed, dried and calcined: Yis
the content of yttrium and other metals in the precipitate was deter-
mined by atomic absorption spectroscopy after acid digestion with where Yfs is the mass (g) of the metal in aqueous solution after strip-
aqua regia. ping, whereas Yis is the mass (g) of the metals in the organic phase be-
Each extraction and stripping test was carried out in separator fore stripping.
funnels, at room temperature with the proper aqueous/organic (A/O)
volume ratio for the required time. Regarding extraction experiments, 3. Results and discussion
10 min were supposed to be a sufficient time to achieve equilibrium
and therefore the maximum extraction yield: in fact, previous tests 3.1. Characterization of fluorescent phosphors and leaching
showed that 5 min were the minimum time required for equilibrium
in pregnant solution coming from leaching of cathode ray tube (CRTs) - Results of quantitative analysis by AAS showed the following metal
fluorescent lamp mixed phosphors. After this time, 1 mL of aqueous concentration in the powder: 9% wt Si, 13% wt Ca and 9% wt Y, as aver-
solution was taken to measure the concentration of metals and the sam- age values. This fluorescent powder was used to carry out the leaching
ple was diluted with a solution of nitric acid (pH ~2) to avoid precipita- stage according to the best conditions found in previous works (De
tion of metals during storage. Michelis et al., 2011; Innocenzi et al., 2013a, 2013b). The grain size of
the powder was −500 μm. The leaching conditions were 2 mol/L sulfu-
2.4. Analyses ric acid, 70 °C, 15%w/v pulp density and 2 h of reaction. The extraction
yields were N 95% for Y and around 4% for Ca, respectively. Concentra-
Atomic absorption spectroscopy method (AAS, Varian AA240FS) tion of Y and Ca, in the leach liquors, was around 15 g/L and 0.6 g/L, re-
was used to determine the concentration of metals in aqueous solutions. spectively. Calcium concentration was rather low, as it precipitated as
Concentration in the organic phase was calculated by subtracting the
raffinate concentration from the initial concentration in the aqueous 100
solution. 90
Calcium and yttrium were analyzed in solvent extraction and strip-
Extraction yield (%)

80
ping tests: yttrium is the most concentrated REE in the lamp's phos-
70
phors, whereas calcium is the greatest impurity in the leach liquor.
60
50
Y
Table 2
40
Ca
List of extraction and stripping tests performed in this research activity. 30

Experiments Scope 20
10
Preliminary tests Study of the effect of pH on metal extractions
Choose the best extractants between Cyanex 272 and D2EHPA 0
Solvent Study of effect of D2EHPA concentration, A/O volume ratio on 0 0.5 1 1.5 2 2.5 3
extraction tests extraction yields Equilibrium pH
Solvent extraction with stages in cross-current
Stripping tests Study of the effect of sulfuric acid, A/O volume ratio and
Fig. 2. Extraction efficiency of Y and Ca as a function of equilibrium pH for 20%v/v Cyanex
contact time on stripping yields
272 in kerosene, A/O = 1/1.
90 V. Innocenzi et al. / International Journal of Mineral Processing 168 (2017) 87–94

70 Table 4
Results of ANOVA and regression analysis for the solvent extraction factorial plan.
60
Extraction yields (%)

ANOVA DF Adj SS Adj MS F-value P-value

50
Regression 2 676.85 338.43 14.89 0.008
40 X1 1 461.78 461.78 20.32 0.006
X2 1 215.07 215.07 9.46 0.028
30 Y Error 5 113.63 22.73
Lack of fit 1 113.55 113.55 6299.72 0.000
Ca
20 Pure error 4 0.072 0.018
Total 7 790.47
10
Regression analysis R2 = 85.63%
0 Term Coeff. SE coeff. T-value P-value
0 0.2 0.4 0.6 0.8 1 1.2 1.4 Yav 11.19 1.69 6.64 0.001
X1 7.60 1.69 4.51 0.006
Equilibrium pH
X2 −5.18 1.69 −3.08 0.028

