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Synthesis of Rare Earth Compounds from Phosphor Coating of Spent

Fluorescent Lamps

Article in Separation and Purification Reviews · May 2020

DOI: 10.1080/15422119.2020.1754240

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SEPARATION & PURIFICATION REVIEWS
https://doi.org/10.1080/15422119.2020.1754240

Synthesis of Rare Earth Compounds from Phosphor Coating of Spent Fluorescent

Lamps
Amit Anand
School of Minerals, Metallurgical and Materials Engineering, Indian Institute of Technology, Bhubaneswar, India

ABSTRACT ARTICLE HISTORY

Ultraviolet (UV) rays are produced during operation of fluorescent lamps (FLs). Fluorescent coating, also Received 18 January 2020
known as phosphor, converts UV rays to visible light. Various chemical compounds, individually or mixed Revised 14 March 2020
in certain weight ratio, are used as phosphor. Phosphor prepared from rare earth (RE) compounds is Accepted 1 April 2020
energy-efficient. Various components including phosphor are meant to be recycled from FLs once they KEYWORDS
cease to operate. Review of literatures related to recycling of phosphor suggested that few papers were Rare earth compounds;
published prior to 2009. However, there was avalanche of relevant research articles in the next decade. phosphor; spent fluorescent
Although RE phosphors were developed in 70s, their use in FLs gained market only after 2009 when lamps; synthesis
energy protection agency passed a resolution to increase the efficiency of the lamps. In the last decade,
researchers have done massive work on recycling of phosphor. In the mean time, they switched from
one extractive technique to another to overcome the limitations of the former process. In this review, we
have investigated the need of switching from one technique to another. We discovered the gaps in
these literatures and proposed what needs to be done to fill these gaps. Flow-sheets prepared by
compiling the most efficient techniques have been proposed at the end.

Introduction There are several compounds and mixtures which convert

UV rays to visible light. These compounds and mixtures are
Rare earth metals (REMs) or simply rare earths (REs) are
classified on the basis of color of the light they emit after
a group of 17 metallic elements viz. scandium, yttrium and
being excited by UV rays. Some common types of phosphor
15 of lanthanides according to International Union of Pure
are as follows:
and Applied Chemistry.[1] The term ‘rare’ refers to unusual
properties of these elements not their abundance in earth
(1) White phosphor
crust and ‘earth’ suggests that they are oxidic, as these
(2) Red phosphor
elements are highly reactive they are found as oxidic com-
(3) Green phosphor
pounds like phosphate, carbonate, etc. Further, in this sec-
(4) Blue phosphor
tion, we will discuss about the role of REMs in fluorescent
(5) Tri-color phosphor: a mixture of red, blue and green
lamps (FLs) and the reason behind recycling these metals
phosphor which emits white light on UV excitation
from the waste ones.
One of the following materials is used as fluorescent coating
in common used FLs
Role of REMs in Fluorescent Lamps
A FL is made from a thin, transparent glass tube. After (1) White phosphor
filling the glass tube with inert gas and mercury in vapor- (2) Tri-color phosphor
ized state, it is sealed with aluminum caps. Additionally, (3) Mixture of white and tri-color phosphor
a glass stem to hold two copper–nickel-connecting wires
and a tungsten filament is provided on either end of the Phosphors are also classified into non-RE phosphor and RE
glass tube. A coating of fluorescent material known as phosphors on the basis of its composition. Some of the non-
phosphor is applied on the inner surface of the glass tube. RE phosphors are listed in Table 1, whereas RE phosphors are
When high potential difference appears across the end of listed in Tables 2–4.
filaments, they discharge electrons which move under the Efficacy and energy conversion efficiency of FLs coated
action of electric field. While moving these electrons collide with non-RE and RE phosphors have been compared with
with mercury atoms, and ultraviolet (UV) rays are gener- incandescent bulb in Table 5. FLs coated with mixture of RE
ated. Fluorescent coating converts these UV rays to visible phosphors are around eight times more efficient than incan-
light.[2] Schematic diagram showing role of phosphor in descent bulbs and consumes 20% less energy than the FLs
working of FL is given in Figure 1. having non-RE phosphor.

CONTACT Amit Anand aa11@iitbbs.ac.in School of Minerals, Metallurgical and Materials Engineering, Indian Institute of Technology, Bhubaneswar, India
© 2020 Taylor & Francis Group, LLC
2 A. ANAND

Figure 1. Schematic diagram showing role of phosphor in working of fluorescent lamp.

Table 1. Some non-RE compounds which convert UV rays to white light.

Name of the compound Chemical formula References
[3]
Calcium halophosphate Ca5(PO4)3(F0.9Cl0.1)
Strontium halophosphate Sr5(PO4)3(F0.9Cl0.1)
Calcium halophosphate doped with Sb3+, Mn2+ Ca5(PO4)3(F, Cl): Sb3+, Mn2+ [2,4]

Calcium strontium halophosphate doped with Sb3+, Mn2+ (Ca, Sr)10(PO4)6(F, Cl)2: Sb3+,Mn2+ [5]

Table 2. Some RE compounds which convert UV rays to red light. Fill Demand Supply Gap for REMs
Name of the compound Chemical formula References Apart from application in FLs components made from REMs,
Yttrium europium oxide (YOX) (Y0.95Eu0.05)2O3 [3,6,7]
their alloys and compounds are used in a variety of
Yttrium oxide doped with Eu3+ Y2O3:Eu3+ [2,4,5,8–12]
modern day appliances ranging from day-to-day necessities
or like mobile phones, display unit, etc. to strategically important
Eu3+ activated yttrium oxide (YOX)
military equipment like night-vision goggles, laser weapons,
sonar, radar, jamming devices, missiles, electromagnetic rail
gun, etc. REs are transforming our world into a better place
Why Do We Need to Extract REMs from Spent Fluorescent
for living, by virtue of their application in wind mills as
Lamps?
permanent magnets: promoting a source of clean energy, in
Spent FLs (SFLs) are non-conventional source of REMs but FLs as phosphors: leading to more efficient light, in catalysts:
we still need to extract REMs from this e-waste. We need to rendering toxic gases harmless, in rechargeable batteries:
recycle REMs from SFLs for following reasons: being used as an alternate to conventional source of energy

Table 3. Some compounds which convert UV rays to blue light.

Name of the compound Chemical formula References
[7]
Barium europium magnesium aluminate (BAM) Ba0.9Eu0.1Mg2Al16O27
Barium magnesium aluminate doped with Eu2+ BaMg2Al16O27:Eu2+ [8]

or BaMgAl10O17:Eu2+ [2,4,5,9–12]

Eu2+ activated barium magnesium aluminate

(BAM)
Calcium strontium chlorophosphate doped with Eu2+ (Ca, Sr)10(PO4)6Cl: Eu2+ [8]

Calcium strontium barium chlorophosphate doped with Eu2+ (Ca, Sr, Ba)5(PO4)3Cl: Eu2+ [4,9–12]

Magnesium calcium strontium barium chlorophosphate doped with Eu2+ (Mg, Ca, Sr, Ba)5(PO4)3Cl: Eu2+ [5]

Table 4. Some RE compounds which convert UV rays to green light.

Name of the compound Chemical formula References
[3]
Lanthanum–cerium–terbium phosphate (LAP) (La0.43Ce0.44Tb0.13)PO4
Lanthanum phosphate doped with Ce3+, Tb3+ (LAP) LaPO4:Ce3+, Tb3+ [2,4,8–12]
[6,7]
Cerium terbium magnesium aluminate (CAT) Ce0.67 Tb0.33MgAl11O19
[2,5,9–11]
(Ce, Tb)MgAl11O19
Cerium magnesium aluminate doped with Tb3+ (CAT) CeMgAl11O19: Tb3+ [4,12]

CeMgAl10O17: Tb3+ [9–11]

[2,9–12]
Cerium gadolinium terbium magnesium borate (CBT) (Ce, Gd, Tb)MgB5O10
Gadolinium magnesium borate doped with Ce3+, Tb3+ (CBT) GdMgB5O10:Ce3+, Tb3+ [4,5,12]
 SEPARATION & PURIFICATION REVIEWS 3

