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Article history: With the promoted use of compact uorescent lamps and the increasing amount of stockpiled compact
Received 21 December 2016 uorescent lamp waste, lamp phosphors are becoming an interesting secondary source for critical metals
Received in revised form (yttrium, europium and terbium). This paper explores on the mechanism of a new potential hydro-
14 March 2017
metallurgical route to improve the recovery efciency of rare-earth elements from the green phosphor
Accepted 23 March 2017
Available online 27 March 2017
LaPO4:Ce3,Tb3 using mechanical activation as a pretreatment step prior to leaching. By applying an
intense frictional action, the leaching yields of rare-earth elements were enhanced from 0.9% to 81% at
room temperature, as a consequence of the change in activation energy. The shrinking core model was
Keywords:
Rare earth elements
employed for modelling the leaching kinetics of the rare-earth elements and to calculate the decreasing
Phosphors apparent activation energy of the unmilled and milled samples (from 68 kJ mol1 to 1.4 kJ mol1). This
Fluorescent lamps difference can be explained by the physicochemical changes, including structural decomposition, specic
Resource recovery surface area increase and particle size reduction, which were related to the corresponding leaching
Ball-milling pattern. The optimized mechanical activation procedure was successfully applied to lamp phosphor
Urban mining waste, containing a mix of different phosphors. After sequential removal of the halophosphate phosphor
and the red YOX phosphor, 99.0%, 87.3% and 86.3% of La, Ce and Tb present in the LaPO4:Ce3,Tb3
phosphor could be dissolved. These observations provide more insight in the mechanical activation
process and may contribute to a more sustainable alternative route to the rare-earth element recycling
industry.
2017 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jclepro.2017.03.160
0959-6526/ 2017 Elsevier Ltd. All rights reserved.
S. Van Loy et al. / Journal of Cleaner Production 156 (2017) 226e234 227
(Bal
az, 2008; Boldyrev, 2006). Recent studies have applied me-
Abbreviations chanical activation for recycling of REEs from the YOX and LAP lamp
phosphors (Tan et al., 2016a; Zhang and Saito, 1998; Zhang et al.,
BPR ball-to-powder ratio 2000). The mechanical activation method investigated by Tan
CFL compact uorescent lamp et al. (2016b) in combination with a leaching process has suc-
D crystallite size ceeded in increasing the dissolution of REEs (Y, Eu and Tb) from
3 lattice strain uorescent lamp waste.
LED light emitting diode Despite the number of publications on the recovery of REEs from
MA mechanical activation lamp phosphors, studies using MA are scarce and lacking infor-
PS particle size mation on the effect of MA on individual phosphors. By milling the
S:L solid-to-liquid (ratio) complete lamp phosphor waste (including HALO and YOX), no
SSA specic surface area denite conclusions can be drawn on the effect of MA for the
wt% percentage weight total phosphors which are difcult to leach (such as LAP). The scope of
this paper is to conduct a systematic study of the effect of MA on the
reactivity of LAP phosphor, with emphasis on the physicochemical
changes and the milling parameters, to reveal the activation
mechanism. In the present study, the potential use of the deter-
Table 1 mined optimal MA parameters for recycling rare-earth metals from
Composition of lamp phosphor waste, analyzed by XRF. lamp phosphor waste was discussed.
Element wt% Element wt%
2. Experimental
Al 11.05 Mn 0.54
Ba 2.10 Na 7.14
Ca 21.42 Px 10.64 2.1. Materials
Ce 3.05 Sb 0.36
Cl 0.50 Si 10.89 The lamp phosphor LAP (La0.57Ce0.27Tb0.16PO4, 99%) was pur-
Eu 1.30 Sr 2.47 chased from Nichia (Japan). Lamp phosphor waste was kindly
La 3.94 Tb 1.28
provided by OSRAM (Munich, Germany). Nitric and hydrochloric
Mg 0.88 Y 19.62
acid solutions were prepared using ultrapure water (Milli-Q, Mil-
lipore; 18.2 MU cm1 at 25 C), concentrated nitric acid (65 wt%,
Chem-Lab) and concentrated hydrochloric acid (37 wt%, Merck).