Fig. 3. Extraction efficiency of Y and Ca as a function of equilibrium pH for 20% D2EHPA in

kerosene, A/O = 1/1, pH range = 0–1.5.
calcium sulfate because of its low solubility. These solutions were used
to carry out solvent extraction tests.
3.2. Solvent extraction tests
3.2.1. Selection of the extractant: effect of pH
20%v/v of D2EHPA or Cyanex 272 in kerosene were used as extract-
ant to conduct the preliminary tests. The aqueous/organic (A/O) volume
ratio was 1/1. In these experiments, the extraction trends of yttrium and
calcium were investigated as a function of pH. The extraction yields of
such elements were carried out by the addition of sodium hydroxide
to the solutions to test several pH levels (maximum pH = 5.2): after
having achieved the desired equilibrium pH, the aqueous and organic
phases remained into contact until the equilibrium was reached, thus
a sample of aqueous solution was taken and analyzed. After sampling,
further NaOH was added to reach the next pH level and this procedure
was repeated several times up to pH 5.2 for D2EHPA and pH 2.5 for
Cyanex 272. During the extraction with Cyanex 272, a dense phase at
the interface between the aqueous and the organic phases formed,
preventing the process from going forward: for this reason, the maxi-
mum pH value achieved in such experiments was 2.5. Therefore, it can
be inferred that use of Cyanex 272 in the investigated conditions re-
quires another substance that should be added to prevent the formation
of the dense phase. Nevertheless, this was not the subject of the present
work. The influence of pH on the extraction with D2EHPA in kerosene is
shown in Fig. 1.
D2EHPA showed a higher selectivity to yttrium at pH 2, when ex-
tractions of 90% and 30% for yttrium and calcium were obtained, respec-
tively. The maximum extractions for yttrium (100%) and calcium (60%)
were achieved at a pH range of 5–6. The second test was performed with
the leach liquor in the same conditions of the first experiment, but the
organic phase was composed of 20%v/v Cyanex 272 in kerosene. In
this case, the influence of pH on the extraction is shown in Fig. 2.
At pH 2.5, the extraction yields were 60% and 10% for yttrium and
calcium, respectively. These results suggested that D2EHPA was more
selective to Y than Cyanex 272 at pH lower than 1, therefore D2EHPA
was selected for the next experiments. A new series of tests was carried
out to study the extraction trend at pH lower than 1.5; the results are
shown in Fig. 3.
The leach liquor was acidified to 0.02 with concentrated sulfuric
acid. Below pH 1.5, indeed, it was found that yttrium can be extracted
efficiently, whereas the extraction of calcium is low and largely concen-
trated in the raffinate. These data confirmed the results of previous tests,
in particular that D2EHPA is very selective to yttrium at low pHs: the ex-
traction yield of yttrium was around 30% at the original pH of the leach
liquor; instead, it was negligible for calcium. The original pH of the leach
liquor was chosen to conduct further solvent extraction experiments.
Other metals like Fe, Mn, Ni, Co are extracted at pH N2, so do not repre-
sent significant impurities (Innocenzi and Vegliò, 2012).
3.2.2. Optimization of the conditions for yttrium solvent extraction
A 22 full factorial design, with three replications of the central point,
was chosen for conducting the solvent extraction tests (Montgomery,
1991). The investigated factors were D2EHPA concentration (5%v/v–
20%v/v) and A/O volume ratio (1/2-2/1). The experiments were carried
out in the funnel glass at pH equal to 0.02. The levels of the factors were
chosen to study the effect of D2EHPA and A/O volume ratio on extrac-
tion yields for Y and Ca; furthermore, it is very useful to have a wide re-
sponse of the system under different operating conditions. Table 3
shows the experimental conditions and the relevant results.
The Yates' algorithm was applied to number each test and three rep-
licated central point experiments (tests 5, 6, 7) were carried out to have
an independent estimation of the variance of the experimental error.
Each test was replicated twice. Y experimental data were worked out
by means of Minitab 17 software package for ANOVA and regression
analysis. Nonetheless, calcium data were not analyzed by ANOVA as
the extraction yield was null for tests 1–4.
The Yates' algorithm was used to evaluate the significance of the
main interaction effects for the investigated factors. The significance

Table 3
Full factorial plan to study the extraction of Y and Ca from lamp leach liquors.