Table 5. Efficacy and conversion efficiency of various commercially available light sources,[2,4] Philips product data sheet.
Light source Efficacy (lumen/watt) Power consumption (watt) Output (lumen) Energy conversion efficiency
Incandescent bulb 13.4–13.5 100 1340–1350 3–5
FLs coated with non-RE phosphor 78–82 40 3040–3360 23–25
FLs coated with mixture of RE phosphors 96–104 28 2688–2900 29–31
321 3072–3328

like petrol. Due to vast application of REs, its’ demand is

continuously rising.[13]
After realizing the importance of REs, China, the largest expor-
ter of this resource, reduced the export to 60% in 2010.[14] This
export-cut by Beijing created a demand-supply gap for REs.
Technically advanced nations like Japan, United States, etc. were
worst hit by this cut. Bauer et al.[15] have placed most of the REMs
important to clean energy are at high supply risk. Consequently,
exploration activities involving discovery of RE deposits and their
production at industrial scale have increased. But the demand can
hardly be met by extracting REs from primary resources as China is
not only the largest supplier but also holds 38% of total RE
reserves.[16] In such scenario, secondary resources like e-waste
will help in reducing the demand supply gap for REMs. Recycling
of SFLs will be help in fulfilling the demand supply gap of Y, Eu, La,
Ce and Tb. For other REEs, we need to recycle other secondary
Figure 2. Spent FLs generation in India during 2014–2019.
resources of REEs like RE magnets, catalyst, batteries, fly ash, red
mud, etc.
Table 6. Content of REMs in phosphors.
Reduce Growing Pile-up of Spent Fluorescent Lamps Content (% w/w)
Among various electrical and electronic equipment, FLs are References Y Eu La Ce Tb Total
[18]
the most common ones as they are used in most of the houses, 34 1.7 12 4.5 2.7 54.9
[19]
31.9 2.2 11.8 – 2.7 48.6
offices and industries. In 2009 environment protection agency
passed a resolution to increase the efficiency of FLs which
boosted the application of energy efficient RE phosphors.
Annually, millions of such FLs are produced worldwide, Although the exact number of SFLs generated by the world
used and discarded after they stop functioning. Life of annually is not known, we can take a hint from the numbers
a typical FL is 10,000–20,000 h.[4] Assuming a FL is used for of India which is around 0.7 billion alone. We can conclude
11–12 h a day one can expect FLs to operate for 2.3–5 years. that a large number of SFLs are getting piled up around the
According to FL, sales figures for India[17] and assuming globe. These large numbers of spent FLs are generally dumped
a maximum life span of 5 years estimated number of SFLs in open or landfill sites. If we recycle this waste, we can reduce
generated in India during 2014–2019 is presented in Figure 2. the pile up and free some land fill sites.

Table 7. Optimum conditions for leaching REMs from phosphor in single stage.
Operating Variables
Literatures Leachant Temperature (°C) Time (h) Pulp Density (% w/v) Stirring speed (rpm)
[9]
0.5 N HNO3 20±1 24 10 200±50
[18]
3 N H2SO4 70 1 3 Not reported
[24]
4 N H2SO4 90 3 20 Not reported
[30]
4 N H2SO4 20±1 168 10 Not reported
[33]
8 N H2SO4/ HNO3 125 °C at 5MPa 8 Not reported Not reported
[34]
4 N H2SO4 100 8 Not available Not available
[35]
4 N H2SO4 + 10% v/v H2O2 70 3 20 Not reported
[36]
2 N HCl 95 0.5 3 500
[37]
6 N HCl 25 24 20 Not reported
[38]
1 N H2SO4 70 1 6 Not reported
[39]
4 N H2SO4 70 2 15 Not reported
[40]
3 N HCl 80 0.5 10 Not reported
[41]
2 N HCl 80 0.125 18 600
[42]
400 mL 0.05 N H2SO4 + 60 mL 30% v/vH2O2 60 1/3 23 200
[43]
1 N HCl + 2 mL H2O2/500 mL LL 50 4 2 360

1
32W FLs are not available commercially. Data displayed for comparison with halophosphate FLs.
4 A. ANAND
Spent Fluorescent Lamps are Rich and Cheap Source of
REMs
The most important aspect of recycling phosphor is the yttrium
content of this material, 30–35% w/w (Table 6), which is the highest
among the resources of this metal like monazite (trace to ~5% w/
w), basnasite (less than 1% w/w), ion adsorption clays (less than 1%
w/w), etc. with the exception of xenotime (~60% w/w).[13] Content
of europium and terbium is also substantial from extraction point
of view. Exploiting phosphor as a rich source of REMs will reduce
the dependence on the primary resources and their prime
suppliers.
Apart from having high RE content spent FLs are cheap
source of REMs. According to price quoted by local dealers
1 million spent linear fluorescent lamps (LFLs) cost
6950–13,900 USD (~0.7 cents to ~1.4 cents per LFL). On an
average, 1.316 g of phosphor can be recovered (amount
recovered in this work) from a single LFL which means
1.316 ton of phosphor can be recovered from 1 million
LFLs. Market price of 1.316 tons phosphor is 78,960–105,280
USD (alibaba.com) which clearly suggest that spent FLs are
cheap source of phosphor and hence cheaper source of REMs.
Literature review
In the previous section, we concluded that there is need for
recovering REMs from SFLs. Following questions may come
across our minds when we think about the recycling of REMs
from SFLs:
(1) What are the processes available for recovering REMs
from SFLs?
(2) Are the existing processes efficient enough or there is
a need of a new process?
Let’s answer the first question by discussing the existing
state-of-the-art for recovery of REMs from SFLs. As dis-
cussed in the first chapter, compounds of REMs are present
in phosphor coating of FLs. First of all, we need to collect
the fluorescent material from SFLs. There are two ways to
collect it:[20]
(1) Crush the entire SFL and sieve out the fluorescent
material. The materials collected by this method con-
tain considerable amount of fine glass particles and
other impurities having size comparable to phosphor
particles. Some of the literatures describing this
method are as follows.[5,9,11,20–31] Materials eroding
out of grinding tools and sieving tools also contam-
inate the phosphor. Phosphor recovered by this
method requires considerable amount of resources
to eliminate these impurities.
(2) End-cut push method: In this method, the two ends
of SFL are cut open and phosphor is pushed out. This
method is time-consuming, however, it helps in col-
lecting phosphor with negligible contamination.
Some of the literatures describing this method are
as follows.[10–12,28,29,32,33] Since the impurities are
absent in the phosphor collected by this method,
content of REMs are comparatively higher as
compared to the material collected by previous
method. The absence of impurities saves the
resources required for producing high purity
products.
End-cut push method can be considered better of the two
methods as it enables the recovery of phosphor with negligible
impurities. The phases in which the REMs are present in
phosphors limit the application of pyro- or electrometallurgy
and make hydrometallurgy the most suitable route for extract-
ing metals from this waste.[10] Leaching is the first unit pro-
cess in hydrometallurgy in which we try to dissolve the
required metal(s) selectively in some liquid solvent. Let us
discuss the literatures which have carried out the leaching
studies of REMs from phosphor.
Leaching
Researchers have employed any one of the following strategies
for dissolving REMs in aqueous solution:
(1) Lixiviation of phosphor with acid.
(2) Pyro-metallurgical treatment of phosphor and/or the
leach residue prior to lixiviation.
(3) Lixiviation of phosphor and leach residue(s) with
acid.
All these strategies serve different purposes and have their
limitation. These strategies have been discussed below.
Single-Stage Acid Leaching
Single-stage acid leaching refers to dissolution of REMs in
single contact of phosphor with acid. Single contact here
means REMs were leached from phosphor during only one
lixiviation operation. Optimum conditions from literature
implementing single-stage leaching of REMs from phosphor
are enlisted in Table 7.
Amount of metals leached from phosphor at respective
conditions given in Table 7 are listed in Table 8. From leach-
ing results listed in Table 8, following observations can be
made:
(1) Single-stage acid leaching is sufficient for extraction
of Y and Eu. Acid leaching of these two metals can be
represented by Equation (1)[9,11]
Y2 O3 : Eu3þ ðSÞ þ 6H þ ðAqÞ
! 2Y 3þ ðAqÞ þ Eu3þ ðAqÞ þ 3H2 O (1)
(2) Under same operating condition, amount of La, Ce
and Tb leached (%) is less or negligible in comparison
to Y and Eu, except for Li.[34] This suggests that LAP,
CAT and BAM are comparatively inert to acid
leaching.
(3) If the leaching of REMs present in phosphor is com-
parable like that of Li.[34] Five to six REMs will be
present in leach liquor. Separation of REMs is very
challenging due to their similar chemical properties.
In such scenario, selective extraction of individual
 SEPARATION & PURIFICATION REVIEWS 5