phosphor waste. Recycling of the green phosphors (LAP or CAT) is
The ICP standards (Fluka, 1000 mg mL1) and lithium metaborate
also very interesting due to the high concentration of the critical
(99.9%) were purchased from Sigma-Aldrich (Diegem, Belgium).
and expensive terbium (Tb). However, the green phosphors are
much more difcult to dissolve than YOX, and often high concen-
2.2. Equipment and characterization
trations of mineral acids in combination with high temperatures
(e.g. 18 M H2SO4, 120e230 C) or cracking with molten sodium
Quantitative analysis of the leachates was performed by
hydroxide or sodium carbonate is required (Porob et al., 2012; Wu
Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-
et al., 2014). These methods are not attractive due to the waste
OES, Optima 8300, Perkin Elmer) for concentrations higher than
generation, the use of corrosive chemicals and the high energy
10 ppb and by Inductively Coupled Plasma-Mass Spectrometry
consumption. Therefore, effective methods for the recovery of REEs
(ICP-MS, 7700X, Agilent) for concentrations lower than 10 ppb. The
from the green phosphors, with a low energy consumption and
concentrations of REEs in the LAP lamp phosphor were determined
high recovery rates are highly desirable.
by quantitative analysis of the solutions (in triplicate) after LAP was
Mechanical activation (MA) by ball-milling has been used to
fully dissolved in a 37% HCl solution via microwave-assisted
enhance the acid digestion of various minerals that are hardly
digestion (Monowave 300, Anton Paar). For the analysis of the
soluble, including monazite, which has a similar structure to that of
waste phosphor, a sample of 100 mg (in triplicate) was dissolved by
LAP (Abdel-Rehim, 2002; Achimovi cova and Bala
z, 2005; Kim et al.,
fusion (1000 C) with lithium metaborate (500 mg). The melt was
2009). This technique has also been applied for the recovery of
dissolved in 50 mL of diluted nitric acid (3% HNO3). XRF analysis
various metals from secondary waste streams (Ou et al., 2015; Tan
was performed using an X-ray uorescence spectrometer (PW
and Li, 2015). Typically MA refers to the application of shear, impact
2400, Philips, Netherlands). The particle size distribution of the
and compression forces that induce a modication in the physi-
activated samples was characterized by laser particle size analyzer
cochemical properties of the solids, enhancing their reactivity
(Mastersizer 3000, Malvern, UK) using the laser diffraction method
in liquid mode. The specic surface area was determined by a
surface area analyzer (NOVA 2200e, Quantachrome, USA)
Table 2 at 196 C. XRD data was recorded using an X-ray powder
Overview of the approximate lamp phosphor waste composition found in lamp
diffractometer (D2 phaser, Bruker, Germany). Amorphous content,
phosphor waste (Binnemans et al., 2013).
crystal size and strain of the material was calculated by total Riet-
Type Name Content Economic veld renement analysis with the TOPAS software (Bruker, Ger-
phosphor (wt%)a value
many). The powder morphology was investigated by scanning
White Ca4.86Mn0.10Sb0.04Sr0.004(PO4)3Cl0.10F0.90 40e50 Low electron microscopy (XL30, Philips, Netherlands).
(HALO)
Red Y2O3:Eu3 (YOX) 20 High
Green LaPO4:Ce3,Tb3 (LAP) 6e7 High 2.3. Mechanical activation of lamp phosphors
CeMgAl11O19:Tb3 (CAT) 6e7 High
Blue BaMgAl10O17:Eu2 (BAM) 5 Low The mechanical activation of the phosphors was conducted
a
Besides the presence of phosphors, the lamp waste consists of ne glass parti- using a planetary ball-mill (P-7 premium, Fritsch, Germany) in air.
