Sustainable Materials and Technologies 32 (2022) e00401

Contents lists available at ScienceDirect

Sustainable Materials and Technologies

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

A critical review of end-of-life fluorescent lamps recycling for recovery of

rare earth values
Nikhil Dhawan *, Himanshu Tanvar
Metallurgical and Materials Engineering, Indian Institute of Technology, IIT-Roorkee, Uttarakhand 247667, India

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

Keywords: The review presents a critical analysis of different recycling processes, recent advancements, market value po­
Fluorescent lamps tential for recycling waste fluorescent lamps (FLs), and recovery of rare earth elements. The limited primary
Recycling resources, strict environmental norms, and the growing demand for rare earth elements call for global phosphor
Mercury
recycling from waste FLs. Commercial-scale collection and recycling of fluorescent lamps are currently practiced
Rare earth elements
Microwave
to separate mercury for safe disposal; however, processing associated phosphor powder rich in rare earth
compounds is still evolving. Phosphor consisting of multiple rare earth minerals (Y, Eu, Ce, Tb, La) can be
considered a potential secondary source. The literature findings show that research efforts lean towards com­
bined pyro-hydrometallurgical processes because of higher recoveries and apparent dissociation of inert phases.
Advanced processing techniques such as microwave processing and mechanical activation can significantly in­
crease the recovery rate; however, limited scale-up guidelines are available. Recycling rare earth phosphor is
analogous to ore processing with the advantage of reduced energy consumption and waste emission. Approxi­
mately 300 g of rare-earth compounds can be recovered from 1 kg of phosphor waste, analogous to the pro­
cessing of 11.9 to 22.5 kg site-specific primary ore. Recycling fluorescent lamps for rare earth recovery may
become inevitable globally because of prevailing looms of the rare earth supply chain.

1. Introduction safe disposal concerning environmental damage and is currently prac­

The usage of rare earth elements (REEs) has significantly developed
because of the transition to a green, low-carbon economy. In the modern
era, exceptional properties such as optical, chemical, catalytic, mag­
netic, and luminescence of REEs lead to numerous applications [25,40].
The enormous demand and relatively limited global distribution of REEs
have led to the increase in prices of most REEs [6]. Therefore, recycling
and utilizing secondary rare earth sources for a sustainable, circular
economy is the only option to meet the future’s raw material demand
[12,77]. REEs’ secondary resources involve phosphor in the fluorescent
lamp, tube light, cathode ray tube, LEDs, magnet in the hard disc drive,
wind turbine, electric motors, and battery waste [3,140]. Phosphors in
fluorescents are a rich source of critical, rare earth elements such as Y,
Eu, Tb, and Ce and nearly, 79% and 63% of global consumption of Y and
Eu are entailed in phosphors; and therefore, recycling is critical for
resource conservation [53].
Florescent lamp (FL) mainly consists of glass, metal casing, plastic,
phosphor, and mercury [13,145]. The presence of mercury demands
ticed on an industrial scale. The phosphor used for luminescence
behavior makes up to 2 wt% of FL and consists of 9 to 26% RE content,
significantly higher than the RE ore deposits [84,126]. The current
recycling rate in some major lamps producing countries is China 4%,
Canada 7% [27], Japan 9% [8], United States 20% [140], and South
Korea 28% [161]. More than 95% of the FLs used in India are manu­
factured domestically, while the phosphor compounds are imported
from China. As per the lighting industry data published by the Electric
Lamp and Component Manufacturer Association of India (Elcoma); it is
reported that the use of FLs in India was highest at 730 million pieces
during the year 2014, which is gradually decreasing by 15–20% annu­
ally and the consumption has reduced to approximately 160 million
pieces in the year 2018–19 [31]. The decreasing FL consumption is
mainly due to increased usage and market share of LED lighting, which
is expected to increase further. Therefore, recycling processes for eco­
nomic and environmental benefits are necessary given the inevitable
generation of discarded FLs [31,104]. The GHG emissions during the life
cycle of different FLs are 145.89 kg and 685.77 kg CO2-equivalent in

* Corresponding author.
E-mail address: nikhil.dhawan@mt.iitr.ac.in (N. Dhawan).

https://doi.org/10.1016/j.susmat.2022.e00401
Received 22 June 2021; Received in revised form 2 February 2022; Accepted 4 February 2022
Available online 11 February 2022
2214-9937/© 2022 Elsevier B.V. All rights reserved.
N. Dhawan and H. Tanvar
compact fluorescent lamps (CFL) and linear fluorescent lamps (LFL),
respectively. The major contributor is the use stage accounting for 82%
of total GHG emissions in CFLs (and 98% in LFLs). The raw material and
FLs manufacturing embody approximately 17.5% (25.49 kg CO2-eq) in
CFL [18,52]. Recycling of waste FL will not only reduce energy usage
and GHG emission but also result in saving natural resources as these
recycled materials will be readily available for remanufacturing [87].
Technically, mineral processing of ores is analogous to processing
waste materials (FL), as shown in Fig. 1. The processing method for both
ore and waste differs in the required processing step and metallurgical
treatment due to differences in underlying phases and complex associ­
ations. Different types of REE-rich waste material require different
processing routes due to heterogeneous composition and associated
complex mineralogy, and thereby once complete, the discrete recycling
process cannot be generalized.
Recycling REEs from FLs is to be considered due to abundant avail­
ability, large amounts of REE, and environmental protection. Few re­
views were published on recycling waste FL in the past years
[4,13,128,145]. These works describe the initial stage recycling,
including direct reuse of phosphor, separation of different phosphor
components, mercury removal, chemical treatments, and Y, Eu extrac­
tion processes. However, limited insight on critical REE (Tb, Eu) re­
covery is presented, and most of the reviews are published more than
half a decade ago, and significant advancements have evolved since
then. Tremendous developments can be observed in the literature to
recover other valuable elements (Ce, Tb, Eu, La) from the waste phos­
phor due to high demand and economics [53,83,101].
Recent advancements in the RE recovery process include applying
advanced processing technologies such as mechanical activation (plan­
etary ball milling); [43,44,84,130], and microwave treatment [116,117]
to unlock the REEs from complex phosphor phases. These processes offer
rapid, economically viable, and environmentally sound processing.
Furthermore, recent development in separating different REEs using
zinc cementation, liquid-liquid extraction, reduction, and precipitation
is significant [42,91,104].
Therefore, this review presents an in-depth study on recent ad­
vancements in recycling and the potential recovery of rare earth ele­
ments in the context of phosphor. An overview of the primary
processing, such as Hg removal and separation of different components,
is provided to understand industrially adopted processes for the safe
disposal of FLs. An assessment of the market value of FLs is carried out,
Fig. 1. Flow diagram showing analogous processing route of ore and FL waste for metal recovery.
2
Sustainable Materials and Technologies 32 (2022) e00401
and a comparison with primary ore is highlighted to delineate the pos­
itive aspects of RE recovery. A detailed study on hydrometallurgical
treatment involving leaching and post-leaching recovery (precipitation,
solvent extraction, reduction) of various phosphor types and REEs
involved is presented. Pre-treatments (thermal/mechanical/microwave
treatment) play a decisive and significant role in downstream recycling
of REEs (or phases) that otherwise exhibit resistance to dissolution. An
exhaustive literature search was performed, and a complete processing
flowsheet is presented to separate and recover different RE compounds
from waste FLs. The prospects of process development for RE recovery
from FL are highlighted to provide future technological development
guidelines for recovering various RE compounds.
1.1. Primary rare earth reserves
RE minerals are several and diverse (around 245 RE minerals in
carbonates, fluorocarbonates, hydroxyl-carbonates, oxides, silicates,
phosphors are identified) with heterogeneous composition [37,68,140].
The list of essential RE minerals and their composition are shown in
Table 1. Bastnasite ((Ce,La)(CO3)F), monazite ((Ce,La)PO4), xenotime
(YPO4), loparite [(Ce,Na,Ca)(Ti,Nb)O3], and apatite [(Ca,REE,Sr,Na,
K)3Ca2(PO4)3(F,OH)] are majorly used for REEs production
[45,123,148]; and 95% of world’s reserve of REEs are of bastnasite,
monazite and xenotime [37]. The distribution of RE reserves, produc­
tion, and application is shown in Fig. 2 [140]. Global reserves of REEs
were estimated on a rare-earth-oxide (REO) basis to be 130 million
metric tons, and significant reserves are in China (38%), Brazil (19%),
Vietnam (19%), Russia (10.35%), and India (6%) [57,140].
Various literature reviews mentioned REE recovery from primary
minerals [71,111,81,144]. Typically, the RE ores processing involves
crushing, grinding, and beneficiation to obtain RE concentrate, followed
by leaching, solvent extraction (SX), precipitation, and reduction to
recover RE salts (Fig. 2). Beneficiation is generally carried out through
froth floatation in which a collector (sodium oleate) is added, which
adheres to the RE bearing particle (bastnasite, xenotime, monazite) and
increases hydrophobicity and is skimmed off from the top of the floa­
tation column [81]. A RE concentrates with a grade of 10–15% REO is
obtained after froth floatation and is further processed through acid
leaching using HCl, HNO3, or H2SO4. The dissolved REEs are recovered
from the solution via SX and ion exchange methods using commercial
reagents such as D2EHPA, HEHEHP, Versatic 10, TBP, and Aliquat 336
N. Dhawan and H. Tanvar Sustainable Materials and Technologies 32 (2022) e00401

Table 1
List of essential REEs minerals and their typical composition [68,81].
(Wt%) Y2O3 La2O3 CeO2 Pr6O11 Nd2O3 Sm2O3 Eu2O3 Gd2O3 Tb4O7 Dy2O3 Er2O3 Yb2O3 Lu2O3

Bastnasite 0.1 32 49 4.4 13.5 0.5 0.1 0.3 – – 0.1 – –

Monazite 2.1 23 45.5 5 18 3.5 0.1 1.8 – – 1 – –
Xenotime 61 0.5 5 0.7 2.2 1.9 0.2 4 1 8.7 5.4 6.2 0.4

Fig. 2. Standard flowsheet for rare earth ore processing with global reserve and production data.

[68,148]. that the actual composition varies widely with the manufacturer and is
difficult to generalize. The dynamically changing FL phosphor compo­
sition reflects that the recycling process needs to be robust and cannot be
1.2. Basic construction, properties, and phosphor composition of
generalized with one type of feed material.
fluorescent lamps
The trichromatic phosphor system consist of major phases as Y2O3:
Eu3+ (YOX), CeMgAl11O19:Tb3+ (CAT), LaPO4:Ce3+, Tb3+ (LAP) and
Different compact and tubular fluorescent lamps (CFL and TFL) are
BaMgAl10O17:Eu2+ (BAM). The crystal structure analysis is critical for
made of thin transparent glass with a phosphor coating inside the lamp’s
any metal recovery process,because the chemical association of different
glass. The lamp is filled with argon and mercury vapors with electronic
elements determines whether the target metal is freely available or in a
or magnetic ballast in CFL and aluminum caps in a TFL. The electric
locked structure in the host matrix, which greatly impacts the energy
current inside the fluorescent lamp ionizes the mercury vapor to produce
required for phase dissociation metal recovery. The crystal structure of
ultraviolet light, further re-radiated as visible light when it strikes the
these phases is shown in Fig. 4. The crystal structure was constructed
RE-containing phosphor coating. Phosphor is the compound that can
using a ball and stick software to arrange atomic species in the unit cell,
absorb the high energy (short wavelength) emitted by electrons and
while the structural parameters for the phases were determined from the
convert them to lower energy (longer wavelength) visible light. Fig. 3
literature [94]. The crystal structure of YOX phosphor is a cubic type of
(a) represents the working principle of a tubular FL. Different features of
structure with coordination of each Y atom with 6 oxygen atoms to form
commercially available FLs, energy consumed, durability, mercury
YO6 octahedra [93]. Eu atoms replace Y atoms on doping to enhance the
content, efficacy, and color rendering index (CRI) are shown in Fig. 3 (b)
luminescence behavior. Y and Eu are only bonded with oxygen, and the
and the critical phosphor systems with their chemical formula and color
underlying structure can be broken by attacking the Y/Eu-O bond. LAP
of the light emitted under UV radiations are illustrated in Fig. 3 (c).
phosphors consist of a monoclinic crystal structure in which La3+ atoms
Phosphor compounds activated with REE emit brighter light and
are bonded in nine-fold coordination with O; four of the oxygen atoms
consume less energy than calcium-based and halo phosphate phosphors
are oriented in a distorted tetrahedron (PO4) [38]. BAM’s crystal lattice
[145]. Calcium based and halo phosphate phosphor are used in old
and atomic arrangement correspond to the hexagonal crystal lattice, like
generation of FLs (8.0% Y, 1.0% Eu, 0.9% Tb, 1.6% La, 1.4% Ce, 19.5%
β-alumina (NaAl11O17). The crystal structure consists of two oxygen
Ca, 16.1% P). The most recent FLs consist of RE activated trichromatic
close-packed spinel blocks of MgAl10O16, separated by the mirror plane
phosphor (29.1% Y, 1.9% Eu, 3.4% Tb, 7.8% La, 5.7% Ce, 34.4% Al,
of BaO, as shown in Fig. 4 (d).
2.8% Ca, 6.6% P) which are retained in red phosphor (54%), blue
Eu2+ atoms partially replace the Ba ion and are present in the mirror
phosphor (12%) and green phosphor (34%) [4,13,48,64,66]. A typical
plane [155]. The CAT structure is the same as that of BAM and is often
SEM micrograph of real phosphor depicting the presence of phosphor
called magnesia-alumina spinel structure consisting of spinel blocks of
particles and waste glass cullet is shown in Fig. 3 (d). The chemical
MgAl11O19 with Ce, Tb in the mirror plane. The rare-earth ions (Ce3+-
composition of the pure tricolor RE phosphors, and the average chemical
Tb3+, Eu2+) are placed at the mirror planes in both phosphors and are
composition and standard deviation in the real phosphor waste samples
locked in the spinel structure. It is depicted in the unit cell
reported in the literature are presented in Fig. 3 (e). These values show