Full factorial plan Results

Test Factor A Factor B Factor A Factor B Y concentration (g/L) Ca concentration (g/L) Y extraction (%) Ca extraction (%)
D2EHPA A/O volume ratio
(%v/v)

1 − − 5 1/2 14.16 0.659 5.00 0.00

2 + − 20 1/2 10.76 0.633 27.80 0.00
3 − + 5 2/1 14.57 0.629 2.20 0.00
4 + + 20 2/1 13.16 0.635 9.67 0.00
5 0 0 12.5 1/1 12.08 0.591 17.00 4.00
6 0 0 12.5 1/1 12.09 0.588 17.02 4.80
7 0 0 12.5 1/1 12.68 0.599 12.97 3.23
 V. Innocenzi et al. / International Journal of Mineral Processing 168 (2017) 87–94 91

Table 5
Results stage by stage of cross current solvent extraction for yttrium and calcium.

Y (g/L) Ca (g/L) Y extraction (%) Ca extraction (%)

Leach liquor 14.9 0.62 – –

I 6.53 0.62 56.2 0
II 4.16 0.62 75.2 0
III 1.69 0.62 91.3 0
IV 0.98 0.58 95.4 6.14

Fig. 4. Scatter diagram of the experimental extraction yields for yttrium versus those
calculated by Eqs. (3) and (4).
was assessed by F-test with a confidence level of 95% (α b 0.05). Data
showed that the second test of the full factorial plan (20%v/v D2EHPA
and A/O = 1/2) gave the best results in terms of extraction yield for
yttrium.
The statistical analysis also showed that factors A (%v/v D2EHPA)
and B (A/O volume ratio) were found to be significant to maximize
the extraction of Y, whereas interaction AB was not statistically signifi-
cant. Factor A had a positive effect, factor B had a negative effect instead:
this means that Y extraction is enhanced when %v/v of D2EHPA in-
creases and A/O volume ratio decreases. The results of this factorial
plan were used to describe an empirical mathematical model able to
fit the experimental extraction data.
the relevant indexes are listed in Table 4, where the coefficients of the
regression analysis are also reported.
The comparison between the experimental extraction yields for
yttrium and those obtained by using the Eqs. (2) and (3) is shown in
the scatter diagram in Fig. 4.
This diagram provides information about the goodness of the math-
ematical model and being close to 0.9 a good data regression was cer-
tainly achieved. Fig. 5 shows the response of the system as a function
of %v/v D2EHPA and A/O volume ratio.
It is possible to highlight that the maximum extraction for yttrium,
around 30% (green band on Fig. 5), was achieved when the coded fac-
tors were equal to 1 and from − 1 to − 0.5. These values correspond
to the higher concentration of D2EHPA (~ 20%v/v) and 0.5–1 as A/O
ratio.
For these reasons, the next extraction tests were conducted in the
following conditions: 20%v/v D2EHPA in kerosene, A/O volume ratio
= 1/1 at the original pH of the leach liquor. A/O volume ratio equal to
1/1 was chosen to reduce the amount of the organic phase in the solvent
extraction circuit.

A B 3.2.3. Cross current solvent extraction

Y Extraction ð%Þ ¼ Yav þ X1 þ X2
2 2
where Yav is the average yield, A, B, X1 and X2 are the real and coded fac-
tors, respectively. The previous equation corresponds to the following
one:
Y Extraction ð%Þ ¼ 11:19 þ 7:60 X1−5:18 X2
where the coefficients of the equation X1 and X2 are the values of the
effects calculated by ANOVA. In the mathematical equation, factors
with significance higher than 95% were considered only. X1 and X2
had a significance equal to 98% (positive) and 95% (negative), respec-
tively, according to the F-test, whereas their interaction X1·X2 was
not significant (negative, 91%).
X1 and X2 were the dimensionless coded factors corresponding to
the two real factors. X1 is the coded factor for %v/v D2EHPA, whereas
X2 is the coded factor for A/O volume ratio. The ANOVA results and
ð3Þ
According to previous results of liquid-liquid extraction, additional
tests were carried out with D2EHPA (20%v/v) in kerosene at pH 0.02
and A/O volume ratio equal to 1/1. Solvent extraction experiments
with four stages in cross current operating mode were carried out.
This number of stages was assumed to be sufficient to separate Y from
leach liquor; the aqueous phase was put into contact with fresh organic
ð4Þ solution (20%v/v D2EHPA in kerosene, A/O = 1) in each stage. Table 5
shows the results obtained stage by stage.
The equilibrium pH decreased slightly with the increase of the ex-
traction stages, because of release of protons in solution. From data in
Table 5, it can be inferred that four stages are able to extract 95.4% of yt-
trium and 6.14% of calcium. These values suggested that three stages are
enough to limit the co-extraction of Ca: in this case the extraction yield
for Y is around 91% and negligible for calcium.
Table 6
Full factorial plan to study stripping of Y from organic phase.