Table 8. Amount of metals leached from phosphor at respective conditions listed in Table 7.
Metal leached (% w/w)
Literatures Y Eu La Ce Tb Al Ba Ca Mn Sr
[9]
97 95 <20 <10 ~10 N.R. N.R. N.R. N.R. N.R.
[18]
92 98 0 0 0 24
[24]
85 A3 A A A A N.R 5 N.R. A
[30]
97.8 96.8 15.6 78.5 88.7 N.R. N.R. N.R. N.R. N.R.
[33]
96.4 92.8 A A A N.R. A A A A
[34]
80.4 82.2 81.4 80.0 86.1
[35]
100 A A A A N.R. A 18 N.R. N.R.
[36]
96 94 <5 <5 5 N.R. N.R. N.R. A A
[37]
98 96 0 0 0 39 40 50 84 71
[38]
100 100 N.A.4 N.A. N.A. N.A. N.A. N.A. N.A. N.A.
[39]
95 N.R. N.R. N.R. N.R. A A 4 N.R. A
[40]
97 91 A A A A A N.R. A N.R.
[41]
98 97 N.R. N.R. N.R. N.R. A N.R. A A
[42]
~90 ~90 A A A N.R. A N.R. A A
[43]
99.9 61.2 A N.R. N.R. N.R. N.R. 35.8 A N.R.

REM from a solution containing 4–5 REMs will be and generate a material having REMs concentration higher
very difficult.2 than that in roasted phosphor. The leach residue generated
(4) 3At operating condition given in Table 7, metals other from water leaching was further subjected to acid leaching.
than REMs 4also get leached along with REMs. The A common flow-sheet for the process has been shown in
generated leach liquor will contain REMs and non- Figure 3. Y and Eu are present in leach liquor 1, whereas
REMs. Separation of individual REMs from the leach leach liquor 2 contains La, Ce, Tb, Gd, etc.
liquor will be resource (reagents and time)-consuming The optimum conditions from the literatures implement-
and purity of the final product might be unsatisfactory ing the flow-sheet are enlisted in Table 10.
due to contaminations. The chemical equations representing roasting of various
phases as hypothesized in various literatures have been given
The observations 2–4 made from Table 8 are actually the below
limitations of single-stage acid leaching. In order to leach (a) Roasting of LAP[25,45]
REMs from the acid-resistant compounds, author has
roasted phosphor and/or the residue left after first-stage 2REPO4 þ 3BaðOH Þ2 ! RE2 O3 þ Ba3 ðPO4 Þ2 þ 3H2 O (2)
acid leaching with some suitable reagent. Roasting con-
verted acid-resistant to acid-soluble compounds. Water
leaching of the roasted product helped in removing silica RE2 O3 þ 3H2 SO4 ! RE2 ðSO4 Þ3 þ 3H2 O (3)
and alumina. [44]
2TbPO4 þ 6KOH ! Tb2 O3 þ 2K3 PO4 þ 3H2 O (4)
Leaching of Roasted Phosphor and Leach Residue Tb2 O3 þ 6HCl ! 2TbCl3 þ 3H2 O (5)
Optimum conditions from the literatures which suggest leach- (b) Roasting of CAT[6,7,22]
ing of REMs from roasted phosphor are enlisted in Table 9.
Few researchers have suggested acid leaching of phos- Ce0:67 Tb0:33 MgAl11 O19 þ NaOH
phor followed by roasting of the leach residue. The roasted ! CeO2 þ Tb4 O7 þ MgO þ NaAlO2 þ H2 O (6)
leach residue was further subjected to water leaching. The
aim was to remove the water-soluble NaAlO2 and Na2SiO3 Roasting of CAT at comparatively lower temperature[11,49]

Table 9. Optimum conditions for leaching REMs from roasted phosphor.

Literatures
[44] [45] [46] [47] [25]
Operating Variables
Roasting agent KOH Ba(OH)2 Alkali NaOH Ba(OH)2
Mixing ratio5 1:1 4:10 2:1 6:1 6:10
Roasting Temp. (°C) 900 950 700 900 950
Roasting time (h) 1 1 3 4 1
Leachant 2 N HCl 4 N H2SO4 3 N HCl 6 N HCl+H2O2 (5% v/v) 2 N H2SO4
Leaching Temp. (°C) 90 52.5 70 80 80
Leaching Time (h) 2 2 1 4 3
Pulp Density (% w/v) 5 10 7.5 Not reported 5
Stirring speed (rpm) Not reported Not reported Not reported Not reported Not reported

2
N.R.: Extent of metal leached (%) not reported in the literature.
3
A: Absent from the phosphor used in the work.
4
N.A.: Not analyzed.
5
Mixing ratio: Roasting agent: Phosphor.
6 A. ANAND

Acid Roasting agent Water

Phosphor Leach Leaching

Leaching Roasting
residue 1

Leach liquor 1 Acid Leaching Leach residue 2

Leach liquor 2

Figure 3. Flow-sheet displaying sequence of acid leaching followed by roasting–leaching.

[12,47]
Table 10. Optimum conditions for acid leaching of REMs followed by roasting
and leaching of the residue. BaMgAl10 O17 : Eu2þ þ NaOH þ O2
Operating variables [6] [22] [48] [49] ! BaO þ MgO þ NaAlO2 þ NaEuO2
Leachant 4 N HCl 4 N HCl 5.3 N H2SO4 3 N HCl þ H2 O (10)
Leaching temp. (°C) 60 60 70 60 [11,49]
Leaching time (h) 4 4 2 4
Pulp density (% w/v) 33.33 33.33 15.5 33.33 BaMgAl10 O17 : Eu2þ þ NaOH þ O2 þ CO2
Stirring speed (rpm) 250 250 Not reported Not reported ! BaCO3 þ MgO þ NaAlO2 þ Eu2 O3
Roasting agent NaOH NaOH Na2CO3 NaOH
Mixing ratio 1.5:1 1.1:1 0.5:1 1.5:1 þ H2 O (11)
Roasting temp. (°C) 800 600 900 800
Roasting time (h) 2 2 1 2 The amount of metals leached from phosphor at respective
Leachant 5 N HCl 5 N HCl 6 N HCl 5 N HCl
Leaching temp. (°C) 60 60 70 60
conditions given in Table 9 have been listed in Table 11.
Leaching time (h) 2 2 2 3 Among literatures discussed in Table 10, Liu et al.[6,22] have
Pulp density (% w/v) 10 20 15 10 reported only the combined efficiencies of first- and second-
Stirring speed (rpm) 250 250 200 Not reported
stage leaching and the respective output has been listed in
Table 12. Yurramendi et al.[48] and Zhang et al.[49] have
Ce0:67 Tb0:33 MgAl11 O19 þ NaOH þ O2 reported efficiencies for respective stages separately and their
results have been presented separately in Table 13. From
! CeO2 þ Tb4 O7 þ MgO þ NaAlO2 þ H2 O (7)
leaching results listed in Tables 11–13, we can conclude the
following points:
Roasting of CAT at comparatively higher temperature[12,47]
(1) Alkali roasting of phosphor and the leach residues
CeMgAl11 O19 : Tb þ NaOH þ O2
3þ converts LAP, CAT, BAM, etc. to acid-/water-
soluble compounds. Therefore, the amount of La,
! Na2 CeO3 þ MgO þ NaAlO2
Ce and Tb leached by this approach is much
þ NaTbO2 þ H2 O (8) higher in comparison to output of single-stage
leaching.
(c) Roasting of BAM[6,22]
(2) Water leaching of roasted sample is essential before
BaMgAl10 O17 : Eu þ NaOH þ CO2 subjecting it to acid leaching. This operation removes
the alumina and silica.
! BaCO3 þ MgO þ NaAlO2 þ Eu2 O3
(3) Overall dissolution of REMs is better in comparison
þ H2 O (9) to single-stage leaching, however, the final leach

Table 11. Amount of metals leached from phosphor at respective conditions given in Table 9.
Metal leached (% w/w)
Literatures Y Eu La Ce Tb Al Ba Ca Mn Sr
[25]
99.8 88 43 59.9 79.5 N.A6 N.A N.R.7 N.A N.A.
[47]
100 100 A 100 100 N.R. N.R. A8 A A
[46]
99.6 99.93 A 98.12 99.37 N.R. N.R. A A N.R.
[45]
92.0 88.5 26.1 41.9 63.8 A 0 N.R. N.R. A
[44]
N.R. N.R. N.R. N.R. 100 N.R. N.R. N.R. N.R. N.R.

