Market analysis: 7.35B USD in 2022 projected to rise to 14.

61B USD by 2029, this

rise is expected due to the increasing acceptance of environmentally friendly lighting
solutions. The cost-effectiveness of fluorescent lamps is higher than LED and other
types of lamps, partly due to its low cost, which drives demand in emerging
countries. Its extensive use in the lighting of industrial and outdoor areas makes it a
big candidate for a market expansion. The process of recycling fluorescent lamps is
highly attractive due to the potential recovery of many REE's included in the
phosphor inner coating included in the bulb section, elements included in the
phosphor include, but are not limited to, Yttrium, Europium, Lanthanum, Cerium and
Terbium, the former two's global consumption being mainly comprised of phosphor
related usage. Europium for one is one of the rarest rare earth elements and that
alone makes its recycling very interesting from an economic perspective.

Base Material analysis: The average fluorescent lamp includes its metallic wiring
components, plastic casing, metal fittings, metal electrodes and the glass bulb which
in turn contains a gas mixture, generally comprised of an inert gas (Argon, Xenon,
Neon or Krypton) and mercury vapor, this gaseous mix is stored in very low
pressure, around 0.8% of earth's atmosphere. The bulb's inner walls are coated with
a blend of rare earth salts, commonly called "phosphor”. The coating is responsible
for the actual light emissions through the physical phenomena of phosphorescence,
hence the lamp's name.

Waste Recovery process: Initially the lamps are disassembled, separating their
metal fittings, casing and plastic parts for direct recycling, the bulb however is
passed through a crusher that separates the phosphor, glass shards and
connections from each other. The mass is then heated in a furnace, the mercury
vaporizes and passes through a condenser, the resulting liquid is then repurposed, it
is important to note that there are carbon HEPA filters in the admission of mass near
the crusher intake which adsorb a small portion of vapor/liquid mercury. The heating
process is effective in removing over 98% of mercury provided there's the addition of
a reductant, this process was carried out at 300 degrees celsius for 2 hours, for
complete removal from the phosphor the process was carried out at 540 degrees
celsius for 5 hours in an inert gas atmosphere and closed system, the resulting gas
was passed through carbon HEPA filters specialized for the recovery of mercury. The
entire mass must be subjected to the heating process due to the mercury
concentrations being distributed through the various components, despite mainly
concentrating in the phosphor throughout the lamp's use (>80%) significant amounts
can be found in the glass and connection components. The REEs composition
present in the phosphor blend is over 50% red phosphor, comprised of
Europium-doped Yttrium oxide (Y2O3:Eu3+), overall per Kg of waste 8.4g of REMs
were present the which being composed of: 6.8g Yttrium and 0.4g Europium
together making up over 85% of the phosphors REEs. After the removal of other
contaminating particles like the glass shards, plastic and metallic fittings, and finally
wiring and connections there was a significant increase in the ratio of REEs to waste:
105.7g per kg of waste, the waste in this final state is comprised of pretty much the
phosphor coating in powder form and trace mercury that could not be removed
through the initial furnace stage.

Waste Leaching: The removal of REEs from the phosphor is typically associated
with direct acid leaching using HCl, H2SO4 or HNO3, the solubility of the REEs is
associated with the phosphor's crystal structure, the which is the limiter in economic
and scalability factors for this route. H2SO4 is preferred due to the precipitation of Ba
and Ca sulfates, which are insoluble in the solution, however the co-precipitation of
REEs does occur generating losses in the process. Efficiency seems to vary
throughout the literature, reportedly a figure up to 97% Yttrium and 95% Europium
was recovered at optimal conditions 0.5M HNO3 for 24h at 10% pulp density and 20
degrees celsius. There is an increased need for more concentrated solutions to
dissolve other REEs like Cerium and Terbium at room temperature, this is due to the
association of the REEs, whilst Yttrium and Europium are mostly found in an oxide
form, which is easily dissolved by acid solutions, other elements like Terbium tend to
occur in complex oxide forms and phosphates, this can be exploited for the
development of a selective leaching method. The one mentioned above uses
relatively low concentrations of nitric acid and removes most Yttrium and Europium
whilst leaving the vast majority of the other elements in the solid portion. Acid
concentration influences directly in the dissolution of other REEs, increasing
dramatically in concentrations above 1M (168h leach time), this could be beneficial
for recovery of multiple metals or detrimental for selective leaching of Yttrium and
Europium as individual elements. Leaching time also makes a dramatic impact on
metal leached percentage for other REEs, whilst Y and Eu are mostly extracted in
the first 24h other elements increase mostly in a linear fashion over time, these
include Cerium, Gadolinium, Lanthanum and Terbium, it is worth noting that these
four elements only reach around 60% leached amount at 2M HNO3 over >100h
regular leaching time. Lanthanum on the other hand is hardly affected over time and
also is mostly extracted in the first 24h, despite that being a low amount (around
25% at most). All of these were evaluated in 0.5M 1M and 2M HNO3 concentration,
in all cases the 2M solution was most efficient in the leaching amount, except for
Lanthanum which was most efficiently leached with a 1M solution, the difference
between 2M solution (2nd most efficient) and 0.5 (least efficient) were, respectively,
5% and 10%. It must be noted that the mercury in the original research is being
ignored here due to pre-processing techniques employed beforehand, in which
negligible amounts of mercury were left in the leftover phosphorus. Solid liquid ratios
had significant effects on the dissolution of Cerium, Gadolinium and Terbium
decreased significantly by about 12% when the ratio was increased from 10% to
20% whilst leaching of Lanthanum was increased to 11.6%, a ratio of 30% almost
ceased leaching as a whole for all REEs, leaching of 1% of all REEs was observed.
The selectivity of the process could be increased by exploiting this difference in solid
to liquid ratios and leaching amount. The dramatic difference observed between 20%
and 30% solid liquid ratios is likely due to the fast consumption of protons by other
metals present in the solid phase, notably Calcium, generally present as calcium
phosphate.