Test Level Value Result

Y Extraction yield (%)

A B C Factor A Factor B Factor C Y stripping

30 Sulfuric acid A/O Contact yields (%)
concentration (M) volume time (min)
20 20-30 ratio
%v/v D2EHPA

10-20 1 − − − 2 1/4 10 8.40

10 1
0-10 2 + − − 6 1/4 10 33.50
0 3 − + − 2 1/1 10 22.10
0 4 + + − 6 1/1 10 48.10
-1
-0.5 5 − − + 2 1/4 30 13.30
0 -1 6 + − + 6 1/4 30 −
0.5
1 7 − + + 2 1/1 30 32.00
A/O volume ratio 8 + + + 6 1/1 30 45.00
9 0 0 0 4 1/2 20 49,80
10 0 0 0 4 1/2 20 40.00
Fig. 5. Yttrium extraction (%) as a function of %v/v D2EHPA and A/O volume ratio (data
11 0 0 0 4 1/2 20 55.10
from Eq. (4)).
92 V. Innocenzi et al. / International Journal of Mineral Processing 168 (2017) 87–94
A
B
AC
C
ABC
AB
BC
Fig. 6. Half-normal plot of the stripping test data: (o) negative values; (●) positive values.
3.3. Stripping tests
Organic solutions underwent stripping tests came from the extrac-
tion process with three stages in cross current, as described in the
Section 3.2.3. Sulfuric acid was used as stripping agent at different con-
centrations. A 23 full factorial design, with three replications of the cen-
tral point, was chosen for conducting the stripping tests (Montgomery,
1991). The factors were sulfuric acid concentration (2–6 mol/L), A/O
volume ratio (1/4-1/1) and contact time between organic and aqueous
solutions (10–30 min). The levels of the factors were chosen to study
the effect of these factors on stripping yields for Y and to have a re-
sponse of the system under several conditions not directly investigated.
Fig. 7. Batch simulation of a five-stage counter current stripping (AP = aqueous phase, 1.5 M sulfuric acid; OP = organic phase; A/O = 1/1).
Calcium was not considered as the concentration in the initial organic
solutions was negligible. Table 6 shows the experimental conditions of
the full factorial design.
The Yates' algorithm was applied with three replicated central point
experiments (tests 9, 10, 11). Yttrium stripping yields were worked out
by ANOVA. The Yates' algorithm was used to evaluate the significance of
the main factors and their interaction effects. The significance was
assessed by F- test with a confidence level of 95% (α b 0.05).
The statistical analysis showed that the factors A (sulfuric acid con-
centration) was found to be significant for the stripping yield of Y, but
the other factors and the interactions were not significant. Factor A
had a positive effect, therefore Y stripping increased with sulfuric acid
concentration. The maximum yields were achieved in test 4 (sulfuric
acid 6 mol/L, A/O = 1/1 with 10 min of contact) and in replicated
tests (sulfuric acid 4 mol/L, A/O = 1/2 with 20 min of contact). The
best conditions seemed to be those applied in the replicated tests,
since in the latter conditions the concentration of sulfuric acid could
be reduced, compared to the case of the test 4. The model for the strip-
ping yields was:
%Y Stripping ¼ 29:60 þ 10:64 X1 þ 7:43 X2 ð5Þ
where the numbers are the coefficients calculated by ANOVA and X1
and X2 are the most significant coded factors. The half-normal plot is
shown in Fig. 6.
As it can be inferred from the half-normal plot, the most significant
factors were A and B.
 V. Innocenzi et al. / International Journal of Mineral Processing 168 (2017) 87–94
Table 7
Yttrium recovery, stage by stage and total, obtained during counter current stripping
experiments.
Stage Stripping yield (%) Total stripping yield (%)
e 17.0 17.0
i 20.6 36.5
n 12.6 50.8
p 15.3 66.1
q 10.3 76.4
3.4. Simulation of the entire process
3.4.1. First series
The results of the previous tests were used to simulate the entire
process starting from the leach liquor of fluorescent lamp. The process
included solvent extraction with three stages, stripping with two stages
and precipitation by oxalic acid. The two-stage stripping process was
chosen as a first attempt, as the best stripping yield obtained in
Table 6 was around 50–55%, so that it was hypothesized that a couple
of stages would have been sufficient to re-extract yttrium quantitative-
ly. 100 mL of leach liquor were put into contact with 100 mL of organic
phase (20%v/v D2EHPA, A/O = 1/1). One sample was taken and ana-
lyzed by AAS for each stage. 300 mL of organic phase were put in a bea-
ker under stirring, together with the aqueous solution (H2SO4 4 mol/L):
this phase included two stages with A/O = 1/2, hence for each stage
150 mL of fresh sulfuric acid solution were used. The total extraction
yield for yttrium was around 90%, and this confirmed the data obtained
with solvent extraction tests described in Section 3.2. Furthermore, the
stripping yield was 80% for yttrium and null for calcium.
The obtained aqueous solution was used to carry out precipitation
and recovery of yttrium: oxalic acid was added in stoichiometric
amount with respect to the amount of yttrium. In this case, it was pos-
sible to notice that no salts precipitated; a white solid precipitated just
after the addition of sodium hydroxide. The amount of the 50% wt