3
N. Dhawan and H. Tanvar
Fig. 3. (a) Schematic representation of the working of a tubular FL, (b) Features of commercially available FLs, (c) Commercially available RE activated phosphor
samples, (d) SEM image of real phosphor waste, (e) Chemical composition (wt%) of commercial and real waste phosphor powder.
representation of the different phosphor phases that REE in YOX and
LAP are freely available in the unit cell for separation, while Tb, Ce, Eu
in BAM, and CAT phases are locked in the mirror plane and are not freely
available. The surface energy of the spinel MgAl2O4 at 300 K is 2.827 J/
m2, which is higher than the oxides of Y, Ce (2.162, 2.296 J/m2),
depicting a high energy requirement for dissociation [132] and exhibit
resistance to acid attack [53].
The REE extraction response from different phosphors is strongly
dependent on the phosphor phases’ crystal structures. These structures
lead to high chemical stability and high energy input requirements to
break the chemical bonds. Phosphors, particularly with a high terbium
content such as LAP, CBT (Gd, Mg) B5O12:Ce3+, Tb3+), CAT, are more
paramagnetic than YOX and others [30]. Knowing the crystal structure
can elucidate the mechanochemical treatment or phase transformation
during alkali fusion. The treatments cause changes in the crystallite
surface and induce strain in the phosphor phases’ crystal lattice. The
disordering of the crystal structures leads to amenable downstream
processing such as leaching or mild alkali treatments [83,155].
1.3. Market value calculation
Urban mining for the REEs is vital because of the high economic
potential and environmental issues associated with waste. The current
world situation during the COVID-19 pandemic revealed that the supply
chain for crucial raw materials (including REE) for manufacturing
electronics is increasingly vulnerable to social, geopolitical, and tech­
nical disruptions [7]. The disruption in the supply chain has led to a
4
Sustainable Materials and Technologies 32 (2022) e00401
dynamic increase in price and global supply risk of these elements. The
alternative solution to overcome the supply risk of these elements is
domestic recovery from waste streams [63]. The rare earth metal prices
have substantially increased in the past few years. The Tb prices have
reached to highest since 2012 (497 US$/kg), showing a 93% price hike
in 2020 (958 US$/kg) [15]. Among the different REEs, the major price
hike can be observed for Nd, Dy, Tb, Eu, and Gd in the range of 20 to
95% during 2020 [7]. The accelerated price hike is due to trade issues
and China’s global heavy RE production dominance.
The market value of any commodity provides an estimate of the
asset’s worth, and the calculation of market value is useful for evalu­
ating waste resource importance. The average material distribution of
discarded FLs is shown in Fig. 5 (a) [4,13,128,130]. A measure of both
quality (REE concentration) and quantity (annual waste stream pro­
duction) quantifies the economic and strategic potential to recover REE
from any waste stream. FL with average RE content of 0.5–1% and
annual global production of more than 1 million units represents a
potentially viable source for domestic recovery of REE [7,34]. The
market value (Mv) was calculated for the discarded fluorescent lamps
using Eq. (1), where Ci and Pi are REEs content and market price of
recoverable REEs and is presented in Fig. 5 (b) [9,124]. The contribution
of different fractions of lamps in the overall market value is shown in
Fig. 5 (c), depicting the significant contribution from phosphor (75%).
The total market value of 1 ton of discarded FLs was calculated as US $
822.2, provided they can be entirely extracted at 100% purity. The
market value of REEs ore was also calculated using the average REEs
content of 1.7%, and it was found that one ton of each REE ore (of Y, Eu,
N. Dhawan and H. Tanvar Sustainable Materials and Technologies 32 (2022) e00401

Fig. 4. Crystal structures of FL phosphors: (a) Y2O3:Eu3+, (b) LaPO4, (c) CeMgAl11O19:Tb3+, (d) BaMgAl10O17:Eu2+.

Fig. 5. (a) Fraction of different components in FL, (b) overall market value discarded fluorescent lamps, (c) contribution of different fractions of lamps to mar­
ket value.

Tb, Ce) can generate a total market value of US $ 20,558.08, i.e., one-ton ∑
phosphor (Y-23%, Eu-3.4%, Tb-2%, Ce-4.8%) retrieved from FLs is Mv = Ci .Pi (1)
equivalent to 19.53 ton of primary ore.
i

5
N. Dhawan and H. Tanvar
2. Recycling of fluorescent lamps: primary processing and
mercury removal
A summarized unit operation and a typical flowsheet for shredding
and separation of waste FL components on an industrial scale are pre­
sented in Fig. 6. The two widely adopted processes for waste FL pro­
cessing are end push method and shredding operations. At the end cut
push method, the end caps of aluminum in the FLs are removed or cut
off, and waste phosphor on the inside walls of glass is pushed out using
scrapper, high-pressure air, or water [5,39,75,112,115,145]. The
metallic mercury and phosphor are collected, and mercury vapors are
trapped with the gas flowing through the activated carbon filters [17].
The metallic caps and glass are crushed to recover metals and build
glass-wares or new lamps [105]. The phosphor collected through the
end-cut method is free of impurities such as fine glass; however, manual
operations and long processing duration are required, and on an in­
dustrial scale, the process has achieved a capacity of 300 million lamps
per year [146]. Several companies have commercialized this method,
namely Mercury Recovery Technology Company in Holland, WEREC,
OS-RAM, BISON, and OSRAM (owned by Siemens) companies in Ger­
many have worked jointly in developing the “end cut/air push” system
[74,95].
The shredding and sieving process involves the dry or wet crushing of
entire FLs and further sieving to separate different components. In
Germany, Switzerland, and Finland, companies have been adopted wet
crushing on an industrial scale [89], wherein the tubes are broken in
ethanol or 30% aqueous acetone to capture mercury vapors and avoid
environmental contamination [13,28,145]. In the dry crushing of FLs, a
closed or vacuum environment is maintained to avoid escaping mercury
vapors; however, many fine glass particles contaminate the phosphor.
Hence, the phosphor recovered requires further resources to eliminate
these impurities. Globally companies such as Eco Recycling Ltd. [26] in
India, Fluorescent Lamp Recyclers Technologies [32] Inc. in Canada,
AERC Recycling Solutions, Veola environmental services in the USA,
and Lampcare in the UK have developed dry crushing equipment to
avoid the leakage of mercury [1,31,72].
The current scenario suggests that reducing mercury pollution is the
key factor in recycling FLs. Recently companies like Air Cycle
Fig. 6. Flowsheet for initial stage recycling and physical separation of waste FLs.
6
Sustainable Materials and Technologies 32 (2022) e00401
Corporation, Terra Cycle in the USA have developed innovative tools
like Bulb Eater drum-top lamp crushers, equipped with a side-mounted
dust filter unit containing HEPA filter [2]. The filter works in conjunc­
tion with an activated carbon filter located in the steel canister [21].
During crushing, the activated carbon filter actively captures and neu­
tralizes the mercury vapor released over 99.99% from the lamps (LFLs/
CFLs). Bulb Eater lamp crusher unit reduces handling, labor cost, time
and is easily portable to local sites of available discarded lamps. Mercury
in the phosphor powder is separated by performing different chemical
and thermal processing routes involving retorting and distillation.
The industrial-scale process developed by Rhodia (Solvay Group)
was commercialized in 2012 and treats more than 2000 tons of phosphor
dust per year. Collected lamps are subjected to the end cut push method
to recover mercury and separate different components. Phosphor pow­
der is then subjected to the separation of halo phosphate phosphor
through physical beneficiation using hydro cyclone and leaching with
18 M sulfuric acid [23,90,121]. The residue is collected, and REE is
further leached in nitric acid, followed by precipitation of Y, Eu oxalate,
and calcination to mixed oxides [86]. Additionally, a German lighting
company NARVA GmbH in Freiberg and phosphor dust recycler, FNF
Freiberg and TU Frieberg have jointly developed a recycling process for
rare earth recovery from phosphor dust and is known as the SepSelsa
process [121,133]. The process includes solid-state chlorination of
phosphor dust with ammonium chloride. Y, Eu chlorides formed during
heating are further dissolved using water and recovered by precipitation
with oxalic acid.
FLs enclose hazardous mercury (present in the solid, liquid, and
gaseous forms, oxidation states of 0 to 2) in the range of 6–21 mg per
lamp depending on the shape and size of linear and compact FLs. They
can interact with the constituents of lamps via physisorption, chemi­
sorption, amalgamation, and oxidoreduction reactions [73]. It is re­
ported that due to continuous working hours (long exposure to UV
radiation and bombardment of mercury metals and ions) of FLs (LFLs/
CFLs), the mercury is mainly absorbed in the phosphor (81.36–89.35%),
and a small amount of it is found in base caps (2.36–3.45%) and glass
(8.27–16.27%) [22,77,109,110]. The literature review of the processes
for mercury removal is summarized in Table 2. The thermal route in­
volves heating at a high temperature (400 ◦ C) above the boiling point of
N. Dhawan and H. Tanvar Sustainable Materials and Technologies 32 (2022) e00401

Table 2
A summary of processes adopted for mercury removal from FL waste.
Process Description
Thermal • Heating at 400 C for 4 h removed 95%
◦
desorption Hg.
method • For complete Hg removal from glass, (in
HgO form) temperature up to 800 ◦ C was
required. Heating with reductant
(sodium borohydride, Fe powder, Na
oxalate) lowers the removal temperature
and at 300 ◦ C for 2 h, > 98% Hg was
removed.
Chemical • Dissolution/Stripping of Hg with the aid
method of acid mixture (HNO3, HCl); 80 ◦ C;
pressurized He; 3 h.
• Recovery of Hg from solution via ion
exchange and SX.
• Maximum 36% Hg removal with a mild
acid solution (6% conc), high conc.
Dissolves phosphor as well.
• Dissolution of >90% Hg using 0.025/
0.05 M I2/KI solution at 21 ◦ C for 2 h.
• Oxidative leaching (0.5 M NaOCl/ 0.2 M
NaCl, pH -7.5) and electrowinning
process (30 g/L citric acid, 6A, 120 min)
to recover 81% of the Hg.
Adsorption Adsorption of Hg vapors emitted during
crushing using carbon, HEPA filters,
functionalized carbon nanotubes (CNT–I,
CNT–S).
acetate (pH 2.5) or sodium dodecyl sulfate (pH 9.6) as the collector
separated (from white phosphor) 80–90% red and green phosphor in the
Reference sink. Zeta potential was negative in the entire pH range, while the red,
green, and blue phosphor had their isoelectric point located around a pH
[11]; [17]; [24];
[67]; [108] of 7.7, 6.8, and 4.8, respectively [47,154]. High gradient magnetic
separation is also reported for separating >90% green phosphor from
waste phosphor mixture using high gradient magnetic separation
(10,000 G) with a purity of 87%. The magnetic susceptibility for
different types of phosphor phases is in the order: green > blue > red >
halo phosphate [149]. A recent study reported that high gradient
magnetic separation is not a suitable method for the separation of FL
[19]; [67]; [69]; phosphors due to limited separation efficiency. However, it may be
[99]; [136]
considered a pretreatment for their separation using superparamagnetic
carriers [14]. Besides physical separation techniques, chemical methods
are also reported to separate calcium halo phosphate phosphor from the
RE-based phosphor and are more efficient. Mild acid washing with
0.5–1 M acid for a short duration (10–15 min) can separate the Ca and P
impurities from the phosphor sample and beneficiate the residue’s RE
values [30,139]. The separation of halo phosphor in mild acidic condi­
tions is due to the decreasing solubility of the phosphors in the order:
halo (Ca10(PO4)6FCl: Sb3+, Mn2+) > YOX (Y2O3:Eu3+) > LAP (LaPO4:
Tb3+, Ce3+) [101]. Chemical methods are preferred over the physical
separation due to efficient removal of calcium-based and halo phosphate
[11,36] phosphor and are relatively easy to operate.
3.2. Hydrometallurgical processing

