PHYSICAL SEPARATION PROCESSES

Physical separation processes are often used as a pretreatment method. These methods are
intended to separate a high REE‐containing fraction from a low REE‐containing fraction and
reduce the amount of material to be transported to the processing plant. Dai et al. (2014)
observed that the finer fraction (<25 µm) was more enriched in REE. Suganal (2018) studied
coal ash from the Pilimanan pilot plant. The REE content in this material is 77.85 ppm. In this
study, the authors attempted to increase the concentration of REEs by using a shaking table and
magnetic separator methods. The shaking table showed that REE concentrations increased up
to twice. However, the results of the magnetic separation technique were not significant. Lin et
al. (2017) compared different physical separation methods (particle size, magnetic, and density
separation) to evaluate their effectiveness on different CCP samples. The results highlighted
that the density separation method showed the highest REE enrichment rates and REE
enrichment varied according to the type of CP.
Pan et al., (2020) used a coal fly ash from a power generation plant, located in Southwest
China. They concentrated the rare earth elements using physical separation techniques and
further leaching. They pointed the separation and extraction methods require an understanding
of the modes of occurrence of REE. With this knowledge, we could design and research
efficient physical and chemical recovery processes. Their raw material has a predominant
glassy aluminosilicate phase, which is difficult to leach using mineral acids. Besides, it is
required to remove impurities, such as unburn carbon, and ferric oxides because they consume
more acid. Hence, physical separation is needed before the leaching. They made a particle size
classification, followed by magnetic separation, as Figure 1 shows. Particle size separation is
necessary since the lowest size particles have the most content of REE. The iron particles were
separated by magnetic separation. They separated at 38 µm and with a magnetic field of 5 A.
The REE content of the raw material was 782.1 ppm and the final product has 1025 ppm, with
a yield of 31.46 %.
To summarize, physical separation processes help to: i) concentrate the REEs in a specific
fraction, thus limiting the quantity of material to be treated; ii) limit the problems related to the
presence of iron oxides in hydrometallurgical processes for the recovery of REEs, and iii)
reduce the quantity of acid used during the recovery of REEs. Although the physical separation
and/or recovery techniques presented here are promising, they are generally only one step in
the recovery of REEs.

1
 Fig. 1 Proposed extraction process for recovering the REE from fly ash

(Pan et al., 2020)

Physical Separation and leaching combined processes

Pan et al., (2021) used a coal fly ash sample from a U.S. coal power plant. The REE content
of the sample was 487.31 ppm. They used NaOH and Na2CO3 as additives in order to break
the glassy (amorphous) sodium silicate and sodium aluminosilicate. In the first stage of the
experiment, they leached the fly ash using the principal mineral acids. Then they calcinated the
samples using NaOH and Na2CO3 and then a leaching with water at 90 °C. After a water
leaching, an acid leaching at 60 °C was made. Figure 2 summarized their experiment. When
the sample is roasted with NaOH, REE recovery was improved to values in the range of 66%
~ 79%. However, the effect of the roasting temperature on the REE recovery was not significant.
Finally, the maximum recovery was around 90 %wt. The Na2CO3 requires a minimum roasting
temperature of 850 °C. On the other hand, NaOH could recover 70 % of REE at a roasting
temperature of 235 °C.

2
Figure 2. Schematic chemical roasting, water leaching and acid leaching for recovering REE.
(Pan et al., 2021)

Shoppert at al., (2023) used a coal fly ash from Reftinskaya TPP in Asbest, Russia. The
REE content was 177.5 ppm. They proved the REE in coal fly ash is associated with mullite
and amorphous glassy phase. Besides, it is encapsulated in the aluminosilicate glassy phase. It
has a strong correlation with Al and Si. After desilication (alkali activation) using NaOH at
11.6 mol/L, L-S ratio of 10 and 110 °C, they can remove the amorphous glassy phase. After
desilication, Al2O3 increased from 26.45 % to 42.01 %, and SiO2 decreased from 62.10 % to
40.00 %, and REE is increased to 339 ppm. They concluded NaOH leaching helps to increase
the amount of acid-soluble phase by dissolving the aluminosilicate phases. In addition, the
presence of ammonia sulfate removes the organic carbon (unburned). Figure 3 shows the
process for recovery of REE from coal fly ash used in this study.

3
 Fig. 3 Flowsheet for the REEs extraction from the coal fly ash.

(Shoppert et al., 2023)

CHALLENGES OF RECOVERY REES FROM CCPS

Coal combustion products (CCPs) have proven to be an interesting source of REEs and
many studies have been carried out on this subject. The techniques for recovering REEs
depended on the type of CCPs studied but also on the mineralogy of each CCP. Thus,
understanding the distribution of critical elements in CCPs is necessary to develop an
appropriate recovery technique. Even if some CCPs contain high levels of REEs, this is not the
case for all CCPs. Thus, co-recovery techniques may be interesting to make this process more
economically profitable. In order to improve the recovery rate of REEs, preliminary steps may
also be required, such as alkaline leaching, heating, physical separation, etc. However, for these
types of methods, significant energy and chemical costs may be associated. From an
environmental point of view, chemical spills, the generation of toxic secondary waste, dust
generation during the transport of CCPs, etc., may be linked to this type of pre‐treatment.
However, these promising techniques need to be optimized. Table 1 highlights the
concentration of REE only using acid leaching. Acid leaching is not enough for recovering
more than 60 %. On the other hand, Table 2 remarks the advantages of alkali fusion of CCPs.