NaOH solution resulted to be 42%v/v with respect to aqueous solution.
The addition of NaOH for neutralization of the solution led to a second-
ary reaction between oxalic acid and sodium: this was a disadvantage
since a greater amount of oxalic acid must be used to precipitate yttri-
um. Moreover, the final product was a mixture of yttrium and sodium
oxalates that produced an oxide concentrate once calcined. As a conse-
quence, it was necessary to wash the final product with distilled water
in order to reduce the amount of sodium. The solid was digested with
aqua regia and the solution analyzed by AAS: the actual concentration
of yttrium was 46.6% wt. In conclusion, the total stripping yield for yttri-
um was 80%, thus at least one more stage is required to increase the re-
claim of such element. Nevertheless, in the cross current stripping
process, there are two main disadvantages: firstly, increasing the num-
ber of stages, the consumption of NaOH required for neutralization is
too high. Secondly, the higher the amount of NaOH, the greater the so-
dium in the final precipitate. For these reasons, the counter current
stripping system was selected for further stripping experiments.
3.4.2. Second series: counter current stripping
In the second series of tests, one counter current stripping process
was performed, as indicated in Fig. 7.
Each box represents a batch separator funnel. This experiment was
carried out to study the possibility to avoid the neutralization with
NaOH during the precipitation of yttrium with oxalic acid: since the
Table 8
Impurities in the final oxalate obtained after counter current stripping.
Element S Zn Fe Mg Si Ti Zr
(%wt) 1.28 0.04 0.02 0.01 0.06 0.002 0.003
93
strong acidity of the solution inhibits the precipitation of oxalates, as
demonstrated in Section 3.4.1, counter current stripping with
1.5 mol/L of aqueous solution was carried out. Stripping experiments
were conducted with an A/O ratio of 1/1 using 1.5 mol/L of sulfuric
acid solutions. In batch operating mode, the final concentration of the
aqueous solution after five stages corresponds to the concentration of
the aqueous phase coming out from the “q” stage. Table 7 shows the re-
sults of this test in terms of stripping yields of yttrium. Stripping yield of
calcium was always null, as in the previous experiments.
Yield was around 15% on average, and the total stripping yield was
76.5% after five stages. The obtained aqueous solution was used to
carry out precipitation and recovery of yttrium: oxalic acid was added
in stoichiometric amount with respect to the amount of yttrium. In
this case, unlike the first series, no sodium hydroxide was necessary to
obtain the precipitation of yttrium oxalate. The precipitation yield was
around 90% and the salt recovered on the bottom was dried and dis-
solved with aqua regia for the determination of yttrium. Other elements
were measured by XRF, reported in Table 8. The analysis showed that
the final product was a concentrate composed of hydrated yttrium oxa-
late (97.5% wt) and traces of other elements. The precipitated salt
underwent X-ray diffraction (XRD, spectrum not shown here) analysis
that confirmed the crystalline structure of Y2(C2O4)3·2H2O.
4. Process analysis: recovery of yttrium from leach liquors coming
from treatment of fluorescent lamps
The experimental results suggested a possible flow-sheet to recover
yttrium from leach liquors from fluorescent lamps: the flow-sheet is
shown in Fig. 8. The process includes the following main stages:
- leaching with sulfuric acid;
- solvent extraction by 20% D2EHPA in kerosene, A/O = 1/1, original
pH of leach liquors, three stages;
- counter current stripping (5–7 stages) by 1.5 mol/L sulfuric acid, A/O
= 1/1;
- precipitation by oxalic acid.
The hypothesized process provided three stages of solvent extrac-
tion, counter current stripping, precipitation with oxalic acid and calci-
nation of yttrium oxalate concentrate to obtain the corresponding
oxide. From the experimental results of the counter current stripping
tests, an average stripping yield of 15% is estimated and five stages are
able to extract 76.4% of Y from the organic phase; in this manner, it is
reasonable that yttrium can be stripped almost completely with seven
stages. In this hydrometallurgical treatment, a concentrate of yttrium
could be recovered (oxalate or oxide) with a recovery yield of nearly
90% with respect to the amount contained in the leach liquor. The ex-
perimental results obtained from this research were also used to work
out a techno-economic profitability analysis (Innocenzi et al., 2016a,
2016b).
5. Conclusions
In this paper a process to recover yttrium from phosphors coming
from fluorescent lamps by solvent extraction was studied. Leach liquors
obtained from leaching of fluorescent phosphors were used in this
work. The main elements in the solutions were Y and Ca. D2EHPA and
Mn Al Cd Cr Pb Eu Tb Gd
0.005 0.01 0.0001 0.07 0.0001 0.2 0.08 0.11
94 V. Innocenzi et al. / International Journal of Mineral Processing 168 (2017) 87–94