mercury for several hours to volatilize and collect Hg via condensation
into decanters [17,67]. Hg was removed from phosphor powder (< 10
mg/L) using a high-temperature furnace (540 ◦ C, 4–5 h) under inert gas
conditions and a closed gas pipe system for the exhaust gas over carbon
filters [101]. Chemical methods involve solubilization of mercury in
organic acids or I2/KI solution; however, co-dissolution of RE from the
phosphor is observed in organic acid [69].
The removal of the phosphor layer and its mercury attached to the
glass surface has been reported by the stirring method using an acidic
extractant (L/S-10) [109]. Mercury can be further recovered from the
solution using Dowex IX anion exchange resin or reducing agents such as
sodium dithionite (Na2S2O4) [136]. The chemical method is more
complicated than the thermal processing route and involves multiple
steps and reagents; therefore, the thermal process is usually opted
commercially to decontaminate Hg from the FL waste stream. The
collected mercury can be recycled for the production of new FLs.
3. Methods for REE extraction from phosphor dust
3.1. Separation of halo phosphate and RE phosphor
The calcium bases and halo phosphate phosphor does not contain
any REE and are used widely in first- and second-generation FL lamps.
The presence of halo phosphor and the tri-colored phosphor activated
with REE makes the REE recovery process difficult due to interference of
unwanted impurities (Ca, P). Therefore, various physical separation
techniques, including sieving, floatation, gravity separation, magnetic
separation, and centrifugal classification, have been carried out to sort
out different phosphor types separately. Takahashi et al. studied the
pneumatic classification to separate calcium phosphate phosphor and
subsequently concentrate RE in the phosphor from 13.3% to 29.3%,
with a yield of 32.9% [125]. Hirajima et al. reported dense medium
centrifugation (di-iodomethane as dense media and sodium oleate as a
surfactant) for the separation of low-density calcium halo phosphate
(specific gravity − 3.1) in a float from high-density RE activated phos­
phor (specific gravity 4.4–5.3) in the sink product [46]. However, dense
media separation has little commercial application and is limited to
laboratory/ batch scale. Two-stage floatation with dodecyl ammonium
Hydrometallurgy is a traditionally accepted method for recovering
REEs and mostly focuses on the direct leaching of phosphor powder in an
acid solution of HCl, HNO3, or H2SO4. The dissolution of REEs depends
essentially on the crystal structure of the phosphors, which in turn
governs the economic, environmentally suited recovery. HCl and H2SO4
behave similarly in RE solubility with RE chloride and sulfate formation
in the solution. During the leaching process, HCl loses H+ ion, and
attacking the oxygen destabilizes the RE oxide lattice while the un­
bounded RE cation forms an aqua complex with chloride ion and results
in the dissolution of RE in the form of chlorides [29]. Leaching with
H2SO4 is preferred because it causes limited co-dissolution of Ca and Ba
due to the formation of insoluble sulphates [12]; however, coprecipi­
tation of REEs also occurs, resulting in losses. Impurities (hal­
ophosphors) consume large amounts due to faster leaching kinetics than
REEs and limit the solid to liquid ratio. Therefore, mild acidic conditions
are preferred for separating halophosphor, which subsequently eases the
downstream processes (pH-dependent). Typical leaching conditions for
phosphor involve acid concentration between 1 and 6 M at temperature
30–95 ◦ C, for 0.5–50 h at a pulp density of 5–30%
[5,12,77,80,84,92,126]. [58] studied the Y recovery by H2SO4 leaching
with 10%v/v H2O2, (2 M, 20% w/v pulp density, 3 h, 70 ◦ C) followed by
purification using NaOH and Na2S; however, 35–45% Y is lost during the
process. Low acid concentration requires extended leaching time
(24–30 h) and higher operating temperature (80–90 ◦ C), while rapid
dissolution is achieved with high acid concentration at the optimal
temperature (40–60 ◦ C). Optimizing different parameters is essential
given desired operating conditions, cost of acid, and time limitations.
[134] reported the recovery efficiencies of 97% Y, 95% Eu at optimal
conditions of 0.5 M HNO3, at 20 ◦ C for 24 h at 10% pulp density, while
[20] found that at operating conditions of 4 N H2SO4, 90 ◦ C, 20% pulp
density 85% Y was extracted. It is observed that Y, Eu leaching in HCl
acid solution follows the empirical model’s logarithmic rate expression
with a mean activation energy of 70–80 kJ/mol. Recently, solid-state
chlorination process (NH4Cl, 300 ◦ C, 70 min) for converting Y, Eu
oxide into chlorides followed by separation (95% Y, 92% Eu) using an
organic mixture of 2, 4- pentanedione diluted in ethanol was also
studied; however, the process is ineffective for dissociation of Tb, Ce
bearing phases. Moreover, a higher HCl concentration protonates the
blue phosphor and releases HPO42-, forming insoluble precipitates of Y3+

7
N. Dhawan and H. Tanvar Sustainable Materials and Technologies 32 (2022) e00401

and Eu3+[104]. /
LaPO4 + 3HCl→LaCl3 + H3 PO4 ΔGo90◦ C = 41.12kJ mol (5)
The thermodynamics of the leaching process of RE in HCl solution
was analyzed using HSC Chemistry 5.1 [49]. The underlying chemical /
MgAl2 O4 + 8HCl→MgCl2 + 2AlCl3 + 4H2 OΔGo50◦ C = 354.64kJ mol (6)
reaction and Gibbs free energy at 90 ◦ C are shown in Eq. (2-6). Due to
the database’s unavailability for CAT and BAM phases, the MgAl2O4
3.2.1. Mechanical activation assisted processing
phase was considered due to the similarity in the crystal structure (spinel
Mechanical activation (MA) induces physiochemical changes in the
form). The negative Gibbs free energy for dissolution of RE (Y, Eu, Tb)
crystal lattice, causes stress, defects, particle size reduction, decreases
oxide in Eq. (2-5) shows the chemical reaction’s thermodynamic feasi­
the specific surface area, lowers the activation energy, and enhances the
bility. The positive Gibbs free energy for the MgAl2O4 spinel phase (Eq.
chemical leaching process. Our recent study found that MA of trichro­
6) shows that the leaching reaction is not thermodynamically favored,
matic phosphor waste for 20 min facilitates the RE leaching with mild
and the dissociation of phase does not occur. Based on the crystal
conditions (2 M HNO3) and more than 90% Y, Eu was recovered [130].
structure analysis, the RE (Tb, Ce) in CAT, BAM phases are locked in the
However, Ce Tb bearing CAT phase was found inert to milling up to 2 h
spinel structure’s mirror plane and can only be freely leached after
at 350 rpm and leaching in 6 M HNO3 solution. Similar results were
liberation through dissociation of the respective phases. The YOX phase
reported recently by Ippolito et al., where the maximum dissolution of
present in phosphor is readily soluble in acid solution, while the other
35% Tb was achieved after MA and sulfuric acid leaching [65]. How­
phases (BAM, CAT, LAP) require additional processing or thermal
ever, the authors found thermal treatment (pyrometallurgical approach)
treatment. The decreasing resistivity of the RE phosphor phase to the
better than mechanical activation, where more than 80% Tb recovery is
mineral acids follows the order: Y2O3:Eu3+ > LaPO4:Ce3+, Tb3+ > >
attained. The MA process (600 rpm, 60 min) reduced the activation
BaMgAl10O17:Eu2+ > CeMgAl11O19:Tb3+.
energy for the leaching process (6 M HCl, 60 ◦ C, 15 min) from 53 kJ/mol
Selective dissolution and extraction of YOX phase from the phosphor
to 11 kJ/mol with the recovery over 90% Y, Eu, and 80% Tb [120,126].
powder were explored using functionalized ionic liquid betainium bis
It was found that the Ce, Tb bearing phases dissociates at a high rotation
(trifluoromethylsulfonyl)imide, [Hbet][Tf2N] to avoid the unwanted
speed (500–600 rpm) and reflected higher energy requirements for the
dissolution of halo phosphors during leaching. The targeted Y and Eu
dissociation of the spinel structure [127]. The alkali mechanical acti­
were then precipitated using oxalic acid to regenerate 80% YOX phase
vation of phosphor with NaOH (300 wt%) at 550 rpm for 60 min, 1:40
(Y2O3:Eu3+). The inefficient solvation of anions (constituents of hal­
powder: ball before leaching (2 M H2SO4, 80 ◦ C, 120 min), dissolved
ophosphor), and thermomorphic properties of the IL are beneficial for
more than 90% Y, Eu, and 80% Ce, Tb values [44]. The results show that
the efficient, selective, and green recovery of REEs [23]. Cheaper and
mechanical activation is an efficient method for recovering heavy REEs
efficient alternatives of [Hbet][Tf2N] ILs in levulinic-ChCl and levulinic
from FL phosphor waste and has a promising potential with less energy
acid were developed [100]. Among different choline chloride-based
consumption, reduced acid consumption, and high efficiency to
eutectic solvents, the higher solubility of YOX and non-selectivity to­
contribute towards sustainable process development for FL lamp recy­
wards the halo phosphor was observed in levulinic-ChCl (H2O vol% =
cling and RE industries.
10; 80 ◦ C; 48 h; L/S-10), and further, simple levulinic acid also showed
similar results. Moreover, the contrast observed in terms of higher Ca co-
3.2.2. RE separation from solution: precipitation, SX, and reduction
dissolution for real phosphor waste predicted a different structure than
The REE dissolved in the leach solution is recovered through pre­
synthetic phosphors [100]. Biohydrometallurgy is also reported for re­
cipitation using different precipitating agents, including sulfate, car­
covery of RE from phosphor dust in literature. One of the major draw­
bonate, phosphate, oxalate, and fluoride [42]. The Eh-pH diagram of the
backs of biological leaching is the longer leaching duration (15–20
Re-O-H system is shown in Fig. 7 (a); all the REEs are soluble in the
days), controlled environment (for microbial cultures), and a large area
acidic range in the form of respective metal ions. It is important to
for industrial application. Hopfe et al., reported that leaching of 7.9%
mention that the following Eh-pH diagram corresponds to the Re-O-H
was obtained with tea fungus Kombucha; however, the slow kinetics and
system, and the presence of common anion (Cl− , HNO3− , SO42− ) in
low leaching efficiency make chemical processing more desirable [158].
leaching facilitates the formation of respective RE complex (ReCl2+, Re
The direct hydrometallurgical process is limited to Y, Eu (YOX) disso­
(NO3)2+, Re(SO4)2− ) [41]. Different precipitating agents such as oxa­
lution, which are easy to dissolve and represent higher concentrations
late, sulfate, carbonate, phosphate, and fluoride can recover RE from the
than other complex oxides. In contrast, other critical and high-valued
solution [42]. Oxalic acid is the widely used reagent in RE precipitation
RE, such as Tb, reports to the residue and needs to be further pro­
because hydrated lanthanide oxalates form readily in an acidic solution
cessed through other extraction techniques. LaPO4:Ce3+, Tb3+ has been
in a densely crystalline and easily filtered form. In contrast, the other
reported to be leached using hot concentrated (18 M) H2SO4 at tem­
precipitating reagents are ineffective unless the pH is relatively high (4-6
peratures 120 to 230 ◦ C [85]. Sequential digestion of red phosphor
pH). Therefore, the solution is subjected to neutralization to precipitate
(0.5-8 M HCl) and green phosphor (8–10 M HCl), thereby facilitating the
the impurities first, resulting in RE’s coprecipitation and reducing the
pure recovery of Tb after Y, Eu (YOX) separation in an initial stage, was
overall RE recovery [42,131]. RE ions (Re3+) precipitation with oxalate
reported [101]. However, the CAT and BAM phase are inert under
and phosphate is relatively better than other precipitating agents, even
similar operating conditions. The dissolution of LAP phosphor was
at high pH (~6). The general order of different reagents to recover RE is
recently observed in concentrated methane sulphonic acid (160–200 ◦ C
as follows: oxalate > phosphate > fluoride > sulfate > carbonate [42].
for 1 h); however, it could not dissolve CAT, BAM phosphor reflecting
Thermal decomposition of RE precipitate (oxalate) yields oxide and is
the high refractory nature of the phases [35]. The heterogeneity in
the most common form of these elements. The separation of mixed RE
phosphor powder poses a serious challenge in the selective recovery of
oxide into individual RE oxides from solution is a big challenge due to
REEs, especially when high purity products are obtained. Moreover, the
their similar physical and chemical properties. Precipitation of RE from
choice of certain acids is governed by the downstream processes, such as
a solution containing different RE ions (Y, Eu, Ce, Tb, La) results in a
H2SO4 is preferred when precipitation is to be followed, while Cl− or
mixed RE product. The majority of the literature for individual separa­
NO3− are suitable options for SX.
/ tion of RE is based on solvent extraction (SX) and selective reduction.
Y2 O3 + 6HCl→2YCl3 + 3H2 OΔGo90◦ C = − 4.54kJ mol (2) But the final recovery after employing SX and reduction is achieved
/ through precipitation with one of the above-mentioned precipitating
Eu2 O3 + 6HCl→2EuCl3 + 3H2 OΔGo90◦ C = − 121.42kJ mol (3) agents, commonly oxalic acid.
Different SX reagents such as Cyanex 572, Cyanex 923, D2EHPA,
/
Tb2 O3 + 6HCl→2TbCl3 + 3H2 OΔGo90◦ C = − 34.37kJ mol (4) DODGAA have been successful. Typical SX operating conditions include