cles (up to 20 wt%), and Al2O3. Phosphor samples were mixed with zirconia balls ( 1, 3 or
228 S. Van Loy et al. / Journal of Cleaner Production 156 (2017) 226e234
Amount of metal in the leachate optimal conditions identied in the previous experiment (1 mm
% (1) grinding balls, 600 rpm). Fig. 2 shows the leaching yield over time,
Total amount of metal in the sample
obtained for two series of experiments; with and without MA of the
The expressed leaching yield represents the average yield of the phosphor. Note the break in the Y-axis. The recovery of REEs from
REEs in the phosphor as leaching percentages are similar for all unmilled LAP is low due to the lower dissolution rate of the large
REEs (La, Ce and Tb). crystalline particles. On the other hand, when the particles are
milled prior to leaching, the leaching yield of mechanically acti-
3. Results and discussion vated LAP (81%) was almost two orders of magnitude higher than
the value observed for a non-activated sample (0.9%) after 240 min
3.1. Effect of mechanical activation prior to leaching of leaching time. The leaching of mechanically activated LAP shows
two regimes: an initial rapid increase in the REE concentration
The milling conditions are of prime importance for evaluation of (during the rst minutes), followed by a gradually decreasing
the different reactions and physicochemical changes that may leaching rate. This pattern can be explained by the initial dissolu-
occur. Therefore, two crucial milling parameters (ball size and tion of the mechanically activated particles which contain a higher
milling speed) were investigated and their effect on the leaching number of defects at the outer surface. As the leaching progresses,
yield of REEs from LAP was analyzed. Fig. 1 shows the leaching yield towards the inner core of the particles, the number of defects
measured for different ball sizes (1e10 mm) and varying rotational decrease, resulting in a decreasing leaching rate. This illustrates
speeds (100e800 rpm). The results indicate that the use of a milling that the use of a combined MA and acid treatment is really
operation has a signicant effect on the leaching yield of LAP. The
use of 1 mm grinding balls and a rotational speed of 600 rpm
resulted in the dissolution of almost 80% of the REEs, which is the
highest yield obtained at room temperature in this study. No large
differences can be observed between the results of 1 mm or 3 mm
grinding balls. The decrease in the leaching yield after increase in
the rotational speed beyond a threshold value, may be explained by
the complex ball motion in the grinding vial. With increasing
milling speed, the milling pattern changes from cascading to cat-
aracting up to centrifugation, which could affect the grinding ef-
ciency (Burmeister and Kwade, 2013). The results show that a
smaller ball size is more benecial for increasing the reactivity of
the lamp phosphor powder which is in contrast to previous reports
where large grinding balls were used (Hiroshi et al., 2001; Tan et al.,
2016a). In general, one can expect that larger grinding balls are
more effective since a larger mass will result in a higher impact
transfer. However, it was also previously observed that the use of
smaller grinding balls could be benecial due to the intense (shear-
induced) frictional action (Suryanarayana, 2001). This promotes the
physicochemical changes of the solids, resulting in more reactive
particles. All further experiments have been conducted with 1 mm
grinding balls and at a rotational speed of 600 rpm, since this gave Fig. 2. Changes in the leaching yield (%) of REEs (by 4N HNO3) from unmilled and
the highest leaching yield. milled ( 1mm grinding balls, rotational speed 600 rpm, 60 min) LAP phosphor as a
The effect of the leaching time was also investigated for the function of leaching time. Note the break in the Y-axis.
S. Van Loy et al. / Journal of Cleaner Production 156 (2017) 226e234 229
signicant on the recovery process. This positive effect could be a difference in leaching model between milled and unmilled sample
consequence of the decrease in activation energy of the leaching is in line with observation described in the literature (Tan et al.,
process. 2016a), who stated that the controlling step changed from chemi-
cally controlled to diffusion controlled due to the milling operation.