6
N.A: Not analyzed.
7
N.R.: Not reported.
8
A: Absent.
 SEPARATION & PURIFICATION REVIEWS 7

Table 12. Literatures from Table 10 which have reported combined output of first- and second-stage leaching.
Metal leached (% w/w)
Literatures Y Eu La Ce Tb Al Ba Ca Mn Sr
[6]
94.6 99.05 A 71.45 76.22 N.R. N.R. N.R. A A
[22]
96 99 A 81 92 N.R. N.R. N.R. A A

Table 13. Literatures from Table 10 which have reported separate output of first- and second-stage leaching.
Metal leached in first-stage leaching (% w/w)
Literatures Y Eu La Ce Tb Al Ba Ca Mn Sr
[48]
99.3 91 0.3 5.7 9 N.A9 N.A N.A N.A N.A
[49]
95.61 96.35 A 8.11 9.83 N.R.10 N.R. N.R. A11 A
Metal leached in second-stage leaching (% w/w)
[48]
N.R. N.R. 81 86 85 N.A N.A N.A N.A N.A
[49]
3.45 1.03 A 90.11 88.32 N.R. N.R. N.R. A A

liquor will contain 4–5 REMs, except where prelimin-
ary acid leaching was done.
(4) Even in cases where preliminary leaching of REM was
done the final leach liquor will contain ample of non-
REMs impurities leached from phosphor.
Last two points are actually the limitations of the roast leach
method as discussed earlier. Multistage acid leaching helps in
overcoming these limitations.
Multistage Acid Leaching
As discussed earlier, selective extraction of a REM from
a solution containing 4–5 REMs is a tough job. To make
the separation job easier, we need to reduce the number of
REMs in leach liquor. While reviewing single-stage acid
(Table 8), we observed that it is possible to dissolve Y and
Eu selectively under certain conditions while leaving La, Ce
and Tb in leach residue. Following literatures have used this
strategy to generate two separate leach liquors first one con-
taining Y and Eu only while the second one rich in La, Ce and
Tb. The first leach liquor containing Y and Eu was generated
by lixiviating phosphor under certain condition hereafter
termed as first-stage leaching. The second liquor was gener-
ated by lixiviating the first-stage leach residue (leach residue
left after Y and Eu leaching) under conditions different from
first-stage leaching. Lixiviation of the first-stage leach residue
is hereafter termed as second-stage leaching. Optimum leach-
ing condition from literatures employing second-stage acid
leaching for separation of REMs into two fractions have been
given in Table 14.
The amount of metals leached from phosphor at respective
conditions given in Table 14 have been listed in Table 15.
Apart from second-stage acid leaching, Eduafo employed
another process where he calcined the first-stage leach
residue at 200°C for 2 h before subjecting it to acid leach-
ing. The calcination improved the leaching extent of La, Ce
and Tb. Extent of metal leached by lixiviation of the cal-
cined leach residue with 6 M HCl are as follows: Y: 0.17%,
Eu: 0.42%, La: 98.97%, Ce:86.66%, Tb: 84.31%, Al: 2.38%,
Ca: 0.65%.

Table 14. Optimum conditions for second-stage acid leaching of REMs from Phosphors.
[29] [50]

Operating variables First stage Second stage First stage Second stage
Leachant 1.5 N HCl 6 N HCl 10 N H2SO4 5 N HNO3
Leaching temp. (°C) 70 90 100 100
Leaching time (h) 1 1 6 6
Pulp density (% w/v) 3 3 5 5
Stirring speed (rpm) 200 200 Not reported Not reported

Table 15. Amount of metals leached from phosphor at respective conditions given in Table 14.
Metal leached ins first stage (% w/w)
Literatures Y Eu La Ce Tb Al Ba Ca Mn Sr
[29]
≈90 ≈90 <5 <5 <5 38.71 A 98.24 A A
[50]
99.5 ± 0.3 95.5 ± 2.9 0 0 0 18.5 ± 0.8 A 39.5 ± 1.6 A 3.2 ± 0.1
Metal leached ins second stage (% w/w)
[29]
0.67 1.76 84.94 69.43 73.61 N.R. A N.R. A A
[50]
≤0.4 ≤4 91.1 ± 3.6 85.9 ± 3.5 >98 ≤6 A 51.1 ± 1.4 A 91.4 ± 2.3

9
N.A: Not analyzed.
10
N.R: Not reported.
11
A: Absent.
8 A. ANAND

Table 16. Optimum conditions from literatures which removed non-REMs prior to leaching of REMs.
[11] [27]

Operating variables First stage Second stage Third stage First stage Second stage Third stage
Leachant 1 M HNO3 2 M HNO3 Second-stage leach residue to 0.5 N HCl 1.5 N HCl 4.5 M HCl
Leaching temp. (°C) 21 21 be processed according to [49] 25 70 90
Leaching time (h) 1/6 24 0.5 1 1
Pulp density (% w/v) 10 10 3 3 N.R.
Stirring speed (rpm) Not reported Not reported 200 200 200

Table 17. Amount of metals leached from phosphor at respective conditions given in Table 16.
Metal leached ins first stage (% w/w)
Literature Y Eu La Ce Tb Al Ba Ca Mn Sr
[11]
<5 <5 N.R.12 N.R. N.R. 20–45 ≤70 80–90 80–85 ≤92
[27]
3.6 5.7 4.3 0.3 0.4 N.R. A13 94 A A
Metal leached ins second stage (% w/w)
[11]
>81 >81 <5 5–10 5–15 N.R. N.R. N.R. N.R. N.R.
[27]
88.6 84.1 1.2 1.4 2.4 N.R. A ~5 A A
Metal leached ins third stage (% w/w)
[27]
0.8 0.9 78.2 78.9 73.9 N.R. A <0.2 A A
12 13
N.R: Not Reported A: Absent

Although these researchers have made the separation
of REMs easier, the leach liquors generated by their pro-
cess are heavily contaminated by non-REMs especially Ca.
In order to generate leach liquor free from non-REMs
impurities literatures listed in Table 16 have selectively
dissolved non-REMs prior to leaching of REMs.
The amount of metals leached from phosphor at respective
conditions given in Table 16 have been listed in Table 17.
After going through the literatures related to phosphor
recycling, we decided to employ multistage acid leaching
for the present work as it provided following advantages as
compared to single-stage leaching and roasting-leaching
method:
(1) Comparatively easier separation of REMs.
(2) Higher leaching yields.
(3) Higher purity products.
During literature review, it often happens that the reviewer
comes across some similar results in some of the papers.

Table 18. Composition of phosphor as reported in various literatures.

Metal leached (% w/w)
Literatures Y Eu La Ce Tb Al Ba Ca Mn Sr Si/SiO2
[6]
15.51 0.95 A 0.7 0.43 7.73 1.51 14.61 N.A N.A 10.27
[9]
9.48 0.47 0.14 0.2 0.09 1.43 1.05 8.83 0.31 A N.R.
[11]
16.47 1.05 0.08 0.07 0.04 0.75 0.47 13.5 0.44 0.18 0.04
[18]
34 1.7 12 4.5 2.7 0.33 1.2 3.3 A 7.8 0.11
[22]1
15.9 1.6 A 2.8 1 10.5 4 13 N.A N.A 31.8
[24]
7.55 A A A A 10−3 3.04 25.54 1.09 A 20.81
[25]
11.21 0.44 0.38 0.49 0.27 N.A N.A 8.13 N.A. N.A. 12.91
[27]
9.65 0.67 1.66 2.15 0.69 2.5 N.A. 17.5 N.A. N.A. 6.33
[29]
8.88 0.59 6.97 1.98 1.05 N.A. N.A. N.A. N.A. N.A. 68
[30]
6.8 0.4 0.3 0.4 0.2 1.1 2.3 70 0.8 A N.R.
[33]1
1.65 1.62 A A A A A 96 A A A
[35]
4.57 A A A A 2.47 A 14.57 0.59 A 13.48
[36]
41.29 2 4.76 4.4 2.65 19.66 2.5 3.14 N.A N.A N.A.
[37]
1.08 0.12 0.08 0.05 0.05 0.63 0.77 13.51 0.22 0.26 82
[38]
25.5 0.5 N.A N.A N.A N.A N.A N.A N.A N.A N.A
[39]
9 N.A N.A N.A N.A N.A N.A 13 N.A N.A 9
[40]
6.82 0.33 N.A. N.A. N.A. N.A N.A. 42.6 N.A. 8.44 0.8
[41]14
9.77 0.73 1.74 1.76 0.59 8.89 A 20.53 A A 24.73
[42]
3.43 0.24 N.A. N.A. N.A. 0.3 N.A. 1.43 N.A N.A 27.38
[43]1
15.21 2.07 A 4.27 3.18 8.92 2.86 24.14 A 0.32 20.45
[47]
29.3 2.95 A 4.4 2.25 22.74 4.51 A A A 0.07
[46]1
0.42 1.65 A 2.69 1.73 76.26 11.89 A A 4.34 0.58
[45]
15.7 0.62 0.53 0.69 0.37 N.A N.A 11.38 N.A. N.A. 6.37
[44]
15.7 0.62 0.53 0.69 0.37 2.12 1.13 11.38 0.12 N.A. 6.37
[48]
6.29 0.43 0.9 0.74 0.32 N.A. N.A. N.A. N.A. N.A. N.A.
[49]1
12.54 0.71 A 9.47 6.52 60.61 0.16 0.77 A A N.R.
[50]1
17.8 1.1 4.1 2.4 0.6 1.9 A 17.4 A 6.2 N.R.