8
N. Dhawan and H. Tanvar
Fig. 7. (a) Combined Eh-pH of Y/Eu/Ce/Tb-O-H system at 25 ◦ C, (b) Extraction behavior of REE with pH in SX (20% v/v D2EHPA in kerosene, O/A = 1), (c)
Separation factor (β = D1/D2) for different SX reagents [61,151]. D1 = [Me1]org/[Me1]aq D2 = [Me2]org/[Me2]aq.
kerosene, xylene as a dilutant for organic solvent, and HCl, H2SO4 for
stripping, with O: A ratio of 1:1–1:2 and contact time of 2–10 min.
[59,62,96,135,138]. According to the Mc-Cabe Thiele diagram reported
for the recovery of RE from solution, approx. 2–3 extraction and 4
stripping stages (using Cyanex 923) are required for complete removal
of Y (94.6%), Eu (5.1%) from solution, and the presence of multiple REE
(Ce, Tb, La) could require up to hundreds of stages of mixer and settler to
separate all the individual RE compounds [137,148]. Three types of
extractants- acidic (D2EHPA), neutral (TOPO), an ionic liquid-(Cyphos
IL 104) were investigated for Y and Eu extraction, and the highest sep­
aration factor (β = DY/DEu) was observed for D2EHPA. = 60.6. The
optimal conditions were 0.1 M D2EHPA; pH; 2.56; two stages; O:A ratio-
1:1.5. Further, precipitation/stripping (oxalate) was opted for the Y
recovery recovery [91].
The extraction of REEs from HNO3 solution using two bifunctional
ionic liquids [A336][P204] and [A336][P507] was studied, with
maximum (95%) recovery of RE at O:A ratio-4:1, pH- 0.56, in 5–7 stages.
However, a third phase is formed, which needs additional modification
using 10% isopropanol [151]. The ionic liquid-based selective extrac­
tion (DODGAA- [C₄mim][Tf₂N]) for the recovery of Y, Eu, La, Ce, Pr, and
Tb from phosphor powders after two-step acid leaching was also studied.
In the first stage (5 M H2SO4), > 99.5% Y and 95.5% Eu were leached,
while 90% of La, Ce, and Tb were leached in the second stage. IL-based
DODGAA system (25–50 mM) resulted in selective extraction of REEs (Y,
Eu, La, Ce, and Tb) at pH- 1.2- 3. [150]. During SX, pH also plays a
decisive role in the individual separation of REEs (Y, Eu); Tunsu et al.
used Cyanex 572 to separate Y and Eu and found that Y can be separated
from Eu at an equilibrium pH of 0 and subsequent recovery of Eu at pH
1, with a contact time of 15 min and O:A ratio of 1. It was reported that
the dissolution of extractants in aliphatic dilutants favors the extraction
compared to aromatic diluents and long-chain alcohols [138]. The pu­
rity of the final Y and Eu product was 99% and 90%, respectively.
Innocenzi et al. presented a comparative study for separating REE using
three different SX reagents (Cyanex 272, Cyanex 572, D2EHPA) from
sulfuric leaching solution of phosphor powder (Ce, Tb, Eu, La, Gd, Y)
D2EHPA (15% (v/v); O:A − 1:1; six extraction stages) performed best to
separate Y and Tb at a pH value less than 1 with no calcium extraction
[59,61,62]. However, 34% Tb and 21% Ce co-extraction were observed.
9
Sustainable Materials and Technologies 32 (2022) e00401
The extraction ratio for different RE using D2EHPA and comparative
analysis of separation factor (Fig. 7(b) and (c)) reveals that D2EHPA is
more suitable for the recovery of individual RE, and negligible separa­
tion efficiency is observed among Ce – La (light RE) and Y – Tb (heavy
RE) [61,151]. The extraction order was determined as Y > Tb > Eu > Ce
> La, with complete recovery of Y, Tb at pH ~ 0.6, Eu at pH 1–2, and Ce,
La at pH ~ 2. Various ILs such Primene 81R, Cyanex-572 IL and Primene
81R were used as extractants from Cl− media for the individual sepa­
ration of Y, Eu, Ce (> 99.9% purity) followed by stripping using 4 M HCl
[102]. The chlorinated RE (Y, Eu) products (after solid-state chlorina­
tion) dissolved in HCl media were efficiently extracted using Cyanex 923
and Cyanex 572 compared to D2EHPA and PC88A [104]. Furthermore,
REE was separated using D2EHPA in xylene; approximately 96% Tb was
extracted in the first stage with 60% D2EHPA, 93% La, and 95% Ce in
the next two stages with undiluted D2EHPA. The loaded organic phase
was subjected to precipitation with oxalic acid and calcination to obtain
the corresponding oxide of Tb (64% purity) and a mixture of Ce, La (90%
purity) [153]. RE phases were processed from the Cl- media sequentially
as follows: recovery of Y, removal of La/Ce, followed by Tb, and sepa­
ration of Gd from Eu using extractants such as HDEHP, Al336, and
involved 15–20 extraction stages. Leach solution was converted to ni­
trate to enrich Tb to recover REEs from the LAP phase while simulta­
neously limiting Ce and La dissolution [101].
Y and Eu separation can also be achieved using the reduction pro­
cess. The reduction process is more straightforward than SX, reduces the
number of steps required, and simplifies the process. Strauss et al. used
zinc powder to reduce Eu in a solution containing Y, Eu, and precipitated
Eu (II) sulfate from solution using sulfuric acid and obtained Eu sulfate
product with a grade of 96% and 73% recovery [122]. Reduction of Eu
(III) to Eu (II) using zinc powder was studied by [91]; however, copre­
cipitation (16% Y) was also observed, thus, entailing losses. Photo­
chemical reduction technique to reduce Eu and precipitate Eu sulfate
from the reduced solution is also reported. Over 95% efficiency was
obtained with more than 98% EuSO4 purity; however, the photochem­
ical reduction process requires long UV exposure, typically up to 24–30
h [141,147].
N. Dhawan and H. Tanvar
3.3. Pyrometallurgical route
The limited solubility of heavy RE (Tb, Ce, La) containing BAM, CAT,
and LAP phosphor phases in hydrometallurgical processes requires
adding a fluxing agent to dissociate the underlying crystal structure at
high temperature using pyrometallurgical techniques. The underlying
RE-bearing phase is heat-treated with alkali metal salts to break the
crystal structure and liberate the RE metals. Zhang et al. and Liu et al.
demonstrated an alkali fusion method with NaOH (400–600 ◦ C, 2 h) to
dissociate the spinel structure of pure blue and green (CAT and BAM)
phosphor sample and subsequently recovered Ce, Tb, and Eu via
leaching process (2–4 M HCl, 2–4 h at 60 ◦ C) [155,159]. The key idea is
to replace the RE ions in the crystal matrix with another cation. The
alkali earth ions have similar atomic radii as the RE ions (Ce3+ 103.4 pm,
Tb3+ 92.3 pm, La3+ 106 pm, Li+ 78 pm Na+ 102 pm, K+ 133 pm) and
have a potential to be replaced by these cations during heat treatment.
The free RE ion combines with the corresponding anion (OH− , CO32− ) to
form freely available RE hydroxide, oxide, or carbonate for leaching [82,
119]. Different alkali metal bearing salt are tested and reported in the
literature, mainly Na based fluxes such as NaOH, Na2CO3, Na2O2 are
used [64,66,76,146,153,160]. Na+ ion replaces the
Ba /Eu /Ce /Tb ion in the mirror plane during the heat treat­
+2 +2 +3 +3
ment, and Na2MgAl10O17 is formed [78,119]. Considering the ions’
valency, two Na+ replace one Ba+2/Eu+2, and three Na+ replace one
Ce+3/Tb+3 in BAM and CAT, respectively. The crystal structure of
Na2MgAl10O17 is like that of the initial phase (BAM/CAT); however, the
introduction of more Na+ ions for charge neutrality causes defects
around Na+ ions, and the lattice parameters are altered. This induces a
defect in the lattice, and the further diffusion of Na+ ion breaks the
structure from the mirror plane; the grouping of adjacent ions of O, Al,
and Na leads to NaAlO2 formation, and Mg2+ interacts with OH− to form
MgO and H2O [155]. RE values are liberated during the initial substi­
tution by Na+ and are oxidized to RE oxide due to the oxidative envi­
ronment. The roasting (Na2CO3; 900 ◦ C) of the leach residue obtained
after Y/Eu leaching in H2SO4 was successful in the conversion of RE
phased (resistant to leaching) into REO which are easy to leach to finally
achieve leaching efficiency of 86%, 81%, and 85% for Ce, La, and Tb
respectively in second leaching using HCl [153].
4CeMgAl11 O19 Tb + 44NaOH + 3O2 →44NaAlO2 + 4MgO + 2Ce2 O3 + 2Tb2 O3 + 22H2 O↑
4BaMgAl10 O17 Eu + 40NaOH + 3O2 →40NaAlO2 + 4MgO + 4BaO + 2Eu2 O3 + 20H2 O↑
The underlying chemical reaction involved in heating CAT, BAM,
LAP, and YOX phases with NaOH is shown in Eq. (7–10). The activation
energy for decomposition reaction of BAM phase with NaOH for Eu, Ba,
Al, and Mg was reported as 52.3, 64.6, 87.1, and 88.9 kJ/mol, respec­
tively [152]. The thermodynamics of reaction behavior and equilibrium
data is lacking in the literature due to the unavailability of the CAT and
BAM phosphor database in the database of thermodynamic software
(FactSage 8.0, ThermoCalc 2021a, HSC Chemistry) [53]. Furthermore,
the thermodynamic data of spinel MgAl2O4 was chosen for thermody­
namic assessment for NaOH reaction due to its similar structure as BAM
phosphor as shown in Eq. (11). The equilibrium calculation at 500 ◦ C
provides negative Gibbs free energy (− 22.1 kJ/mol), showing thermo­
dynamic feasibility in dissociating the spinel plane of the magneto
10
Sustainable Materials and Technologies 32 (2022) e00401
plumbite structure with NaOH. Hua et al. thermodynamically studied
the reaction behavior of MgAl2O4 with Na2CO3 and found that the Gibbs
free energy of the reaction is negative above 940 ◦ C at a total pressure of
1 atm and is approximately − 9 kJ/mol at 1000 ◦ C [53].
In our recent study, it was found that direct heating of trichromatic
phosphor with NaOH results in the formation of the NaYO2 phase as per
Eq. (10), which decreases the overall Y recovery after acid leaching
[119]. Therefore, it is envisaged that the separation of acid-soluble YOX
phase consisting of Y, Eu in an initial acid washing provides a higher RE
recovery rate. Based on the experimental results, it was found that heat
treatment with 150 wt% NaOH at 400 ◦ C for 1 h and leaching in 0.5 M
HCl for 1 h at 60 ◦ C separated more than 90% RE with final product
consisting of 79% Y, 7% Eu, 5% Ce, and 4% Tb [119]. Similar results
were reported by Liu et al., where the authors compared the direct heat
treatment of phosphor and acid leaching (to separate Y, Eu) followed by
heat treatment of residue with NaOH and acid leaching heat-treated
mass to recover RE values. Direct heat treatment (phosphor: NaOH =
1:1.5, 800 ◦ C, 2 h, leaching in 5 M HCl, 2 h, 60 ◦ C) of trichromatic
phosphor resulted in separation of 42.1% total RE (41.5% Y, 67.8% Eu,
94.5% Tb, 86.1% Ce), while two-step process separated more than
94.6% RE (94.6% Y, 99.1% Eu, 71.4% Tb, 76.2% Ce) [80]. Ippolito et al.
used Ba(OH)2 as a flux during heat treatment (phosphor: Ba(OH)2 = 2:1,
950 ◦ C, 1 h) of halo phosphate-rich phosphor followed by leaching with
sulfuric acid (3 M, 60 ◦ C, 2 h) to dissolve the underlying RE values and
obtained more than 90% recovery rate. The final product is of approx­
imately 98% purity consisting of 82.2% Y, 8.2% Eu, 2.4% Ce, 2.3% Gd,
1.8% La, and 1.5% Tb [64,66].
Direct heat treatment of trichromatic phosphor with alkali material
results in the dissolution of all the REE, and the final REO product ob­
tained after precipitation is a mixture of more than four REE (Y, Eu, Ce,
Tb, La, Gd) and makes further separation using SX and ion exchange
difficult and more complex. On the other hand, a two-step process (acid
leaching for Y, Eu, and alkali treatment for Ce, Tb, La) produces two
products: Y, Eu, and other with Ce, Tb, La which simplifies the separa­
tion process to a great extent. Therefore, a two-stage process is favorable
regarding the required reagents and complexity of the downstream
separation process.
(7)
(8)
/
2LaPO4 + 6NaOH→La2 O3 + 2Na3 PO4 + 3H2 OΔGo500◦ C = − 37.8kJ mol
(9)
Y2 O3 + NaOH→NaYO2 + H2 O (10)
/
MgAl2 O4 + 2NaOH→2NaAlO2 + MgO + H2 OΔGo500◦ C = − 22.1kJ mol
(11)
3.3.1. Microwave processing
The application of microwave heating in mineral processing and
metal extraction industries has been investigated for several decades.
Microwave heating technology is energy-efficient and green production
N. Dhawan and H. Tanvar
technology; the most crucial advantage is the material’s rapid, selective,
and volumetric heating [106]. Recently microwave processing of rare
ore mixed earth concentrates, and minerals are reported [54,55]. The
critical application of microwave processing in FL recycling can be for
the recovery of La, Tb, Eu, Ce from refractory CAT, BAM, and LAP
phosphor phases. The typical method in literature for dissociation of
these phases includes heat treatment or mechanical activation with an
alkali-based salt, which can be achieved using microwave application in
a more sustainable way making the process rapid, energy-efficient, cost-
effective. Based on our experience with microwave processing of phos­
phor material with alkali (NaOH), it was found that a temperature of
more than 900 ◦ C can be attained within 5–10 min of microwave
exposure at 900 W [116]. Microwave heating of leach residue after Y, Eu
separation (consisting of CAT, BAM, and LAP phases; 6.2% La, 5.1% Ce,
2% Eu, 3.2% Tb) with NaOH (1:1 weight ratio) for 10 min at 900 W
power resulted in dissociation of the active phases and formation of
water-soluble NaAlO2 with corresponding oxides of REE (Ce, Tb, Eu, La).
Approximately 65% La, 51% 20% Ce, 64% Eu, 72% Tb were recovered
after leaching with 1 M HNO3, at 80 ◦ C for 20 min and a mixed RE oxide
consisting of 6% Y, 47% La, 7% Ce, 8% Eu and 18% Tb was obtained
after precipitation with oxalic acid. It was observed that high tempera­
ture during exposure oxidized Ce to CeO2 and Ce7O12 phases, which
were inert to acid leaching under mild conditions and required high acid
concentration for dissolution. HCl may promote Ce (IV) reduction to Ce
(III); however, the leaching kinetics is very slow compared to other
REEs. It is desirable to leave Ce in the residue during the leaching for
achieving better separation from other REEs. A similar process is also
employed to process high Ce-containing mineral concentrates such as
Monazite and Bastnasite [68,148]. Dissolution of CeO2 can be carried
out using high concentrated acid (HCl, HNO3, H2SO4), in the presence of
F− ion or with the aid of reducing species (KI, H2O2) and extraction from
solution using SX with Cyanex 923, HEHEHP [59,62,148,153].
Recently, at optimal microwave baking conditions (800 W, 3 min, 1 mL/
g acid), complete dissociation of RE phases resulted in overall 82.5% RE
dissolution, including 93% Tb, 40% La, and ~ 100% Eu and Y extrac­
tion. The overall thermal activation energy is reported as 409.5 kJ/mol,
and the low solubility of Ce (IV) led to its concentration in the residue
phase [118].
Fig. 8. Processing flowsheet of the commercial operation developed by Rhodia-Solvay and OSRAM (GmbH) [16,98].
11
Sustainable Materials and Technologies 32 (2022) e00401
4. Industrial recycling processes
Recovery of REE from the phosphor of waste FLs is important due to
instability in RE’s supply and the growing pile of waste materials. RE
phosphor collected from waste FL cannot be directly reused for new
lamps because of mercury contamination and deterioration of the
chemical and physical properties due to extended usage. A commercial
process for recovering REE from phosphor waste was developed by
Rhodia (Solvay Group) in France and OSRAM GmbH (owned by
Siemens) in Germany [13]. The typical flowsheets of the process
patented by Rhodia-Solvay and OSRAM GmbH are shown in Fig. 8
[16,98,157]. The primary stage of treatment is similar in both the
flowsheets and includes crushing and size classification to obtain
phosphor, connections, and glass fraction. The phosphor dust is further
leached with HCl to remove Ca and P impurities. In the case of the
Rhodia-Solvay process, the filter cake is further heated with sodium
carbonate to dissociate the Ce, Tb phase, followed by the dissolution of
the calcined mixture in the HNO3 and H2O2 mixture. The resulting ni­
trate leach liquor consists of 78 g/L of RE oxide equivalent with
approximately a total recovery. 85–90% RE [16]. The nitrate liquor is
further processed through solvent extraction and/or precipitation to
separate individual REEs. On the other hand, the OSRAM process in­
cludes an acid leaching process to dissolve acid-soluble Y and Eu fol­
lowed by alkali/acid breakdown of Ce, Tb bearing phase at high
temperature and pressure in an autoclave [98]. The collected RE solu­
tions are further processed through liquid-liquid extraction to recover
different RE compounds. The Rhodia and OSRAM processes are typical
examples of industrial processes for recycling lamp phosphors world­
wide operated commercially (since 2010). However, one the major
drawbacks is the wide range of phosphor composition collected from
different types of lamps. These processes are specifically optimized for
recycling phosphor dust from French and German FLs; however, the
composition variation is expected around the world. Therefore, more
work to commercially recycle phosphor is still required [12]. Recently, a
design and construction of mobile industrial plant containing a hydro­
metallurgical section for the treatment of FL is proposed [59,62]. The
cost analysis shows the plant to be economical if it works at its maximum
capacity at optimized operating conditions and is highly dependent on
N. Dhawan and H. Tanvar Sustainable Materials and Technologies 32 (2022) e00401