The apparent activation energy was calculated by the Arrhenius
3.2. Kinetic modelling of the leaching process equation (Simha et al., 2016a, 2016b) (eqn (4)):
To investigate the effect of the leaching kinetics, the leaching A expEa =RT ka (4)
process was investigated, using the shrinking core model
The apparent activation energy for leaching of REEs was calcu-
(Levenspiel, 1999). The use of the model is justied as the lamp
lated to be 68 kJ mol1 for the unmilled and 1.4 kJ mol1 for the
phosphors are a non-porous material (Tan et al., 2016a; Verma
milled sample (rst stage) (Fig. 4). Both values t the observed
et al., 2013). Data obtained from the leaching of milled and un-
mechanism limiting step, as in general, chemically-controlled re-
milled LAP at varying temperatures (ranging from 40 C to 80 C)
actions have an Ea > 40 kJ mol1, while diffusion-controlled re-
was used for this kinetic study (Fig. 3). The diffusion-controlled
actions have a lower Ea (<40 kJ mol1) (Abdel-Aal and Rashad,
(eqn (2)) and chemical-controlled model (eqn (3)) were both
2004; Uar, 2009).
tested for the leaching of REEs:
1
1 1 x3 ka t (2) 3.3. Physicochemical changes by mechanical activation
2
As explained in the previous section, the decrease in activation
1 31 x3 21 x ka t (3) energy and consequential improvement in reactivity by prolonged
milling can be attributed to the accumulated energy, stored in the
Here x represents the leached fraction of REEs at time t (min),
particles, in the form of defects or other structural modications.
with ka the apparent reaction rate constant (min1). Fig. 3 shows
Mechanical treatment of the solids leads to the introduction of
the effect of temperature on the leaching yield of the unmilled
linear defects, e.g. ion and atom vacancies, interstitial ions and
(bottom) and milled (top) samples. The results show that temper-
dislocations besides a change of specic surface area (SSA) and
ature has a large effect on the leaching of the unmilled sample, with
particle size (PS). A change in the bond angles and broken bonds
the leaching yield increasing from 0.74% at 40 C to 11.0% at 80 C
will result in an increase in the amorphous content (Boldyrev,
within a period of 40 min. The effect is less pronounced with the
2006). The leaching yield of REEs from LAP phosphor as a func-
milled sample, with the leaching yield increasing from 80.9% to
tion of milling time is shown in Fig. 5. Previous experiments were
87.0% by the increase in temperature from 40 to 80 C. The
conducted using nitric acid as leaching agent, but could also be
diminished effect of the temperature after mechanical activation is
replaced by hydrochloric acid as a cheaper alternative. Both acids
consistent with previous reports (Tang et al., 2010; Zhao et al.,
showed similar leaching patterns, however a higher leaching yield
2009). The unmilled sample could be tted with the chemically-
was obtained by the use of nitric acid. The duration of the milling
controlled model as the leaching was controlled by the chemical
process had a positive inuence on the leaching yield, with an in-
reaction at the surface of the core of the unreacted particle. On the
crease in leaching yield from 42% to 79% from 15 to 60 min using
contrary, the milled sample could not the tted with the same
4 N HNO3. The largest increase in leaching yield was observed from
chemically-controlled model. The initial leaching of the milled
0 to 15 min of milling time. An extended milling period, longer than
sample (Fig. 3) is a very fast process in which more than 70% is
30 min, represents a marginal increment in leaching yield due to
dissolved within 20 min (at 40 C). Therefore, the process is
the possibly increasing difculty to modify the crystal structure.
diffusion-controlled during the rst leaching period (the rst
Therefore, it can be recommended to mill for a shorter period and
20 min). Afterwards, there is a shift to chemically-controlled due to
remill the solid residue after leaching, to improve the overall ef-
the consumption of all mechanically activated particles. The
ciency of the system.
The fraction of amorphous phase can be calculated from the
Fig. 3. Effect of leaching temperature on the leaching yield (%) of unmilled (bottom)
and milled (top) LAP phosphor with 4 N nitric acid ( 1 mm grinding balls, 600 rpm,
60 min). Note the break in the Y-axis. Fig. 4. Arhennius plot for unmilled and milled LAP phosphor.
230 S. Van Loy et al. / Journal of Cleaner Production 156 (2017) 226e234
Table 3
Overview of the calculated amorphous content, crystallite size and strain of the
LAP phosphor under different activation times.
Fig. 7. Changes in mean numerical particle size (-, left Y-axis) and specic surface
Fig. 6. Changes in the XRD pattern of the LAP phosphor for different activation times area (C, right Y-axis) of the LAP phosphor under different activation times ( 1 mm
( 1 mm grinding balls, rotational speed 600 rpm). grinding balls, rotational speed 600 rpm).