12
N.R.: Not reported.
13
A: Absent.
14
All the marked literatures have reported weight percentage of respective oxide of metals.

However, while reviewing the literature related to phosphor
leaching, we could not find a single pair having same out-
put. One of the obvious reasons behind the difference in
output is difference in employed optimized leaching condi-
tions. Even at same leaching conditions (different from
optimized conditions) literatures reported different output
which were not close to each other. Most probable reason
for difference in leaching input and output is the variation
in composition of phosphor (Table 18) used in a particular
literature.
The main reasons for variation in composition are as follows:
(1) Variation in source of SFLs: Recycling units collect
and process SFLs of various brands to recover phos-
phor. Composition of the recovered phosphor
depends on the quality of the SFLs collected.
Quality refers to composition of phosphor used in
a particular FL. Meyer and Bras[51] have stated that
the composition of fluorescent coating varies from
company to company. Composition of fluorescent
coating varies according to the region/country tar-
geted by the respective companies. Composition of
phosphor controls the price of FL where as the stan-
dard of living in a particular region/country influ-
ences the buying capability of the people living
there. Hence, Binnemans et al.[26] have stated in
their review that composition of phosphor varies
from country to country and recycling companies.
(2) Difference in method of phosphor collection: the metal
concentration depends on the way of collection of phos-
phor from SFLs. If entire SFL is crushed, it is bound to
have more impurities such as glass, aluminum, etc. and
eventually the concentration of REMs will go down. On
the other hand, if end-cut push method is used as was the
case in this work, contamination will be low and RE
contents will be high.
Separation of REMs from non-REMs
Leaching is done to dissolve required metal (REMs in our case)
selectively; however, metals other than the targeted one(s) often get
dissolved in the leach liquor. As presented above, lixiviation of
phosphor dissolves many non-REMs like Ca, Sr, Mn along with
REMs. These non-REMs, if not separated from the stream of
REMs, will keep getting extracted during the downstream processes
and contaminate the final product. These non-REMs also increase
the consumption of resources required for production of pure RE
compounds. In order to produce RE compounds of high purity at
optimum consumption of resources we need to separate REMs
from non-REMs. Separation of REMs from non-REMs involves
either of the following processes:
(1) Selective precipitation of non-REMs from leach
liquor
(2) Selective precipitation of REMs from leach liquor
(3) Selective extraction of REMs from leach liquor by
organic solvents
SEPARATION & PURIFICATION REVIEWS 9
Selective Precipitation of non-REMs from Leach Liquor
Innocenzi et al.[52] adjusted pH to 2 by adding 40 mL of NaOH
solution (35% v/v) to 60 mL of leach liquor, respectively. At the
given pH 3% of Zn, 17.6% of Ca and 31.4% of Y precipitated. After
filtering the precipitate, they further added 4.9 mL of Na2S solution
(10 g/L) to 95.1 mL of the supernate. Addition of Na2S increased
pH of the supernate to 2.5 where additional 23% of Zn and 18.8%
of Y precipitated. Yu et al.[53] used ammonia and sodium sulfide
solution as precipitating agent for selective precipitation of non-
REMs. Addition of ammonia and sodium sulfide solution to the
leach liquor increased its pH and at pH 4.5 maximum amount of
non-REM impurities precipitated as hydroxides or sulfides.
Selective Precipitation of REMs from Leach Liquor
Selective precipitation of REMs from leach liquor produces
a precipitate in which RE content is much higher than non-
RE. Most of the non-REMs remain dissolved in supernate. As
discussed earlier, we add precipitating agent to leach liquor
for precipitation. Anions of precipitating agents combine with
RE cations present in aqueous phase to form insoluble com-
pounds which can be separated from leach liquor by filtration.
RE bromate, nitrate, perchlorate, bromide and chloride are
soluble in water. RE acetate, iodate and iodides are compara-
tively less soluble in water. RE sulfates are sparingly soluble in
water and their solubility decreases with increase in tempera-
ture. RE carbonates, fluoride, hydroxide, oxalate, phosphate
and sulfides are insoluble in water.
For production of individual RE compound, the precipitate
needs further processing for which it is re-dissolved in some
leaching medium. The leaching medium which will assist in
achieving maximum separation of REMs can be chosen for re-
dissolving the precipitate and it need not be same as the initial
lixiviant. Concentration of REMs in leach liquor plays an
important in separating them from one another. By re-
dissolving requisite amount of the precipitate in required
leaching medium, we can prepare leach liquor having desir-
able concentration of REMs, the concentration needs not be
same as that in the original leach liquor.
Tunsu et al.[10] have reviewed that precipitation of REMs as
hydroxides or oxalate prior to solvent extraction produces high
purity RE compounds. They have argued that separation from the
solution generated by re-dissolving the precipitate is easier in
comparison to the original leach liquor as there are fewer impu-
rities. They have proposed Equations (14) and (15) for precipitation
of RE cations by oxalic acid and ammonia solution, respectively.
þ
ðAqÞ þ 3H2 C2 O4ðAqÞ ! RE2 ðC2 O4 Þ3ðSÞ þ 2H
2RE3þ (12)
þ
ðAqÞ þ 3NH4 OHðAqÞ ! REðOH Þ3ðSÞ þ 3NH4
RE3þ (13)
As discussed earlier, the precipitates need re-dissolution for
further processing. Hydroxyl-ions are neutralized when RE
hydroxides are re-dissolved in acid but oxalate ions remain
intact in the leach liquor. The oxalate ions, if not removed
from the solution, might precipitate the dissolved RE again
during downstream processing. RE oxalates are generally cal-
cined to remove oxalate as per the following Equation (10).
10 A. ANAND
Δ Apart from precipitation, another method for separation of
2RE2 ðC2 O4 Þ3 þ 3O2 ! 2RE2 O3 þ 12CO2 (14)
Rare earth oxide (REO) thus obtained is dissolved in some
acidic medium as per the downstream process requirements.
Calcination is done at high temperature and thus it is energy-
intensive process. Apart from calcination, dissolution also
requires heating at 70–90°C. Thus, we can say that producing
oxalate-free RE solution from RE oxalates is an energy-
intensive affair. De Carolis et al.[37] have suggested an alter-
native method for producing oxalate-free RE solution from
RE oxalates in which calcination of RE2(C2O4)3 and heating
for dissolution of RE2O3 is not required. They added 1 M H2
C2O4 solution to their leach liquor to precipitate Y and Eu as
oxalates. Thereafter, they filtered RE oxalates out of the leach
liquor and re-dissolved it in an acidic solution (HCl, pH
0.5–1) containing 0.1 N KMnO4. Potassium permanganate
was used for removing oxalate ions from the solution as it
oxidizes C2O42− to carbon dioxide as per the following
equation.
RE2 ðC2 O4 Þ3 þ 6HCl ! 2RE3þ þ 6Cl þ 6H þ
þ 3C2 O4 2 (15)
 