Fluorescent powder Acknowledgements

The authors acknowledge the partners of HydroWEEE projects

H2SO4 funded by the European Union (grant number FP7-305489 and FP7-
Leaching
H2O 231962) (University of L'Aquila, Italy; SAT, Austria; University of Anco-
na, Italia; University of Rome, La Sapienza, Italy; Pupin Institute, Serbia;
Relight Srl, Rho, Italy; Greentronics, Romania; SET-Trade, Serbia). Au-
thors are also grateful to Mr. Marcello Centofanti and Ms. Fabiola
Residual solid Ferrante for their collaboration in the experimental work.
Filtration

D2EHPA
Solvent
Extraction Raffinate
Kerosene
H2SO4
Stripping Organic phase
H2O
H2C2O4 Y policies/raw-materials/files/docs/report-b_en.pdf, Accessed date: 17 January 2017.
precipitation
Yttrium oxalate concentrate
Filtration
Residual solution
Fig. 8. Flow-sheet of the process to recover yttrium from lamp's leach liquors by solvent
extraction.
Cyanex 272 in kerosene were investigated as extractants and the main
results were the following:
- D2EHPA was more efficient to extract yttrium from leach liquors at
the original pH, i.e. around 0.02, than Cyanex 272;
- three stages of extraction are enough to remove Y from the leach li-
quor. The conditions for each step were A/O = 1/1, room tempera-
ture, equilibrium pH equal to 0.02. In these conditions, around 90%
of Y was extracted. Calcium was not extracted from the pregnant so-
lution;
- stripping tests demonstrated that the sulfuric acid solution is effec-
tive to remove yttrium from the organic phase and two stages of
stripping were sufficient if 4 mol/L sulfuric acid solution is used
with A/O volume ratio equal to 1/2;
- counter current stripping should be carried out to reduce the amount
of sulfuric acid, lower the acidity of the aqueous solution and remove
the addition of sodium hydroxide during precipitation of oxalates by
oxalic acid. The stripping yield for each stage was around 15%.
In conclusion, from these results it can be inferred that the recovery
process includes three stages of extraction with 20%v/v of D2EHPA in
kerosene and seven stages of counter current stripping with 1.5 mol/L
H2SO4 solution, from which two liquid phases are obtained. The raffinate
can be sent to wastewater treatment or recycled back; the residual or-
ganic phase, after stripping, could be reused for another extraction
step, whereas the liquid containing yttrium is sent to the precipitation
with oxalic acid, followed by calcination in order to have yttrium oxide.
The final recovery of yttrium from leach liquor is nearly 90% and the
grade of the final product around 97.5% as hydrated yttrium oxalate
Y2(C2O4)3·2H2O, that can be calcined to obtain a concentrate of yttrium,
europium, terbium and gadolinium oxides.
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