Table 3
REEs extraction with different separation processes. (SX – Solvent extraction, MW – microwave).
Process Physiochemical Separation Hydrometallurgy Mechanical activation Pyrometallurgy Microwave processing
3+ 3+ 2+
Feed Ca3(PO4)2Ca(F,Cl)2, (Y,Eu)2O3, (La,Ce,Tb)(P,B)O4, (Sr,Ca,Ba,Eu)10(PO4)6Cl2, Y2O3∶Eu , CeMgAl10O17∶Tb , BaMgAl10O17∶Eu , SiO2, Al2O3
Target RE phosphors Y, Eu Y, Eu, La, Ce, Tb
Method Enrichment by centrifugation, Acid leaching of in different lixiviants Milling and flux Roasting with alkali and MW alkali roasting and
dense medium separation, and SX and/or precipitation for activation followed by single/multi-step single/multi-step
flotation, magnetic separation recovery fusion and/or water and leaching leaching; MW acid
acid leaching baking
Reagents Surfactant: Sodium Oleate Leaching: Organic acid, HNO3, HCl, Milling additive: NaOH, Heating flux: NaOH, KOH, Ba(OH)2, LiBO2, Na2CO3,
(NaOl), 1-pentanol, H2SO4, SX: Cyanex 923, 572, 272, Chelating agents Na2O2, Leaching: 0.5–5 M HNO3, HCl, H2SO4; SX:
choloroform, CH2I2. Collector: Primene JMT, DODGAA, and (EDTA, EDDS, MGDA, Cyanex 923, 572, 272, Primene JMT, D2EPHA;
DAA, SDS, Na2SiO3, DMF/ D2EPHA; Diluent: xylene, kerosene. HIDS) dilutent–xylene, kerosene; Precipitation – oxalic acid;
heptane system, 1-octane Precipitation: oxalic acid Leaching: 2–3 M H2SO4, 1 mL/g H2SO4.
sulfonate. 2 M HCl
Parameters 4000–8000 rpm, 0.03–0.06 m3/ Leaching: 0.5–5 M, 20–120 ◦ C, 1–48 h, Milling: 100–150 wt% Heating: 100–150 wt% Heating: 50–100 wt%
s air flow rate, 30–400 S/L ratio, 500–600 rpm flux, 5–8 h, 400–550 flux, 400–1000 ◦ C, 1–3 flux, 800- 900 W MW
Magnetic strength- 2 T SX - pH (0.5–2.5), O:A ratio (1:1–2), rpm; 1:9–40 sample: h power, 2–20 min
and conc. (15–65%), 1–10 min contact ball. Fusion: 800 W, 3 min
time 500–600 C, 2 h
◦

Leaching: 40–80 ◦ C, 1–2 h, 1:5–50 S/L (g/mL), 900 rpm

66–90% RE phosphor (sink/
Products/ concentrate fraction), 90%
Recovery white phosphor (float/tailing
product)
Advantages Convenient and easier process
Phosphors deteriorate after
Disadvantages
extended usage
Physical separation equipment
Economic
(floatation cell, centrifugal
considerations/
classifier), reagent cost related
Scale-up
to surfactant, collector
[46,47]; [88]; [97]; [88]; [154];
References
[149]; [129]; [14].
95% mixed Y–Eu
84–98%-Y and 84–90% 95–99% Y, 99–100%
Oxides, 40–65% Ce and
64–97% Y, 71–94% Eu leaching. Eu, 61–85% Ce, Eu, 72–98% Ce, 76–99%
70–95% Tb with mixed
Recovery as mixed oxide of Y, Eu 53.1–89.8% La Tb, 51.9% Gd, 43–95%
Ce–Tb Oxides; 98%
recovery La recovery.
pure Y-Eu-Tb oxides
Lower acid High efficiency,
Low energy consumption consumption and Efficient RE recovery selective, rapid; Fast, Tb
effluent generation maximum
Large effluent generation and High energy Energy extensive, time-
Lack of scale-up studies
ineffective to Ce, Tb consumption consuming
Flux required (alkali), Flux (alkali), heating Large scale microwave
Low capital expense, high operation
planetary ball mill, high furnace, high capital furnace, High capital
expense
capital cost cost cost, low operating cost.
Leaching setup reactor (stirring tanks), acid for leaching, SX precipitation reagent, solid-liquid separation
[5]; [29]; [43]; [59,62]; [20]; [102],
[43]; [44]; [84]; [120]; [60]; [64,66]; [76]; [116]; [119]; [118];
[103]; [107]; [113]; [131];
[126]; [130]; [65]. [79]; [80]; [153]; [156] [131]
[134,135,137,138]; [142]; [150].

the market price of oxide of Y and Eu. typically combined flowsheet for the recovery of individual RE com­
A comprehensive summary of different processes for recovering REE pounds from waste FL is presented in Fig. 9. Physical beneficiation for
from phosphor dust is shown in Table 3. Based on the literature search of separating different phosphor phases is not preferable due to limited
acid dissolution, heat treatment, precipitation, SX, and reduction, a separation efficiency. On the other hand, direct microwave acid baking

Fig. 9. Overall flowsheet for recycling of discarded FLs: available processing options.

12
N. Dhawan and H. Tanvar Sustainable Materials and Technologies 32 (2022) e00401

with sulfuric acid results in the dissolution of multiple REEs making Table 4
downstream separation difficult. The most viable option is the recovery Comparative cost analysis of the different processes (37% HCl, 120$/ton; NaOH
of Y Eu during the first stage of treatment while further processing the 350$/ton; 96% H2SO4, 150$/ton).
residue for Tb, La, and Ce recovery. The valuable phosphor waste dust Process Dual step Alkali Milling – HCl Acid baking –
collected after crushing and physical separation of FLs can be processed acid roasting – leaching water leaching
through multistage leaching, wherein the halo phosphate phosphor can leaching HCl
leaching
be separated first via a mild acid washing step. Further, RE enhanced
phosphor can be leached to dissolve Y, Eu values, and the pregnant leach Equipment Stirrer (1 Heating Planetary ball Microwave
kW) furnace mill (1.25 reactor (2.45
solution can be subjected to reduction of Eu (III) to Eu (II) in the pres­
(2.25 kW, kW, GHz, 0.8 kW),
ence of SO42− to precipitate EuSO4. The resultant solution is subjected to 0.75 kW), Efficiency- Stirrer (1 kW)
precipitation (of Y) to yield EuSO4 and Y2O3 finally. stirrer (1 0.30), stirrer
The Y, Eu leaching stage residue is processed through alkali assisted kW) (1 kW)
heat treatment route as shown in Fig. 9. Microwave heat treatment is Batch mass 10 50 200 (T.Wt- 5
(MT/run) 3.2 kg)
advantageous over conventional heating due to rapid and volumetric Pre-treatment – – 1 h (3× –
heating, high recovery rate, and short processing time. The heated residue NaOH)
is then water washed to separate NaAlO2 and acid leached to dissolve Ce, milling
La, Tb values. Separation of Tb from Ce, La is further carried out using Pre-treatment – 1190.5 –
energy kWh/
solvent extraction and precipitation route. Finally, two products, Tb4O7
ton
and mixed oxide (Ce, La)2O3, are generated. Moreover, microwave- Reagents 2052 L 2 ton NaOH, 3 ton NaOH, 1000 L 96%
assisted baking can be a prospective efficient method of recycling, 37% HCl 1850 L 37% 2246 L 96% H2SO4
which can cause dissociation of interlocked phases (LAP, CMAT). The HCl H2SO4
disintegrated phases are dissolved with the maximum value recovered by Reagent cost 295.6 966.4 $/ton 1670 $/ton 276 $/ton
$/ton
Tb. Based on the material balance of the combined recycling process, it is
Temperature/ – 700 ◦ C, 3 h, – 800 W (3 min)
possible to recover 187 kg Y2O3, 14 kg Eu2O3, 17 kg Tb4O7, and 55 kg (Ce, Power
La)2O3 from 1 metric ton of phosphor sample containing 19.3% Y2O3, Energy, kWh/ – 231.43 – 134.95
1.4% Eu2O3, 3.7% La2O3, 3.2% CeO2, and 1.9% Tb4O7. ton
Water (L/t) 15,948 L 20,650 L 17,754 L 24,000 L
Secondary 1 M HCl, 3 M HCl, S/L 2 M H2SO4, 2 –
5. Overview and discussion treatment 10 min, S/ 1:5, 70 ◦ C, 1 h, 80 ◦ C, S/L
L:1:10; 2 M h 1:5
Although waste FLs are being collected around the globe for several HCl, 48 h,
years, mainly due to the environmental concern regarding mercury S/L:1:10
Leaching 48.16 1 2 1
emission, the recovery of high purity REE has gained pace recently. Pri­
energy kWh/
mary recycling of FL is adopted commercially and includes crushing ton
mercury capture, and separation of different components. The phosphor Total process 48.16 232.43 1192.50 135.95
dust collected after separation consists of most REE (Y, Eu, Ce, Tb, La) and energy
(kWh/t)
represents a potential recovery source. Based on the average composition
Metal recovery Y: 98%; Eu: Ce: 98.12% Ce: 85% Eu: Eu: 99.6%, Y:
of RE phosphor, processing of 1 kg of phosphor waste yields approxi­ (%) 90%; La: Eu: 99.93% 94.5% Tb: 99.3%, Tb:
mately 203–383 g of RE product (Y, Eu, Ce, Tb, La oxide), which is 15%, Tb: 99.37% 89.8% Y: 93.6% TREE:
equivalent to the processing of 11.9–22.5 kg of primary ore (considering TREE: 80% Y: 99.60%, 98.5%. TREE: 82.5%
1.5% grade for all REE). Also, generally radioactive materials (0–0.5 wt% TREE: 95%
99.3%
Th, 0–0.3 U) are associated with the RE-bearing minerals (Bastnasite,
Reference [103], [76] [44] [118]
Monazite, Xenotime) and need to be processed separately to have a low [59,62]
radioactive product [33]. Processing large quantities of RE ore leads to the
accumulation of highly radioactive waste material, causing significant
damage to health and the environment. One of the significant challenges reduce energy consumption up to 90% and make the processing rela­
in the processing of FL phosphor is the varying incoming feed material tively cheaper and rapid.
composition. The processing route cannot be generalized for one type of Furthermore, literature consists of limited information on the isola­
feed and must be robust to accept a wide range of input feed compositions. tion and recovery of various/all rare earth elements from leach solution
A summarized overview of the capital, reagent cost, and energy obtained from phosphor dust. Although, there is a wide range of liter­
consumption for different processing options based on the literature is ature available related to solvent extraction and ion exchange of solu­
given in Table 4. The cost of equipment and reagents is determined and tion obtained from acid leaching of mineral ore concentrate. However,
calculated as per Eq. (12-14). At present, limited industrial-scale pro­ the phosphor waste’s actual conditions and reagents may differ due to
cessing is carried out to recover Y, Eu values through the hydrometal­ differences in elemental composition and phase association. Addition­
lurgical route, whereas other rare earth elements with high value, ally, the rare earth recovery process involves using inorganic acid and
including Tb, La, Ce, are neglected in the residue. Research efforts are generates a huge quantity of acidic waste solution on the environmental
leaning towards alkali activation of phosphor for enhanced recovery of aspect.
these elements; however, the conventional heating system consumes a
lot of energy and adds to the process’s operational cost. On the other
hand, microwave processing and mechanical activation routes can

( )
$ $ mLH2 SO4 gH2 SO4 gPhosphor 1 TonH2 SO4
Cost = Price × X1 × 1.84 × 1000 × (12)
TonPhosphor TonH2 SO4 gphosphor mLH2 SO4 kgPhosphor 1000000 gH2 SO4