KMnO4 þ 3HCl ! K þ þ Mn2þ þ 3Cl þ 3H2 O þ ½O
3
(16)
6H þ þ 3C2 O4 2 þ 3½O ! 6CO2 " þ3H2 O (17)
Overall reaction
RE2 ðC2 O4 Þ3 þ 3KMnO4 þ 15HCl
! 2RE3þ þ 3K þ þ 3Mn2þ þ 15Cl (18)
þ 12H2 O þ 6CO2 "
Thereafter, they added NH4OH to the supernate to raise its
pH to 2 at which Mn2+ precipitated out.
Benefits of precipitating REMs from leach liquor prior to
individual separation are summarized below:
(1) We have most of the non-REM separated thereby
facilitating the production of high purity RE com-
pounds at optimum consumption of resources.
(2) Altering the leaching medium and concentration
might assist in the separation of individual REMs.
Disadvantages of precipitating REMs from leach liquor prior
to individual separation are given below:
(1) Precipitation is basically a purification process and it
inherits the drawback that all these processes have.
Precipitation reduces the recovery (%) of REMs to
some extent.
(2) Selective precipitation of REMs followed by re-
dissolution consumes significantly high amount of
energy in comparison to selective precipitation of
non-REMs for producing pure solution of REMs.
REMs from non-REMs is solvent extraction. In solvent extrac-
tion, REMs are selectively extracted from leach liquor by
organic solvent, whereas non-REMs remain un-extracted in
raffinate or vice-versa, thereby facilitating the separation of
two entities.
Selective Extraction of REMs by Organic Extractants
Tunsu et al.[54] used 0.7 M Cyanex 923 for selective extraction
of REMs from a leach liquor containing La, Ce, Eu, Gd, Tb, Y,
Fe and Hg. Contact time was 1 min and temperature was
maintained at 23 ± 1°C. At the given extraction condition,
most of the REMs got extracted by the organic solvent while
iron and mercury remained in raffinate. Tunsu et al.[11] selec-
tively extracted more than 99.9% of Y and Eu from a leach
liquor containing 18.02 g/L Y, 1.2 g/L Eu, other REMs
(95 mg/L) and non-REMs (Al, Ba, Ca, Mn, Sr, etc. total
<0.9 g/L) by using 35% v/v Cyanex 923 in kerosene at O/A:
2/1 in three stages. Yang et al.[50] selectively extracted more
than 95% of Y and Eu from first-stage leach liquor by using
10 mM/25 mM DODGAA at pH 2.9/1.2. They extracted more
than 95% of La, Ce, Pr and Tb from second-stage leach liquor
50 mM N,N-di-octyl di-glycol amic acid (DODGAA) at pH 3.
Separation of REMs from One Another
Separation of REMs from one another is one of the most
challenging jobs related to these metals. Separation job is so
challenging that it nearly took 160 years for scientists to
isolate individual REMs from RE bearing minerals. RE-
bearing minerals are supposed to contain all REMs in which
concentration of some will be considerable while others might
be low. Separation of two metals generally involves exploita-
tion of the differences in chemical properties, greater the
difference easier and better the separation. Separation of
REMs is challenging because they exhibit close chemical simi-
larity. Strikingly similar electronic configuration leads to
uncanny similarity in the chemical properties of REMs and
their compounds.[13] Therefore, isolation of REMs is one of
the biggest challenges while working with these metals.
As discussed earlier, a commercial phosphor may con-
tain three or more RE compounds. Lixiviation of phosphor
is a chemical interaction between these compounds and
lixiviants. Nature and extent of reaction of an individual
RE compounds with leachants differ from each other.
However, dissolution extent of REEs from an individual
compound remains similar under a particular leaching con-
dition due to the chemical similarity of these metals. Based
on these facts, it was possible to separate REMs into two
streams: first one containing Y and Eu, whereas the second
one containing La, Ce and Tb. Separation of Y from Eu
involves selective extraction of Y or Eu from leach liquor.
Leach liquors generated by selective dissolution of Y and
Eu were processed by one of the following techniques to
generate separate solutions of Y and Eu.
(1) Selective extraction of Y or Eu from the leach liquor
using organic solvents.
 SEPARATION & PURIFICATION REVIEWS 11

Table 19. Optimum conditions for reducing Eu3+ to Eu2+ followed by sulfate precipitation of Eu2+.
[61] [62]
References
Leach liquor REOs Eu2O3 1
Y2O3 13
Leaching conditions Leachant 12 M HCl 12 M HCl
Pulp density 100 g/L
Optimum conditions for reduction and precipitation Reducing agent Zn (5 × stoichiometric req.) 5 g Zn
Reduction time 2h 1h
pH 3 3
2−
Precipitating agent 1 M H2SO4 H2SO4; SO4 /Eu: 10 × stoichiometric req.
Precipitating/aging time 2h 3h
Degassing agent H2
Recovery (% w/w) Eu 88 73.32
Y –
Grade (% w/w) Eu 95.7 94.58
Y 1.4

(2) Selective reduction of Eu3+ to Eu2+ followed by pre-
cipitation of Eu2+ as EuSO4.
Let us discuss the literatures employing solvent extraction
technique to separate Y and Eu.
Separation of Y and Eu by Solvent Extraction
Banda et al.[55] did preliminary separation studies with a model
solution containing Y (3145 mg/L), Eu (215 mg/L), CaCl2
(3 mol/L) and NH4SCN (0.8 mol/L). Optimum values of oper-
ating parameters obtained from preliminary studies were used
for separation of Y (2886 mg/L) and Eu (165 mg/L) from
original leach liquor. NaOH was added to the leach liquor to
increase the pH to 4.2. Yttrium was selectively extracted from
the leach liquor by tri-hexyl(tetradecyl)phosphonium thiocya-
nate, [C101][SCN] in four counter-current stages keeping
organic to aqueous volume ratio (O/A) at 0.1, contact time
was 30 min. At the given extraction condition, majority of Eu
remained in raffinate. Co-extracted Eu was scrubbed from
loaded organic with a solution containing CaCl2 (3 mol/L) and
NH4SCN (0.8 mol/L). Yttrium was stripped from the scrubbed
organic with de-ionized water in two stages.
De Carolis et al.[37] performed initial separation experi-
ments on a simulated hydrochloric solution containing
0.01 M Y and Eu. 91.6% of Y and 8.5% of Eu was extracted
from the leach liquor by 0.1 M PC88A in a single-stage
keeping organic to aqueous volume ratio at unity, contact
time was 60 min. They applied the optimum extraction
condition on original leach liquor 0.02142 M Y and
1.213424 mM Eu. 95% of Y and Eu were stripped from
loaded organic with 2 M HCl keeping O/A ratio 1.
Contents of Y and Eu in the loaded stripped liquor were
76.7% and 6.2%, respectively.
Mishra et al.[56] carried separation studies with 0.25 M HCl
solution containing 1.8923 g/L Y and 0.1642 g/L Eu. 97.4% of
Y and 39% of Eu were extracted from the leach liquor at
initial pH of 2.6 (equilibrium pH = 2.03) by 0.1 M
D2EHPA. They simulated two-stage counter-extraction with
above conditions at O/A: 1/1.5. Second-stage raffinate con-
tained 5.0 mg/L Y and 0.10 g/L Eu. Yttrium extraction was
99.7%, whereas the co-extraction of Eu is 36.5%. They
stripped Y completely from their organic phase, containing
2.83 g/L Y and 0.06 g/L Eu, with the help of 0.4 M oxalic acid
in 30 min.
Tunsu et al.[31] were able to generate individual solutions
of Y and Eu from a 4 M HCl solution containing 18 g/L Y and
1 g/L Eu. More than 99.9% of Y was selectively extracted by
1 M Cyanex 572 at equilibrium pH 0 during a contact time of
15 min keeping O/A ratio 1. More than 99.9% of Y was
stripped from the loaded organic with 3 M HCl during a con-
tact time of 15 min keeping O/A at unity. More than 99.9% of
Eu was selectively extracted from the raffinate, left after selec-
tive extraction of Y, by 1 M Cyanex 572 at equilibrium pH 1
during a contact time of 15 min keeping O/A at unity. More
than 99.9% of Eu was stripped from the loaded organic with
3 M HCl during a contact time of 15 min keeping O/A ratio 1.
pH adjustment at any stage was done with the help of addi-
tion of NaOH.
Yang et al.[50] conducted separation experiments on
a simulated leach liquor containing 10 ppm of Y and Eu
dissolved in 0.05 M H2SO4. More than 96% of Y and 11% of
Eu was extracted by 10 mM PC88A at equilibrium pH 2.5
during contact time of 12 h keeping O/A ratio 1. The separa-
tion factor was 194.2.
Eu Separation by Reduction-Precipitation Technique
Most of the works involved in separation of Eu from other
REMs are based on the fact that Eu can be selectively reduced
to stable bivalent state.[57,58] After reducing Eu3+ to Eu2+ it
can be separated from other REMs by precipitating it as
EuSO4. Chemical properties of Eu in bivalent state are similar
to that of group IIA elements.[57–60] Reduction of Eu3+ to Eu2+
can be achieved chemically by using reducing agent or by
electrochemical or photochemical treatment.[60] However, the
review here has been limited to literatures reporting chemical
reduction of Eu3+ to Eu2+. Reactions involved in chemical
reduction of Eu3+ to Eu2+ followed by sulfate precipitation
of Eu2+ are given below:[59]
ðAqÞ þ ZnðSÞ ! 2EuðAqÞ þ ZnðAqÞ
2Eu3þ 2þ 2þ
(19)
For pH<1.9  þ
ðAqÞ þ HSO4 ðAqÞ ! EuSO4 ðSÞ þ H
Eu2þ (20)
For pH>1.9
ðAqÞ þ 2SO4 ðAqÞ ! 2EuSO4 ðSÞ
2Eu2þ 2
(21)
12 A. ANAND
Optimum conditions from literature suggesting chemical
reduction of Eu3+ to Eu2+ followed by sulfate precipitation
of Eu2+ for selective extraction of Eu from leach liquor con-
taining Y and Eu are given in Table 19.
Bogaert et al.[63] dissolved red phosphor in 0.5 M HCl
solution at a pulp density of 0.6% w/w. Molar ratio of Y and
Eu in leach liquor was 30/1. Thereafter, they added (NH4)2
SO4 to the leach liquor to raise its concentration to 50 mM. By
adding 1 M NaOH pH of the leach liquor was increased to 4.
About 50 mL of isopropanol was added to the leach liquor as
scavenger. The resulting solution was illuminated with low-
pressure mercury lamps (having their main spectral output at
185 nm and 254 nm) for a period of 50 h to selectively reduce
Eu3+ to Eu2+. The photochemical reduction of Eu3+ to Eu2+ is
as follows:
 3þ 188 nm  2þ
EuðH2 OÞn ! EuðH2 OÞn1 þ OH : þ H þ (22)
Recovery of Eu was 50% while the purity of the precipitated
EuSO4 was 96%. Bogaert et al.[64] dissolve hydrated chlorides
of Y (100 mM) and Eu (10 mM) in a 50/50 v/v mixture of
ethanol and isopropanol. Thereafter, 220 mM LiCl was added
to the solution. Water content of the solution was kept at
0.18 wt.%. The solution was illuminated with medium-
pressure mercury lamp for a period of 3 h to selectively
reduce Eu3+ to Eu2+. The photochemical reduction of Eu3+
to Eu2+ followed by precipitation of Eu2+ takes place as
Equations (18) and (19), respectively:
230 nm
Eu3þ þ R2 CHOH ! Eu2þ þ R2 C: OH : þ H þ (23)