There have been better efficiency figures reported, however these either have a
leach time of over 24h, are done over heated solutions or demand HPAL processes.
Better efficiency was also reported for other metals such as Cerium and Terbium by
way of a 2M H2SO4 solution at 37 degrees celsius for 8h. In general terms sulphuric
acid has been avoided due to poor precipitation after the leaching process which
could generate secondary waste streams and increase the risk of co-precipitation.
Moreover the extraction of Yttrium and Europium should be favored due to these
being the REEs with the highest concentration in the base material on average, there
is a case to be made for mechanically activated solution leaching, where the
activation energy for leaching is potentially reduced thus reducing the usage of acid
and improving the time of retrieval for the PLS, specially for the recovery of Yttrium
and Europium, which are the focus of this study.

In sum the optimal economic and efficient conditions for the leaching of Yttrium and
Europium are as follows: leaching on weak nitric acid solution (0.5M) up to 24h at 20
degrees celsius in a 10% solid to liquid ratio, an increase of the ratio to 20% leads to
greater consumption of protons, in which case it is recommended the use of a 1M
solution of acid. The leaching of the other present REEs requires considerably more
concentrated solutions (4M) and an extended period of time (up to a week), despite
that there isn't a big incentive to perform the leaching of other metals due to the lack
of feasibility of recovery from the waste, the small quantities of Gadolinium and
Terbium also don't justify their recovery in economic terms, moreover Lanthanum
and Cerium are not yet viewed as critical as other REEs contained in the studied
waste. Therefore the main focus of this study should be on the recovery of Yttrium
and Europium as highlighted in this piece, due to mainly economic factors. Recovery
of Lanthanum, Cerium and Terbium will be outlined in this work, however it must be
noted that there are several limitations due to factors such as low concentrations
within the waste, economic relevance and overall cost of investment.

Recovery from Leachate (PLS): In general terms REEs can be recovered from the
leachate through solvent extraction (SX) followed by precipitation and calcination of
the precipitate. Many precipitating agents are candidates to be used including
Oxalates, Phosphates, Fluorites and Carbonates. The focus of this work will be on
Oxalate induced precipitation due to its quick formation of insoluble compounds with
lanthanide-series metals in acidic solutions and densely crystalline forms, which
makes filtering easier than its counterparts, which tend to only start precipitating in
pH values between 4-6. Moreover pyrolysis of mixed REM-Oxalic compounds yields
mixed REM-Oxides which is the most common form of occurrence for REMs.

Individual separation of REMs is seen as a big challenge and generally done through
solvent extraction (SX), different reagents have successfully separated REEs, these
agents include but are not limited to Cyanex 572, Cyanex 923, D2EHPA and
DODGAA. To maximize the extraction of Yttrium and Europium, the focus of this
study, the best agent was observed, due to the presence of HNO3, to be
[A336][P204] IL and [A336][P507] IL with a maximum recovery for REMs of 95% at
pH 0.56 in 5-7 stages with an O:A ratio of 4:1 on a countercurrent extraction, there
needs to be an addition of 10% iso-octanol to prevent the formation of an unwanted
third phase located between the aqueous and organic phases. The stripping was
shown to be easy in low acidity, using an n-heptane solution of Bif-ILEs (217g/L) to
recover REEs(III), it also became evident that with small variations on initial acid
concentration the stripping yield changed dramatically, above 0.02M the stripping
percentage reached 100%. The regeneration of the extractants was also proven to
be high with experiments yielding little to no change in extractability up to five
regeneration cycles.