13
N. Dhawan and H. Tanvar
( )
$ $ mLHCl gHCl
Cost = Price × X1 × 1.84 × 1000
TonPhosphor TonHCl gPhosphor mLHCl
( )
kWh h 1 Run
Energy = Power rating(kW) × T1 × (14)
TonPhosphor run X TonPhosphor
6. Conclusion
Waste FLs are collected and processed industrially for safe disposal
due to concerns with enclosed mercury. FLs are crushed/dismantled,
and mercury is collected via the thermal desorption process or captured
with activated carbon, while other components are separated individ­
ually. Among the components present in FL (glass, metal connections,
phosphor, mercury), fluorescent phosphor powder rich in REEs (Y, Eu,
Ce, Tb, and La) is the most critical component and can be considered a
next generation RE source that is widely available around the globe.
Mainly, waste FLs are being collected around the globe for several years
due to environmental concerns regarding mercury emission; however,
the recovery of REE has gained significant interest recently.
Recent developments in the REE recycling from FL include the
changing focus on recovering high valued heavy REEs such as Tb (Y -
$3/kg, Tb - $958/kg, Eu - $140/kg). Processing routes involve liquid-
liquid extraction, reduction, and precipitation techniques to separate
different RE compounds with high purity. Other energy-efficient, envi­
ronmentally sound processing routes such as mechanical activation and
microwave processing are reported, making the extraction process rapid
and economically favorable; however, the current application is limited
to lab-scale study and lacks proper scale-up guidelines.
The leaching process successfully recovers Y and Eu, while another
RE (Ce, Tb, La) phase behaves inert. Y, Eu dissolved in leaching can be
separated into RE compounds by selective reduction and precipitation.
Inert behavior of Ce, Tb, La phases can be considered a potential benefit
for the recycling route, making the separation process easy and conve­
nient. The leach obtained after Y separation; Eu is processed through the
alkali activation route to recover the remaining rare earth values. The
inert phases CAT (CeMgAl11O19:Tb3+) and BAM (BaMgAl10O17:Eu2+)
are successfully dissociated by employing alkali activation routes. Alkali
activation can be performed using mechanical activation or heat treat­
ment route. Heat treatment using microwave technology is better than
conventional heating and yields better recovery in less time and energy
consumption. The leach solution rich in REEs is processed through SX to
recovery individual RE compounds. Recovery of REE from the waste
phosphor is expected to become more prominent with the dual benefit of
environmental waste management and generating secondary RE re­
sources. Advanced processing techniques such as microwave and me­
chanical activation should be implemented as they offer higher recovery
rates, and their scale-up should be evaluated. Eco-friendly, non-toxic,
low-cost, novel and regenerative lixiviants for selective and preferential
leaching of certain phosphors should be considered from the perspective
of economic and environmental incentives. Design and construction of
mobile industrial plants combining hydro-pyrometallurgical operations
are expected to come up for the treatment of mixed FLs.
Declaration of Competing Interest
On behalf of all authors, the corresponding author states that there is
no conflict of interest.
Acknowledgment
The author acknowledges the discussions with Shaila Mir and Shrey
Agrawal during the preparation of the manuscript.
Sustainable Materials and Technologies 32 (2022) e00401
gPhosphor 1 TonHCl
× (13)
kgPhosphor 1000000 gHCl
References
[1] AERC, Recycling Solutions. Lamp Recycling, Retrieved from, http://www.aerc.
com/, 2021. Accessed: December 2021.
[2] Air Cycle Corporation (A TerraCycle Company), Retrieved from, https://www.
aircycle.com/, 2021. Accessed: December 2021.
[3] T.G. Ambaye, M. Vaccari, F.D. Castro, S. Prasad, S. Rtimi, Emerging technologies
for the recovery of rare earth elements (REEs) from the end-of-life electronic
wastes: a review on progress, challenges, and perspectives, Environ. Sci. Pollut.
Res. 27 (2020) 36052–36074, https://doi.org/10.1007/s11356-020-09630-2.
[4] A. Anand, R. Singh, Synthesis of rare earth compounds from phosphor coating of
spent fluorescent lamps, Sep. Purif. Rev. 50 (2021) 96–112, https://doi.org/
10.1080/15422119.2020.1754240.
[5] A. Anand, R. Singh, A.R. Sheik, M.K. Ghosh, K. Sanjay, Leaching of rare earth
metals from phosphor coating of waste fluorescent lamps, Trans. Indian Inst.
Metals 72 (3) (2019) 623–634.
[6] A. Akcil, Y.A. Ibrahim, P. Meshram, S. Panda, Hydrometallurgical recycling
strategies for recovery of rare earth elements from consumer electronic scraps: a
review, J. Chem. Technol. Biotechnol. (2021), https://doi.org/10.1002/
jctb.6739.
[7] S. Althaf, C.W. Babbitt, Disruption risks to material supply chains in the
electronics sector, Resour. Conserv. Recycl. 167 (2021), 105248.
[8] M. Asari, K. Fukui, S.I. Sakai, Life-cycle flow of mercury and recycling scenario of
fluorescent lamps in Japan, Sci. Total Environ. 393 (1) (2008) 1–10.
[9] G. Belardi, N. Ippolito, L. Piga, M. Serracino, Investigation on the status of rare
earth elements contained in the powder of spent fluorescent lamps, Thermochim.
Acta 591 (2014) 22–30.
[11] P.A. Bhat, D.W. Johnson, Activated carbon flue gas desulfurization systems for
mercury removal, in: Patent Application US5672323A, 1997.
[12] K. Binnemans, P.T. Jones, B. Blanpain, T.V. Gerven, Y. Yang, A. Walton,
M. Buchert, Recycling of rare earths: a critical review, J. Clean. Prod. 51 (2013)
1–22.
[13] K. Binnemans, P.T. Jones, Perspectives for the recovery of rare earths from end-
of-life fluorescent lamps, J. Rare Earths 32 (3) (2014) 195–200.
[14] P. Boelens, Z. Lei, B. Drobot, M. Rudolph, Z. Li, M. Franzreb, K. Eckert, F. Lederer,
High-gradient magnetic separation of compact fluorescent lamp phosphors:
elucidation of the removal dynamics in a rotary permanent magnet separator,
Minerals 11 (10) (2021) 1116.
[15] E. Bouri, K. Kanjilal, S. Ghosh, D. Roubaud, T. Saeed, Rare earth and allied sectors
in stock markets: extreme dependence of return and volatility, Appl. Econ. 53
(49) (2021) 5710–5730, https://doi.org/10.1080/00036846.2021.1927971.
[16] J.J. Braconnier, A. Rollat, Method of recovering rare earths from a solid mixture
containing a halophosphate and a rare earth compound and solid mixtures
suitable for this method, in: Patent US 9,102.998 B2; US8501124B2;
WO2010118967A1 (Rhodia-Solvay operation), 2010.
[17] T.C. Chang, S.J. You, B.S. Yu, C.M. Chen, Y.C. Chiu, Treating high-mercury-
containing lamps using full-scale thermal desorption technology, J. Hazard.
Mater. 162 (2009) 967–972.
[18] S. Chen, J. Zhang, J. Kim, Life cycle analysis of greenhouse gas emissions for
fluorescent lamps in mainland China, Sci. Total Environ. 575 (2017) 467–473.
[19] S. Coskun, G. Civelekoglu, Recovery of mercury from spent fluorescent lamps via
oxidative leaching and cementation, Water Air Soil Pollut. 226 (2015) 196,
https://doi.org/10.1007/s11270-015-2391-9.
[20] I. De Michelis, F. Ferella, E.F. Varelli, F. Vegliò, Treatment of exhaust fluorescent
lamps to recover yttrium: experimental and process analyses, Waste Manag. 31
(12) (2011) 2559–2568.
[21] E.J. Domanico, Fluorescent lamp disposal system, in: Patent Application
US7118056B2, 2004.
[22] E.J. Dos Santos, A.B. Herrmann, F. Vieira, C.S. Sato, Q.B. Correa, T.A. Maranhao,
L. Tormen, A.J. Curtis, et al., Determination of hg and Pb in compact fluorescent
lamp by slurry sampling inductively coupled plasma optical emission
spectrometry, Micro Chem J 96 (2010) 27–31.
[23] D. Dupont, K. Binnemans, Rare-earth recycling using a functionalized ionic liquid
for the selective dissolution and revalorization of Y2O3:Eu3+ from lamp
phosphor waste, Green Chem. 17 (2) (2015) 856–868.
[24] W.A. Durao Jr., C.A. Castro, C.C. Windmoller, Mercury reduction studies to
facilitate the thermal decontamination of phosphor powder residues from spent
fluorescent lamps, Waste Manag. 28 (11) (2008) 2311–2319.
[25] N. Dushyantha, N. Batapola, I.M.S.K. Ilankoon, S. Rohitha, R. Premasiri,
B. Abeysinghe, K. Dissanayake, The story of rare earth elements (REEs):
occurrences, global distribution, genesis, geology, mineralogy and global
production, Ore Geol. Rev. (2020) 103521.
[26] ECORECO Eco Recycling Limited, Lamp Recycling, Retrieved from, https://ec
oreco.com/services-lamp-recycling.aspx, 2021. Accessed: December 2021.
[27] M.J. Eckelman, P.T. Anastas, J.B. Zimmerman, Spatial assessment of net mercury
emissions from the use of fluorescent bulbs, Environ. Sci. Technol. 42 (22) (2008)
8564–8570.
14
N. Dhawan and H. Tanvar
[28] P.M. Eduafo, Investigation of Recovery and Recycling of Rare Earth Elements
from Waste Fluorescent Lamp Phosphors, Ph.D. Dissertation, Colorado School of
Mines, Colorado, USA, 2016.
[29] P.M. Eduafo, B. Mishra, Leaching kinetics of yttrium and europium oxides from
waste phosphor powder, J. Sustain. Metall. 4 (4) (2018) 437–442.
[30] P.M. Eduafo, M.L. Strauss, B. Mishra, Experimental investigation of recycling rare
earth metals from waste fluorescent lamp phosphors, in: In Rare Met. Technol.
Proceedings of TMS2015, Orlando, FL, USA, Mar 15–19, 2015, 2015.
[31] ELCOMA, Electric lamp and component manufacturers association of India,
Lighting industry data 2018-19. http://www.elcomaindia.com/wp-content/up
loads/Lighting-Data-2018-01.05.2019.pdf, 2019 (Accessed: Jan, 2021).
[32] FLR. Fluorescent Lamp Recyclers Technologies Inc, Retrieved from, http://www.
flr.ca/Recycle lamps.htm, 2021. Accessed: December 2021.
[33] A.C. García, M. Latifi, A. Amini, J. Chaouki, Separation of radioactive elements
from, Rare Earth Element-Bearing Minerals 10 (11) (2020) 524, https://doi.org/
10.3390/met10111524.
[34] G. Gaustad, E. Williams, A. Leader, Rare earth metals from secondary sources:
review of potential supply from waste and byproducts, resources, Conservat.
Recycl. 167 (2021), 105213.
[35] L. Gijsemans, F. Forte, B. Onghena, K. Binnemans, Recovery of rare earths from
the green lamp phosphor LaPO4: Ce3+, Tb3+ (LAP) by dissolution in
concentrated methanesulphonic acid, RSC Adv. 8 (46) (2018) 26349–26355.
[36] A. Gupta, S.R. Vidyarthi, N. Sankararamakrishnan, Enhanced sorption of mercury
from compact fluorescent bulbs and contaminated water streams using
functionalized multiwalled carbon nanotubes, J. Hazard. Mater. 274 (2014)
132–144, https://doi.org/10.1016/j.jhazmat.2014.03.020.
[37] C.K. Gupta, N. Krishnamurthy, Extractive metallurgy of rare earths, Int. Mater.
Rev. 37 (1) (2017) 197–248. GUPTA, CRC Press.
[38] S.K. Gupta, P.S. Ghosh, M. Sahu, K. Bhattacharyya, R. Tewarib, V. Natarajan,
Intense red emitting monoclinic LaPO4:Eu3+ nanoparticles: host–dopant energy
transfer dynamics and photoluminescence properties, RSC Adv. 72 (5) (2015)
58832–58842.
[39] M. Gyorgy, S. Lukacs, E. Cserteg, E. Toth, G. Kamenar, Method for recovering
fluorescent material from faulty glass bodies of discharge lamps, in: Patent
Application US 20020063509, 2002.
[40] F. Habashi, Extractive metallurgy of rare earths, Can. Metall. Q.Canadian Metall.
Quart. 52 (3) (2013) 224–233.
[41] K.N. Han, Effect of anions on the solubility of rare earth element-bearing minerals
in acids, Min. Metall. Explor. 36 (2019) 215–225, https://doi.org/10.1007/
s42461-018-0029-3.
[42] K.N. Han, Characteristics of precipitation of rare earth elements with various
precipitants, Minerals 10 (2020) 178, https://doi.org/10.3390/min10020178.