ðAlchoholÞ þ 2ClðAlchoholÞ ! 2EuCl2 ðSÞ
Eu2þ (24)
Recovery of Eu was 94.7% while the purity of the precipitated
EuCl2 was 96.7%. Wu et al.[43] added (NH4)2SO4 to their leach
liquor so as to increase its strength to 50 mM, adjusted the pH
to ~4 and illuminated the resulting solution with a 254-nm
UV lamp irradiation for 42 h. Recovery of Eu was 98.5% while
the purity of the precipitated EuSO4 was 96.7%.
Apart from reduction-precipitation technique, Rabah[33]
exploited the difference in solubility of europium and yttrium
nitrate in ethyl alcohol. He used tri-methyl-benzyl ammo-
nium chloride for simultaneous extraction of Y and Eu from
a thiocyanate solution. 98.8% of Y and 96.5% of Eu were
extracted by using the organic extractant in a molar ratio of
2:1. He stripped 99.9% of Y and Eu from the loaded organic
with n-tributyl phosphate (dissolved in 1 M HNO3). Gentle
heating of the loaded strip solution evaporated n-tributyl
phosphate leaving behind a nitrate salt of Y and Eu. When
the nitrate salt was added to ethyl alcohol Y(NO3)3 dissolved
while Eu(NO3)3 remained in solid state thereby enabling the
separation of the two REMs.
The leach residue left after selective dissolution of Y and
Eu was rich in La, Ce and Tb. The residue was subjected to
acid lixiviation which resulted in a leachate containing most
of the La, Ce and Tb hereafter termed as second-stage leach
liquor. Separation of La, Ce and Tb involves selective extrac-
tion of either of the REMs present in second-stage leach
liquor. Let us discuss the selective extraction of Tb of
from second-stage leach liquor.
Separation of Tb from La and Ce
Yurramendi et al.[48] generated a second-stage leach liquor
containing 0.331/L La, 0.264 g/L Ce and 0.129 g/L Tb by
dissolving first-stage leach residue in 6 M HCl. D2EHPA
(60% v/v in xylene) extracted 96.1% of Tb along with 5.1%
of La and 6.8% of Ce from second-stage leach liquor
(pH = −0.8) in single-stage keeping O/A ratio 1. The raffinate
containing majority of La and Ce was diluted by adding
ultrapure water equal to its volume. Resulting chloride (Cl−)
concentration was 3 mol L−1 and pH increased to −0.5.
Undiluted D2EHPA was able to extract 93% of La and 95%
of Ce from the diluted raffinate in two stages at O/A ratio 1.
Thereafter, 1.5 M oxalic acid was added to both the loaded
organic in the ratio 1:20 to precipitate REMs as oxalates.
Precipitation of Tb was 94% while that of La and Ce were
quantitative. RE oxalates were calcined at 700°C for 4 h to
obtain RE oxide. Composition of obtained terbium oxide: Tb:
63.7%, Y: 10.8%, Ce: 8.6%, La: 7.7%, Eu: 5.4%; Gd: 3.8% while
that of mixed lanthanum and cerium oxide was: La: 55.5%,
Ce: 43.5%, Tb: 1%.
Recovery of REMs from Leach Liquor
Pure solutions of individual REMs obtained after separation
are not marketed as they produced liquid form probably due
to large volume and handling issues. They are generally mar-
keted as solid REOs. Precipitation followed by calcination is
one of the most common and easiest techniques for produ-
cing REOs, mixed or individual, from solutions containing
REMs. For precipitation of REMs, we generally add oxalic
acid or OH−-releasing reagents such as ammonia solution or
NaOH. Precipitate thus obtained is calcined to obtain REOs.
Calcination of RE oxalate has been described earlier through
Equation (16). RE hydroxides are calcined to REOs as per the
following equation
Δ
2REðOH Þ3ðSÞ ! RE2 O3 þ 3H2 O (25)
[55]
Banda et al. added ammonia solution to their loaded
stripped liquor (containing Y) and the raffinate (containing
Eu) to precipitate REMs as hydroxides. RE hydroxides were
further subjected to calcination at 400–450°C to produce
REOs. Purities of Y2O3 and Eu2O3 were over 98.2% and
98.7%, respectively while the overall recovery for Y and Eu
were 94% and 98%, respectively. De Michelis et al.[24] added
stoichiometric amount of oxalic acid to their synthetic leach
liquor to precipitate more than 98% of Y. They added 20%
more than the stoichiometric requirement of oxalic acid to
their original leach liquor to precipitate 80% of Y. The pre-
cipitate was roasted at 800–1000°C to obtain 90–95% pure
yttrium oxide. Eduafo[29] was able to precipitate 100% of the
REMs in 2 h by adding oxalic acid to his leach liquors. RE
oxalates were calcined at 900°C for 45 min to obtain REOs.
Innocenzi et al.[52] added 10% excess of stoichiometric
amount of oxalic acid (40 g/L) to precipitate Y from non-
REM depleted leach liquor. The precipitate was calcined at
 SEPARATION & PURIFICATION REVIEWS 13

Spent Fluorescent Tube Lights End-cut push process Phosphor

Glass tubes, Aluminium caps, connecting wires with tungsten filament

Dilute H2SO4 Lixiviation 1

Leach liquor 1 [Y, Eu and some Non-REMs] Filtration

Precipitation Oxalic acid

Filtration Supernate 1 containing Non-REMs

Y-Eu oxalate Dissolution Dilute HCl + KMnO4 SO42-

Solution [Y, Eu] Selective Reduction of Eu3+ to Eu2+ Precipitation

YCl3 Evaporation Supernate 2 containing Y Filtration EuSO4

Dilute HCl Lixiviation 3 Leach residue [La, Ce, Tb and some Non-REMs]

Filtration Leach residue containing Non-REMs

Leach liquor 2 Selective oxidation of Ce3+ to Ce4+ Strong Oxidising agent

[La, Ce, Tb] followed by precipitation of Ce4+ cum Precipitating agent

Supernate 3 [La, Tb] Filtration Precipitate containing Ce

Organic
Solvent Extraction Loaded Organic [La/Tb]
solvent
Stripping
Raffinate [Tb/ La] Loaded Stripping soln. [La/Tb] Stripping
Solution

Evaporation Tb/La Salt La/ Tb Salt Evaporation Regenerated Organic

Figure 4. Producing individual RE compounds from phosphor using precipitation, reduction, oxidation and solvent extraction.