Yttrium and Europium can be separated through an easier reduction process, it is

simpler, less energy intensive and takes less steps. By adding zinc powder to a
solution containing both Y(III) and Eu(III) reduces to Eu(II) and by using sulphuric
acid it precipitates as EuSO4, this reduction of Eu(III) to Eu(II) has the side effect of
co-precipitation of Yttrium (16%). The Sulfate grade was 96% and 73% recovery.
Photo-chemical reduction can also be successfully applied to precipitate EuSO4 with
95% efficiency with over 98% purity, however the UV exposure required is achieved
in long periods of time, typically between 24 and 30 hours which could potentially
hinder its economic viability.

The Yttrium remains concentrated and largely untouched in the liquid phase in this
procedure, to remove it oxalic acid is introduced into the system, causing the Yttrium
to precipitate as an oxalate complex, this precipitate is then subjected to calcination
which in turn yields solid Yttrium oxide(III), the recovery is over 95% and the purity
over 98%.

It is worth noting that other REEs, like Lanthanum, Cerium and Terbium are
concentrated in the leaching solid phase, and can be sent to be processed through
other means (explored later in this work) since as highlighted in previous sections,
they don't represent a big portion of the waste in terms of REEs, moreover they also
do not represent economic interest due to low concentration and high energy and
reactants usage to separate and concentrate (generally through another round of
solvent extraction and subsequent precipitation to isolate products). There is also the
need to process radioactive elements separately due to their radioactivity and
potential harm to both environment and human health, despite their low
concentration in the waste there could be the need to process them regardless, once
the system is designed to receive multiple waste products with varying composition,
the possibility of receiving radioactive material shouldn't be overlooked.

Other REEs recovery from previous leachate: After the previous processes of
recovery from the initial phosphor and the stripping of Yttrium and Europium as
significant REEs there can be employed a mechanically aided reduction of activation
energy for the optimized leaching of Lanthanum, Cerium and Terbium, which the
regular leaching with concentrated nitric acid was unable to extract significant
amounts.

After a filtration and precipitation of Yttrium and Europium, which was described in
the previous piece, the residue can be then dried and, with the aid of a ball mill using
1mm alumina spheres, be ground at 600 RPM for the optimal time of 60 minutes
using 4N HNO3 as the liquid medium. This process manages to reduce the
activation energy for leaching REEs from an average of 68kJ/mol (unmilled) to
1.4kJ/mol (milled as above). The extended milling modifies the crystalline lattices
and amorphous phase contents to an extent where the limiting mechanism goes
from chemically controlled to mainly diffusion controlled, the latter of which tends to
have lower activation energies (<40kJ/mol).

The milled sample can then be subjected to a regular room temperature acid
leaching with the same 4N HNO3 as the leaching agent, the optimal time was found
to be 120min with an acid concentration of 50 g/L. The Leachate can then be
subjected to the extraction of the REEs with an efficacy of 99% for Lanthanum,
87.3% for Cerium and 86.3% for Terbium. This process is considerably more efficient
compared to the currently employed methods of highly concentrated 18M H2SO4 at
high temperatures and molten alkali (NaOH or NaCO3).

Separation of the individual REEs: As was explored above it is possible to secure

a concentrated stream of Cerium Lanthanum and Terbium through the mechanical
activation method. However the solution still has the three elements mixed, to
separate them multiple methods will be employed. The first fraction, comprised of
Terbium can be extracted from the solution through a solvent extraction using
D2EHPA in a Xylene solution, in the organic phase the Terbium will be separated
almost entirely from the Lanthanum and Cerium aqueous phase, the organic can
then be stripped using a strong acid and precipitated using oxalic acid, the
precipitate is then calcined in a high temperature oven producing the end product:
Terbium Oxide (Tb4O7) with a purity of over 90%, the recovery is also close to
80-85%. The remaining fraction comprised of Cerium and Lanthanum is also
precipitated with the aid of oxalic acid and calcined in a high temperature oven
producing the final product: Cerium-Lanthanum Mixed Oxide [(Ce, La)2O3] with a
purity of over 85%, the recovery is also close to 80-85%.

Economic Viability: It remains to be seen whether this method is economically

viable due to the low concentration of the elements explored present in the initial
fluorescent lamp phosphor despite the economic value of these elements being quite
considerable. Current techniques suggest that the process would not be feasible,
however, the mechanical activation technique seems to lower the costs massively
and the overall process resembles the Yttrium and Europium recovery in many
aspects utilizing the same relatively cheap reactants. The biggest bottleneck for
economic viability seems to be the milling which is notoriously energy intensive in
large scales, although in smaller scales the costs might not be so high.