[43] H. Hasegawa, Z.A. Begum, R. Murase, K. Ishii, H. Sawai, A.S. Mashio, T. Maki, I.
M.M. Rahman, Chelator-induced recovery of rare earths from end-of-life
fluorescent lamps with the aid of mechano-chemical energy, Waste Manag. 80
(2018) 17–25.
[44] L. He, W. Ji, Y. Yin, W. Sun, Study on alkali mechanical activation for recovering
rare earth from waste fluorescent lamps, J. Rare Earths 36 (1) (2018) 108–112.
[45] N.N. Hidayah, S.Z. Abidin, The evolution of mineral processing in extraction of
rare earth elements using liquid-liquid extraction: a review, Miner. Eng. 121
(2018) 146–157.
[46] T. Hirajima, K. Sasaki, A. Bissombolo, H. Hirai, M. Hamada, M. Tsunekawa,
Feasibility of an efficient recovery of rare earth-activated phosphors from waste
fluorescent lamps through dense-medium centrifugation, Sep. Purif. Technol. 44
(3) (2005) 197–204.
[47] T. Hirajima, A. Bissombolo, K. Sasaki, K. Nakayama, H. Hirai, M. Tsunekawa,
Floatability of rare earth phosphors from waste fluorescent lamps, Int. J. Miner.
Process. 77 (4) (2005) 187–198.
[48] J. Hobohm, K. Kuchta, O. Krüger, S. van Wasen, C. Adam, Optimized elemental
analysis of fluorescence lamp shredder waste, Talanta 147 (2016) 615–620.
[49] HSC Chemistry 5.11, Chemical Reaction and Equilibrium Software, Outokumpu
Research Oy, Piori, Finland, 2002.
[52] A.H. Hu, C.H. Kuo, L.H. Huang, C.C. Su, Carbon footprint assessment of recycling
technologies for rare earth elements: a case study of recycling yttrium and
europium from phosphor, Waste Manag. 60 (2017) 765–774.
[53] Z. Hua, A. Geng, Z. Tang, Z. Zhao, H. Liu, Y. Yao, Y. Yang, Decomposition
behavior and reaction mechanism of Ce0.67Tb0.33MgAl11O19 during Na2CO3
assisted roasting: toward efficient recycling of Ce and Tb from waste phosphor,
J. Env. Manage 249 (2019), 109383.
[54] Y. Huang, T. Zhang, Z. Dou, G. Lv, G. Han, W. Peng, Microwave strengthens
decomposition of mixed rare earth concentrate: microwave absorption
characteristics, J. Rare Earths 37 (2019) 541–546, https://doi.org/10.1016/j.
jre.2018.08.010.
[55] Y. Huang, T. Zhang, J. Liu, Z. Dou, J. Tian, Decomposition of the mixed rare earth
concentrate by microwave-assisted method, J. Rare Earths 34 (2016) 529–535,
https://doi.org/10.1016/S1002-0721(16)60058-3.
[57] IBM, Indian Minerals Yearbook 2019 (Part- III: Mineral Reviews), 58th edition,
Rare Earths, 2020.
[58] V. Innocenzi, I. De Michelis, F. Ferella, F. Vegliò, Recovery of yttrium from
cathode ray tubes and lamps’ fluorescent powders: experimental results and
economic simulation, Waste Manag. 33 (2013) 2390–2396, https://doi.org/
10.1016/j.wasman.2013.06.002.
[59] V. Innocenzi, I. De Michelis, F. Ferella, F. Vegliò, Secondary yttrium from spent
fluorescent lamps: recovery by leaching and solvent extraction, Int. J. Miner.
Process. 168 (2017) 87–94.
15
Sustainable Materials and Technologies 32 (2022) e00401
[60] V. Innocenzi, N.M. Ippolito, I. De Michelis, F. Medici, F. Vegliò,
A hydrometallurgical process for the recovery of terbium from fluorescent lamps:
experimental design, optimization of acid leaching process and process analysis,
J. Env. Manage. 184 (2016) 552–559.
[61] V. Innocenzi, N.M. Ippolito, L. Pietrelli, M. Centofanti, L. Piga, F. Vegliò,
Application of solvent extraction operation to recover rare earths from
fluorescent lamps, J. Clean. Prod. 172 (2018) 2840–2852.
[62] V. Innocenzi, I.D. Michelis, F. Vegliò, Design and construction of an industrial
mobile plant for WEEE treatment: investigation on the treatment of fluorescent
powders and economic evaluation compared to other e-wastes, J. Taiwan Inst.
Chem. Eng. 80 (2017) 769–778.
[63] N.M. Ippolito, A. Amato, V. Innocenzi, F. Ferella, S. Zueva, F. Beolchini, F. Vegliò,
Integrating life cycle assessment and life cycle costing of fluorescent spent lamps
recycling by hydrometallurgical processes aimed at the rare earths recovery,
J. Environ. Chem. Eng. 10 (1) (2022), 107064.
[64] N.M. Ippolito, V. Innocenzi, I. De Michelis, F. Medici, F. Vegliò, Rare earth
elements recovery from fluorescent lamps: a new thermal pre-treatment to
improve the efficiency of the hydrometallurgical process, J. Clean. Prod. 153
(2017) 287–298.
[65] N.M. Ippolito, F. Ferella, V. Innocenzi, F. Trapasso, D. Passeri, G. Belardi,
F. Vegliò, Effect of mechanical activation on terbium dissolution from waste
fluorescent powders, Miner. Eng. 167 (2021), 106906.
[66] N.M. Ippolito, G. Belardi, L. Piga, Determination of mineralogical composition of
spent fluorescent powders by coupling ICP-spectroscopy and electronic
microprobe analyses, TrAC Trends Anal. Chem. 94 (2017) 14–20.
[67] M. Jang, S.M. Hong, J.K. Park, Characterization and recovery of mercury from
spent fluorescent lamps, Waste Manag. 25 (2005) 5–14.
[68] M.K. Jha, A. Kumari, R. Panda, J.R. Kumar, K. Yoo, J.Y. Lee, Review on
hydrometallurgical recovery of rare earth metals, Hydrometallurgy 165 (2016)
2–26.
[69] A.R. Kadam, G.B. Nair, S.J. Dhoble, Insights into the extraction of mercury from
fluorescent lamps: a review, J. Environ. Chem. Eng. (2019), https://doi.org/
10.1016/j.jece.2019.103279.
[71] A. Kumari, R. Panda, M.K. Jha, J.R. Kumar, J.Y. Lee, Process development to
recover rare earth metals from monazite mineral: a review, Miner. Eng. 79 (2015)
102–115.
[72] Lampcare, Lamps, Retrieved from, http://www.lampcare.com/, 2021. Accessed:
December 2021.
[73] M.T. Lecler, F. Zimmermann, E. Silvente, A. Masson, Y. Morèle, A. Remy,
A. Chollot, Improving the work environment in the fluorescent lamp recycling
sector by optimizing mercury elimination, Waste Manag. (2018), https://doi.org/
10.1016/j.wasman.2018.02.037.
[74] C.H. Lee, S.R. Popuri, Y.H. Peng, S.S. Fang, K.L. Lin, K.S. Fan, T.C. Chang,
Overview on industrial recycling technologies and management strategies of end-
of-life fluorescent lamps in Taiwan and other developed countries, J. Mater.
Cycles Waste Manage. 17 (2) (2015) 312–323.
[75] H.M. Li, Technology of comprehensive utilization of waste resources of rare earth
fluorescent lamps, China Rare Earths 29 (2008) 97–101.
[76] Y. Liang, Y. Liu, R. Lin, D. Guo, C. Liao, Leaching of rare earth elements from
waste lamp phosphor mixtures by reduced alkali fusion followed by acid
leaching, Hydrometallurgy 163 (2016) 99–103.
[77] H. Liu, S. Li, B. Wang, K. Wang, R. Wu, C. Ekberg, A.A. Volinsky, Multiscale
recycling rare earth elements from real waste trichromatic phosphors containing
glass, J. Clean. Prod. 238 (2019), 117998.
[78] H. Liu, S. Zhang, D. Pan, Y.F. Liu, B. Liu, J.J. Tian, A.A. Volinsky, Mechanism of
CeMgAl 11 O 19: Tb3+ alkaline fusion with sodium hydroxide, Rare Metals 34 (3)
(2015) 189–194.
[79] H. Liu, S. Zhang, D. Pan, J. Tian, M. Yang, B. Li, B. Liu, Recycle rare earth from
waste phosphor by a two-step method, in: Proceedings of the 8th Pacific Rim
International Congress on Advanced Materials and Processing, Springer, Cham,
2013, pp. 1813–1820.
[80] H. Liu, S. Zhang, D. Pan, J. Tian, M. Yang, M. Wu, A.A. Volinsky, Rare earth
elements recycling from waste phosphor by dual hydrochloric acid dissolution,
J. Hazard. Mater. 272 (2014) 96–101.
[81] W. Liu, X. Wang, J.D. Miller, Collector chemistry for Bastnaesite flotation – recent
developments, Miner. Process. Extr. Metall. Rev. 40 (2019) 370–379, https://doi.
org/10.1080/08827508.2019.1647840.
[82] Y. Liu, S. Zhang, H. Liu, B. Liu, A.A. Volinsky, C. Chang, Free oxoanion theory for
BaMgAl10O17: Eu 2+ structure decomposition during alkaline fusion process,
RSC Adv. 5 (62) (2015) 50105–50112.
[83] Y.F. Liu, S.G. Zhang, B. Liu, H.L. Shen, An alkaline fusion mechanism for
aluminate rare earth phosphor: cation–oxoanion synergies theory, Rare Metals 38
(4) (2019) 299–305.
[84] S.V. Loy, K. Binnemans, T. Gerven, Recycling of rare earth from lamp phosphor
waste: enhanced dissolution of LaPO4: Ce3+, Tb3+ by mechanical activation,
J. Clean. Prod. 156 (2017) 226–234.
[85] S.V. Loy, K. Binnemans, T. Van Gerven, Mechanochemical-assisted leaching of
lamp phosphors: a green engineering approach for rare-earth recovery,
Engineering 4 (2018) 398–405, https://doi.org/10.1016/j.eng.2018.05.015.
[86] E. Machacek, J.L. Richter, K. Habib, P. Klossek, Recycling of rare earths from
fluorescent lamps: value analysis of closing-the-loop under demand and supply
uncertainties, Resour. Conserv. Recycl. 104 (2015) 76–93.
[87] A. Malakahmad, M.S. Abualqumboz, S.R.M. Kutty, T.J. Abunama, Assessment of
carbon footprint emissions and environmental concerns of solid waste treatment
and disposal techniques; case study of Malaysia, Waste Manag. 70 (2017)
282–292.
N. Dhawan and H. Tanvar
[88] G. Mei, P. Rao, M. Matsuda, T. Fujita, Separation of red (Y2O3:Eu3+), blue
(BaMgAl10O17:Eu2+) and green (CeMgAl10O17:Tb3) rare earth phosphors by
liquid/liquid extraction, J. Wuhan Univ. Technol. Mater. Sci. Ed. 24 (4) (2009)
603–607.
[89] G.J. Mei, K.F. Xie, G. Li, Research progress of harmlessness and reuse of waste
fluorescent lamp, Res Renew Resour 6 (2007) 29–35.
[90] N. Menad, WEEE Recycling: Physical Separation Processes in Waste Electrical and
Electronic Equipment Recycling, Elsevier Inc., 2016.
[91] B.B. Mishra, N. Devi, K. Sarangi, Yttrium and europium recycling from phosphor
powder of waste tube light by combined route of hydrometallurgy and chemical
reduction, Miner. Eng. 136 (2019) 43–49, https://doi.org/10.1016/j.
mineng.2019.03.007.
[92] A. Miskufova, A. Kochmanova, T. Havlik, H. Horvathova, P. Kuruc, Leaching of
yttrium, europium and accompanying elements from phosphor coatings,
Hydrometallurgy 176 (2018) 216–228.
[93] M. Mitric, A. Kremenovic, R. Dimitrijevic, D. Rodic, Structure and microstructure
of SmY2− O3, Solid State Ionics 101–103 (1) (1997) 495–501.
[94] K. Momma, F. Izumi, VESTA 3 for three-dimensional visualization of crystal,
volumetric and morphology data, J. Appl. Crystallogr. 44 (2011) 1272–1276.
[95] MRT, Lamp Processing: Flexible & Efficient Crush & Separation, Retrieved from,
http://www.mrtsystem.com/products/, 2013.
[96] T. Nakamura, S. Nishihama, K. Yoshizuka, Separation and recovery process for
rare earth metals from fluorescence material wastes using solvent extraction,
Solvent Extr. Res. Dev. Jpn. 14 (2007) 105–113.
[97] A. Otsuki, G. Dodbiba, A. Shibayama, J. Sadaki, G. Mei, T. Fujita, Separation of
rare earth fluorescent powders by two-liquid floatation using organic solvents,
Jpn. J. Appl. Phys. 47 (2008) 5093.
[98] R. Otto, A.W. Kasprzak, Method for recovery of rare earths from fluorescent
lamps, in: Patent US7976798B2 (OSRAM GmbH operation), 2006.
[99] C. Ozgur, S. Coskun, A. Akcil, M. Beyhan, I.S. Üncü, G. Civelekoglu, Combined
oxidative leaching and electrowinning process for mercury recovery from spent
fluorescent lamps, Waste Manag. 57 (2016) 215–219, https://doi.org/10.1016/j.
wasman.2016.03.039.
[100] I.M. Pateli, A.P. Abbott, K. Binnemans, N. Rodriguez Rodriguez, Recovery of
yttrium and europium from spent fluorescent lamps using pure levulinic acid
and the deep eutectic solvent levulinic acid-choline chloride, RSC Adv. 10
(2020) 28879–28890, https://doi.org/10.1039/d0ra05508e.
[101] A.B. Patil, M. Tarik, R.P.W.J. Struis, C. Ludwig, Exploiting end-of-life lamps
fluorescent powder e-waste as a secondary resource for critical rare earth
metals, Resour. Conserv. Recycl. 164 (2021), 105153, https://doi.org/10.1016/
j.resconrec.2020.105153.
[102] S. Pavón, A. Fortuny, M.T. Coll, A.M. Sastre, Rare earths separation from
fluorescent lamp wastes using ionic liquids as extractant agents, Waste Manag.
82 (2018) 241–248.
[103] S. Pavon, A. Fortuny, M.T. Coll, A.M. Sastre, Improved rare earth elements