S. Van Loy et al. / Journal of Cleaner Production 156 (2017) 226e234 231
Fig. 8. SEM images of non-activated and activated LAP phosphor: A) non-activated 2500, B) activated 25000, 15 min, C) activated 25000, 45 min, D) activated 25000, 60 min.
milling process (rst 15 min) a sharp decrease in numerical PS is phosphor (HALO) and the REE-bearing phosphors, up to 20% ne
found, accompanied by an increase in the SSA. However, prolonged glass particles (cullet) and small amounts of alumina. The pres-
milling caused a gradual increase in the mean numerical PS from ence of other components could alter the mechanical activation
0.30 mm to 0.39 mm, after respectively 30 and 60 min of milling. The efciency of the LAP phosphor. Therefore, a full recycling process
SSA values changed from 13.6 m2/g to 7.8 m2/g in that same time was adopted from the schemes proposed by Tunsu et al. (2015)
interval. A clear inverse correlation is observed between the PS and
the SSA. After 15 min, the rate of re-welding or agglomeration of
particles exceeds the particle breakage rate, which cannot be
avoided at intensive grinding conditions (Bal a
z, 2000). For longer
grinding periods, agglomeration of the particles was more pro-
nounced. This was supported by SEM images (Fig. 8), which showed
the increasing degree of agglomeration and particle growth of the
ne particles. In general, agglomeration will negatively affect the
mass transfer of the leaching process, resulting in a decreasing
leaching rate.
There is a clear correlation between the determined deterio-
rated crystal structure, reected in the change in amorphous con-
tent, D and 3 , and the leaching rate of activated LAP. It can be
observed 3 is strongly correlated to the leaching yield (Fig. 9). The
agglomeration could explain the decreasing correlation at longer
grinding times as an increase in PS limits the mass transfer.
Consequentially, the dissolution of REEs from LAP is not only
associated with the SSA (and correlated PS), but to a much larger
extent to the mechanical deformation of the crystal structure.
Table 4
Leaching rates of rare earth in three steps acid leaching tests (%).
Element First step acid leaching Second step acid leaching Third step acid leaching without MA Third step acid leaching with MA Total leaching rates (with MA)
Ca 94.6 4.5 2.5 0.1 0.1 0.1 0.8 0.1 97.9 4.7
Y 4.2 0.1 95.7 1.9 0.1 0.1 0.1 0.1 100.0 2.1
Eu 6.6 0.1 88.5 1.4 0.5 0.1 1.0 0.1 96.1 1.6
La 0.4 0.1 0.3 0.1 0.1 0.1 99.0 1.1 99.7 1.3
Ce 0.4 0.2 0.5 0.1 0.2 0.1 87.3 1.5 88.2 1.8
Tb 0.6 0.2 0.3 0.1 0.2 0.1 86.3 1.4 87.2 1.7
S. Van Loy et al. / Journal of Cleaner Production 156 (2017) 226e234 233
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Acknowledgments rare earth elements recovering: process optimization and mechanism explo-
ration. Sci. Rep. 6, 1e10. http://dx.doi.org/10.1038/srep19961.
Tan, Q., Deng, C., Li, J., 2016b. Enhanced recovery of rare earth elements from waste
This research is supported by KU Leuven (projects GOA/13/008 phosphors by mechanical activation. J. Clean. Prod. 142, 2187e2191. http://
and IOF-KP RARE3). SVL thanks the IWT Flanders (1S23516N) for a dx.doi.org/10.1016/j.jclepro.2016.11.062.
Tan, Q., Li, J., 2015. Recycling metals from wastes: a novel application of mecha-
PhD fellowship. The authors would like to thank Tobias Hertel for
nochemistry. Environ. Sci. Technol. 49, 5849e5861. http://dx.doi.org/10.1021/
the help with XRD Rietveld renement analysis.
234 S. Van Loy et al. / Journal of Cleaner Production 156 (2017) 226e234