600°C for 1 h to obtain 95% pure Y2O3. Innocenzi et al.[44]
added 250 kg of oxalic acid to leach liquor prepared by
lixiviating 1000 kg of phosphor to precipitate 666 kg of wet
RE oxalates. RE oxalates were calcined at 900°C to obtain
159 kg of 99% pure REOs. Innocenzi et al.[25] added oxalic
acid 20% more than the stoichiometric requirement to their
leach liquor to precipitate RE oxalate. Precipitation time was
1 h and was carried at room temperature. RE oxalates were
calcined at 600°C for 1 h to obtain ~98% pure RE2O3. Ippolito
et al.[45] added oxalic acid to their leach liquor and left the
solution for 1 h to precipitate 97% of the REMs. The pre-
cipitate thus obtained was calcined at 600°C to obtain 98.62%
pure RE2O3. Composition of the obtained REO was 82.22%
Y2O3, 8.38% Eu2O3, 2.43% Ce2O3, 2.29% Gd2O3, 1.77% La2O3
and 1.52% Tb2O3. Impurity contained 0.62% of phosphor
oxide, 0.48% of calcium oxide and 0.28% silica. Lee et al.[38]
compared precipitation capacity of Na2CO3, NaHCO3, NH4
HCO3, Na2SO4, K2SO4 and (NH4)2SO4 to screen most suita-
ble agent for recovery of Y and Eu from their leach liquor.
They added 20 mL solution of the precipitating agents with
20 mL of leach liquor and the resulting solutions were left for
24 h at 27°C. They found that carbonates and bicarbonates
have better precipitation capacity than sulfates. NaHCO3 and
NH4HCO3 were the best reagents for precipitating REMs
from leach liquor in terms of recovery. They were able to
precipitate 100% of Y and Eu in a precipitating time of 1 h.
Nakamura et al.[19] used three equivalent amounts of oxalic
acid (6.8 × 10−3 mol/L) to precipitate Eu selectively from
a raffinate containing Eu (8.4 × 10−4 mol/L) and Al (1.1 ×
10−3 mol/L). Takahashi et al.[18,65] added aqueous ammonia
(six times the molar quantity of REEs) to their leach liquor to
precipitate REEs as hydroxide which was re-dissolved in HCl.
Thereafter, they added oxalic acid (three times the molar
quantity of REEs) solution to precipitate REEs as oxalates.
Takahashi et al.[18] calcined RE oxalate thus obtained at 900°C
to obtain dissolution mixed REOs produced a mixed oxide
[Y2O3 (93%) + Eu2O3 (6%) + other REOs (~0.3%)]. Tanvar
and Dhawan[66] compared two routes for recovery of REMs
from leach liquor. In route A, they added NH4OH to their
leach liquor to increase its pH to 6.5. At pH 6.5, most of the
non-REM impurities precipitated out while REMs remained
in the leach liquor. Thereafter, they adjusted the pH to ~1.5
with the help of HNO3 and added oxalic acid. In route B, they
added oxalic acid and adjusted pH to ~1.1 with the help of
NH4OH. For both routes, RE precipitated as oxalates at the
respective given pH values. RE oxalates were subjected to
14 A. ANAND

Spent Fluorescent Tube Lights End-cut push process Phosphor

Glass tubes, Aluminium caps, connecting wires with tungsten filament

Leach liquor 1 [Y, Eu and some Non-REMs] Dilute H2SO4 Lixiviation 1

Organic Raffinate
Solvent Extraction Filtration
solvent [Non-REMs]

Loaded Organic [Y, Eu] Stripping Stripping Solution

Loaded Stripping Solution [Y, Eu] Regenerated Organic

Organic Raffinate
Solvent Extraction Evaporation Eu/Y salt
solvent [Eu/ Y]

Loaded Organic [Y/ Eu] Stripping Stripping Solution

Regenerated Organic Loaded Stripping Solution [Y/ Eu]

Y/Eu Salt Evaporation

Dilute HCl Lixiviation 3 Leach residue [La, Ce, Tb and some Non-REMs]

Filtration Leach residue containing Non-REMs

Leach liquor 2 Selective oxidation of Ce3+ to Ce4+ Strong Oxidising agent

[La, Ce, Tb] and precipitation of Ce ions cum Precipitating agent

Supernate 3 [La, Tb] Filtration Precipitate containing Ce

Organic
Solvent Extraction Loaded Organic [Tb/La]
solvent
Stripping
Raffinate [La/ Tb] Loaded Stripping soln. [Tb/ La] Stripping
Solution

Evaporation La/ Tb Salt Tb/ La Salt Evaporation Regenerated Organic

Figure 5. Producing individual RE compounds from phosphor using solvent extraction and precipitation.

calcination for obtaining REOs. Recovery through route
B (>90%) was far more in comparison to route A (~40%).
Tunsu et al.[11] used oxalic acid for precipitating REEs out of
their leach liquor. The precipitate was calcined at 800°C for
2 h to produce a mixed REOs [Y2O3 (94.61%) + Eu2O3
(5.09%) + REO (0.26%)]. Tunsu et al.[31] subjected loaded
stripped liquors containing Y and Eu to oxalate precipitation
and calcination at 800°C. Purity of Y2O3 and Eu2O3 thus
produced were 99.7% and 91.6%, respectively. Wu et al.[43]
have suggested adding ammonia water for precipitating
Y from Eu-separated filtrate. The precipitate can be dissolved
in sulfuric acid and Y2(SO4)3 can be obtained by evaporating
the solution at 70–80°C. Yu et al.[53] added oxalic acid to their
leach liquor to precipitate Y and Eu as oxalates. Oxalic acid
was added to the leachate in the mass ratio 2.5:1 (H2C2O4:
REEs), pH of the solution was 2; its temperature was main-
tained at 80°C; precipitating time was 4 h. Zhao et al.[67]
added ammonium carbonate their loaded strip liquor to pre-
cipitate REMs as carbonates.
Based on the literature studies generalized flow-sheet that
seemed most suitable to reviewer for production of pure
individual RE compounds have been provided in Figures 4
and 5.
Summary
The following quote from Binnemans et al. (2016) clearly
answers the second question asked at the beginning of this
chapter about the efficiency of the existing processes, “Despite
the vast literature dealing with lab-scale research efforts of
recycling REMs from phosphor, less than 1% of REEs were
commercially recycled in 2011”.[21,26] Existing literatures have
so far failed in suggesting a commercially acceptable process
for recycling REMs from phosphor.
Probable reason behind the failure: “The recycled lamp
phosphor has a very complex chemical composition, with
large compositional variations between countries and between
lamp recycling companies”.[26] There is a need of process

which can yield comparable extractions with phosphors of
different origin. On the contrary, operating condition sug-
gested by any existing literature is suitable for the phosphor
utilized in their work. The same value of input parameters
might not yield similar extraction for a phosphor of different
composition.
Possible approach to trounce the failure: instead of disco-
vering a single optimum value of input parameters, finding
a range for working variables would be more helpful in
processing phosphors of different compositions thereby devel-
oping a robust process. Moreover, flexibility in working vari-
ables is essential to run an industry or a small plant where
values of operating parameters are required to be varied,
without influencing the extractability, as per the price and
supply of input resources.
Literature gap: To the best of our knowledge, there is a lack
of study suggesting a range for input parameters which can
yield maximum extraction. In order to fill this gap, we need to
explore range for operating parameters while carrying out any
study rather than stopping at a single optimum condition for
the process.
Inspiration: “Even though an economical, industrial scale
phosphor recycling process does not exist, there is great interest
within industry”.[51] We believe that once a robust process for
recycling phosphor is developed recycling industries will imple-
ment them for mass production of RE compounds.
ORCID
Amit Anand http://orcid.org/0000-0002-1691-6967
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