recovery from fluorescent lamp wastes applying supported liquid membranes to
the leaching solutions, Sep. Purif. Technol. 224 (2019) 332–339.
[104] S. Pavón, T. Lorenz, A. Fortuny, A.M. Sastre, M. Bertau, Rare earth elements
recovery from secondary wastes by solid-state chlorination and selective organic
leaching, Waste Manag. 122 (2021) 55–63.
[105] T.J. Perry, F. Bryant, Fluorescent Tube Crusher with Particulate Separation and
Recovery. Patent Application US, 1992, p. 5092527.
[106] C.A. Pickles, Microwaves in extractive metallurgy: part 2 - a review of
applications, Miner. Eng. 22 (2009) 1112–11184, https://doi.org/10.1016/j.
mineng.2009.02.01.
[107] M.A. Rabah, Recyclables recovery of europium and yttrium metals and some salts
from spent fluorescent lamps, Waste Manag. 28 (2) (2008) 318–325.
[108] C. Raposo, C.C. Windmoller, W.A. Durao Jr., Mercury speciation in fluorescent
lamps by thermal release analysis, Waste Manag. 23 (10) (2003) 879–886.
[109] N. Rey-Raap, A. Gallardo, Determination of mercury distribution inside spent
com-pact fluorescent lamps by atomic absorption spectrometry, Waste Manag. 32
(2012) 944–948.
[110] S.W. Rhee, H.H. Choi, H.S. Park, Characteristics of mercury emission from linear
type of spent fluorescent lamp, Waste Manag. (2013), https://doi.org/10.1016/j.
wasman.2013.07.029.
[111] F. Sadri, A.M. Nazari, A. Ghahreman, A review on the cracking, baking and
leaching processes of rare earth element concentrates, J. Rare Earths 35 (8)
(2017) 739–752.
[112] R.G. Saratale, H.Y. Kim, Y. Park, H.S. Shin, G. Ghodake, R.N. Bharagava, S.
I. Mulla, D.S. Kim, G.D. Saratale, Hydrometallurgical process for the recovery of
yttrium from spent fluorescent lamp: leaching and crystallization experiments,
J. Clean. Prod. 121009 (2020).
[113] N. Schaeffer, X. Feng, S. Grimes, C. Cheeseman, Recovery of an yttrium europium
oxide phosphor from waste fluorescent tubes using a Brønsted acidic ionic liquid,
1-methylimidazolium hydrogen sulfate, J. Chem. Technol. Biotechnol. 92 (10)
(2017) 2731–2738.
[115] D.W. Shin, J.G. Kim, Study on the separation and extraction of rare-earth
elements from the phosphor recovered from end of life fluorescent lamps, Arch.
Metall. Mater. (2015) 60.
[116] N. Shukla, N. Dhawan, Investigation of different processing routes for rare earth
extraction from discarded tubular lights, J. Sustain. Metall 6 (2020) 269–280.
[117] N. Shukla, N. Dhawan, Rapid microwave processing of discarded tubular lights
for extraction of rare earth values, Process. Saf. Environ. Prot. 142 (2020)
238–249.
16
Sustainable Materials and Technologies 32 (2022) e00401
[118] N. Shukla, S. Agrawal, N. Dhawan, Microwave acid baking process for recovery of
rare-earth concentrate from phosphor of end-of-life fluorescent lamps, J. Clean.
Prod. 307 (2021), 127235.
[119] N. Shukla, H. Tanvar, N. Dhawan, Evaluation of alkali processing for the recycling
of rare earth values from spent fluorescent lamps, Physicochem. Probl. Miner.
Process. 56 (4) (2020) 710–722, https://doi.org/10.37190/ppmp/124748.
[120] G. Song, W. Yuan, X. Zhu, X. Wang, C. Zhang, J. Li, J. Bai, J. Wang, Improvement
in rare earth element recovery from waste trichromatic phosphors by mechanical
activation, J. Clean. Prod. 151 (2017) 361–370.
[121] M.L. Strauss, Investigation into the Separation and Purification of Europium and
Yttrium Oxides from Waste Fluorescent Lamps, Ph.D. Dissertation, Worcester
Polytechnic Institute, Worcester, MA, USA, 2018.
[122] M.L. Strauss, B. Mishra, G.P. Martins, Selective reduction and separation of
europium from mixed rare-earth oxides recovered from waste fluorescent lamp
phosphors, in: Rare Met. Technol. 2018, Proceedings of TMS2018, Phoenix,
Arizona, USA, Mar 11-15, 2018, p. 2018.
[123] L.M. Suli, W.H.W. Ibrahim, B.A. Aziz, M.R. Deraman, N.A. Ismail, A review of rare
earth mineral processing technology, Chem. Eng. Res. Bull. (2017) 20–35.
[124] Z. Sun, Y. Xiao, H. Agterhuis, J. Sietsma, Y. Yang, Recycling of metals from urban
mines a strategic evaluation, J. Clean. Prod. 112 (2016) 2977–2987.
[125] T. Takahashi, A. Takano, T. Saitoh, N. Nagano, S. Hirai, K. Shimakage, Separation
and recovery of rare earth elements from phosphor sludge in processing plant of
waste fluorescent lamp by pneumatic classification and sulfuric acidic leaching,
Shigen-to-Sozai 17 (7) (2001) 579–585.
[126] Q. Tan, C. Deng, J. Li, Innovative application of mechanical activation for rare
earth elements recovering: process optimization and mechanism exploration, Sci.
Rep. 6 (2016) 19961.
[127] Q. Tan, C. Deng, J. Li, Enhanced recovery of rare earth elements from waste
phosphors by mechanical activation, J. Clean. Prod. 142 (4) (2017) 2187–2191.
[128] Q. Tan, Jinhui Li, Xianlai Zeng, Rare earth elements recovery from waste
fluorescent lamps: a review, Crit. Rev. Environ. Sci. Technol. 45 (7) (2015)
749–776, https://doi.org/10.1080/10643389.2014.900240.
[129] M. Tanaka, T. Oki, K. Koyama, H. Narita, T. Oishi, Chapter 255 – recycling of rare
earths from scrap, in: Handb. Phys. Chem. Rare Earths 43, 2013, p. 159.
[130] H. Tanvar, N. Dhawan, Extraction of rare earth oxides from discarded compact
fluorescent lamps, Miner. Eng. 135 (2019) 95–104.
[131] H. Tanvar, N. Shukla, N. Dhawan, Recycling of discarded tubular lights for
recovery of rare earth values, JOM 72 (2) (2020) 823–830.
[132] G. Triantafyllou, G.N. Angelopoulos, P. Nikolopoulos, Surface and grain-
boundary energies as well as surface mass transport in polycrystalline yttrium
oxide, J. Mater. Sci. 45 (2010) 2015–2022.
[133] T.U. Freiberg, New Method for Recycling Rare Earths from Fluorescent Waste
[Online]. Accessed at: http://tu-freiberg.de/en/presse/new-method-for-the-recyc
ling-rare-earth-from-fluorescent-waste, 2014.
[134] C. Tunsu, C. Ekberg, T. Retegan, Characterization and leaching of real fluorescent
lamp waste for the recovery of rare earth metals and mercury, Hydrometallurgy
144 (2014) 91–98.
[135] C. Tunsu, C. Ekberg, M. Foreman, T. Retegan, Studies on the solvent extraction of
rare earth metals from fluorescent lamp waste using Cyanex 923, Solvent Extr. Ion
Exch. 32 (6) (2014) 650–668, https://doi.org/10.1080/07366299.2014.925297.
[136] C. Tunsu, C. Ekberg, M. Foreman, T. Retegan, Investigations regarding the wet
decontamination of fluorescent lamp waste using iodine in potassium iodide
solutions, Waste Manag. 36 (2015) 289–296.
[137] C. Tunsu, C. Ekberg, M. Foreman, T. Retegan, Targeting fluorescent lamp waste
for the recovery of cerium, lanthanum, europium, gadolinium, terbium and
yttrium, Miner. Process. Ext. Metall. 125 (2016) 199–203, https://doi.org/
10.1080/03719553.2016.1181398.
[138] C. Tunsu, J.B. Lapp, C. Ekberg, T. Retegan, Selective separation of yttrium and
europium using Cyanex 572 for applications in fluorescent lamp waste
processing, Hydrometallurgy 166 (2016) 98–106, https://doi.org/10.1016/j.
hydromet.2016.10.012.
[139] C. Tunsu, M. Petranikova, C. Ekberg, T. Retegan, A hydrometallurgical process for
the recovery of rare earth elements from fluorescent lamp waste fractions, Sep.
Purif. Technol. 161 (2016) 72–186.
[140] USGS, Rare earth statistics and information, Accessed from, https://pubs.usgs.
gov/periodicals/mcs2020/mcs2020-rare-earths.pdf, 2020.
[141] B. Van den Bogaert, D. Havaux, K. Binnemans, T. Van Gerven, Photochemical
recycling of europium from Eu/Y mixtures in red lamp phosphor waste streams,
Green Chem. 17 (4) (2015) 2180–2187.
[142] H.R. Verma, S.K. Sahu, P. Meshram, B.D. Pandey, T.R. Mankhand, Kinetics of
hydrometallurgical extraction of rare earth metals from waste phosphor, Int J Res
Eng Technol (IJRET) 2 (5) (2013) 251–255.
[144] S. Wu, L. Wang, L. Zhao, P. Zhang, H. El-Shall, B. Moudgil, X. Huang, L. Zhang,
Recovery of rare earth elements from phosphate rock by hydrometallurgical
processes – a critical review, Chem. Eng. J. 335 (2018) 774–800.
[145] Y. Wu, X. Yin, Q. Zhang, W. Wang, X. Mu, The recycling of rare earths from waste
tricolor phosphors in fluorescent lamps: a review of processes and technologies,
Resour. Conserv. Recycl. 88 (2014) 21–31.
[146] Y. Wu, B. Wang, Q. Zhang, R. Li, C. Sun, W. Wang, Recovery of rare earth
elements from waste fluorescent phosphors: Na2O2 molten salt decomposition,
J. Mater. Cycles Waste Manag. 16 (4) (2014) 635–641.
[147] Y. Wu, Q. Zhang, T. Zuo, Selective recovery of Y and Eu from rare-earth tricolored
phosphorescent powders waste via a combined acid-leaching and photo-reduction
process, J. Clean. Prod. 226 (2019) 858–865.
N. Dhawan and H. Tanvar
[148] F. Xie, T.A. Zhang, D. Dreisinger, F. Doyle, A critical review on solvent extraction
of rare earths from aqueous solutions, Miner. Eng. 56 (2014) 10–28, https://doi.
org/10.1016/j.mineng.2013.10.021.
[149] M. Yamashita, T. Akai, M. Murakami, T. Oki, Recovery of LaPO4: Ce, Tb from
waste phosphors using high-gradient magnetic separation, Waste Manag. 79
(2018) 164–168.
[150] F. Yang, F. Kubota, Y. Baba, N. Kamiya, M. Goto, Selective extraction and
recovery of rare earth metals from phosphor powders in waste fluorescent lamps
using an ionic liquid system, J. Hazard. Mater. 254 (2013) 79–88.
[151] H. Yang, W. Wang, H. Cui, D. Zhang, Y. Liu, J. Chen, Recovery of rare earth
elements from simulated fluorescent powder using bifunctional ionic liquid
extractants (Bif-ILEs), J. Chem. Technol. Biotechnol. 87 (2012) 198–205, https://
doi.org/10.1002/jctb.2696.
[152] X. Yin, Y. Wu, L. Wang, T. Zuo, Recovery of Eu from waste blue phosphors
(BaMgAl10O17: Eu2+) by a sodium peroxide system: kinetics and mechanism
aspects, Miner. Eng. 151 (2020), 106333.
[153] L. Yurramendi, L. Gijsemans, F. Forte, J.L. Aldana, C. Río, K. Binnemans,
Enhancing rare-earth recovery from lamp phosphor waste, Hydrometallurgy 187
(2019) 38–44, https://doi.org/10.1016/j.hydromet.2019.04.030.
[154] M. Yu, G. Mei, Y. Li, D. Liu, Y. Peng, Recovering rare earths from waste phosphors
using froth flotation and selective flocculation, Mining, Metall. Explorat. 34
(2017) 161–169, https://doi.org/10.19150/mmp.7855.
17
Sustainable Materials and Technologies 32 (2022) e00401
[155] S. Zhang, H. Liu, D. Pan, J. Tian, Y. Liu, A.A. Volinsky, Complete recovery of Eu
from BaMgAl10 O17: Eu2+ by alkaline fusion and its mechanism, RSC Adv. 5 (2)
(2015) 1111–1113.
[156] S.G. Zhang, M. Yang, H. Liu, D.A. Pan, J.J. Tian, Recovery of waste rare earth
fluorescent powders by two steps acid leaching, Rare Metals 32 (6) (2013)
609–615.
[157] J.J. Braconnier, A. Rollat, Method of recovering rare earths from a solid mixture
containing a halophosphate and a rare earth compound and solid mixtures
suitable for this method, in: Patent US 9,102.998 B2 (Rhodia-Solvay operation),
2015.
[158] S. Hopfe, S. Konsulke, R. Barthen, F. Lehmann, S. Kutschke, K. Pollmann,
Screening and selection of technologically applicable microorganisms for
recovery of rare earth elements from fluorescent powder, Waste Manag. 79
(2018) 554–563, https://doi.org/10.1016/j.wasman.2018.08.030.
[159] H. Liu, S. Zhang, D. Pan, Y.F. Liu, B. Liu, J.J. Tian, A.A. Volinsky, Mechanism of
CeMgAl 11 O 19: Tb3+ alkaline fusion with sodium hydroxide, Rare Metals 34 (3)
(2015) 189–194.
[160] H. Liu, S. Zhang, D. Pan, J. Tian, M. Yang, M. Wu, A.A. Volinsky, Rare earth
elements recycling from waste phosphor by dual hydrochloric acid dissolution,
J. Hazard. Mater. 272 (2014) 96–101.
[161] B. Swain, L. Kang, C. Mishra, J.W. Ahn, H.S. Hong, Materials flow analysis of
neodymium, status of rare earth metal in the Republic of Korea, Waste Manag 45
(2015) 351–360, https://doi.org/10.1016/j.wasman.2015.07.020.