4
In fact, an alkali fusion using NaOH at 450 ºC and further acid leaching using HNO3, can
recover the 70 % of REE.

Table 1. Summary of acid leaching controlling parameters investigated by different studies

Parameter study Conditions REE recovery

Acid leaching: 20, 30, 45,

Below 45°C
Leaching 60, 75, and 90°C; 2 mol/L
(Cao et al., 2018) <30%, 90°C
temperature HCl; 1:10 ratio; 200 rpm 120
50%
min
Acid leaching: 50, 100, 200,
300, and 500 rpm; 60°C; 2
(Cao et al., 2018)
mol/L HCl; 1:10 ratio; 120
Stirring min
speed
Acid leaching: 100, 200, 0 rpm < 36%,
(Tang et al., 2019) 300, 400, 500, 600 rpm; 2 400 rpm >
mol/L HCl; 1:10 ratio 49%
Acid leaching: 1:5, 1:10, 1:5 <
(Tang et al., 2019) 1:15, 1:20, and 1:30 ratio; 2 50%,1:20 >
Solid to mol/L HCl; 400 rpm 60%
liquid ratio Acid leaching: 1:5, 1:10,
1:5 40%; 1:10
(Cao et al., 2018) 1:15, 1:20; 200 rpm, 60°C; 3
60%
mol/L HCl; 120 min
Acid leaching: 30, 60, 90,
30 min < 50%,
120, 150, 180 min; 3 mol/L
(Cao et al., 2018) 120 min >
HCl; 60°C; 200 rpm; 1:10
Leaching 60%
ratio
time
Acid leaching: 0 to 120 min; 0 min < 40%,
(Tang et al., 2019) 2 mol/L HCl; 1:10 ratio; 200 120 min >
rpm 50%

Acid leaching: 0.1, 0.5, 1, 0.1 mol/L

(Tang et al., 2019) 2,4 mol/L HCl; 1:10 ratio; 0.03%, 2
400 rpm mol/L 59.78%

Acid Acid leaching:1, 2, 3, 5, and 1 mol/L <

concentration (Cao et al., 2018) 7 mol/L; 200 rpm, 60 °C, 30%, 3 mol >
1:10 ratio; 120 min. 60%
Acid leaching: 0.0501–
0.6001, 0.06–0.61, 0.366–
(Taggart et al., 2018)
0.916, 2 mol/L HNO3, room
temp

5
Table 2. Summary of alkali fusion controlling parameters investigated by different studies.
REE
Parameter Study Conditions
recovery
CaSO4,
Roasting: CaSO4, CaO, Na2CO3, NaOH, CaO,
(Taggart et al., and Na2O2, 150, 250,350 and 450 °C; 1:1 Na2CO3
Flux type
2018) and 1:6 ratio; 30 mins <50%
Acid leaching: 2 mol/L HNO3 NaOH, and
Na2O2 >90%
150 and
Roasting: NaOH, 150, 250,350 and 450 °C; 250°C
(Taggart et al.,
1:1 ratio, 30 mins <60%, 350
2018)
Acid leaching: 1 mol/L HNO3 and 450 °C
>70%
Roasting: NaCO3, NaOH, 680, 740, 800,
and 860 °C; 1:1 ratio; 30 min
(Tang et al., 2019)
Acid leaching: 2 mol/L HCl, 1:10 ratio, 200
Roasting rpm
temperature Roasting: NaCO3, 400, 600, 800, and
79 % for
851 °C; 1:1 ratio; 30 min: NaOH 235, 318,
NaOH and
(Pan et al., 2021) 400, 600 and 800 °C; 1:1 ratio; 30 min
89 % for
Acid leaching: 6 mol/L HNO3, 1:50 ratio,
Na2CO3
400 rpm, 60 °C, 2 hr.
From 600 to
(Zhang and Roasting: 600 to 1000 °C; 120 mins 750 °C the
Honaker., 2020) Acid leaching: 2 mol/L HNO3 recovery was
80 to 90 %
NaOH 1:05
Roasting: 1:1 and 1:6 ratio; CaSO4, CaO,
(Taggart et al., 50%, 1:1
Na2CO3, NaOH, and Na2O2; 450 °C; 30
2018) 80%, 1:6
mins Acid leaching: 2 mol/L HNO3
90%
Roasting: 1:05, 1:1, 1:1.2, 1:1.5 ratio,
1:1.2
Flux to NaCO3, 30 min,
(Tang et al., 2019) 55.98%,
CFA ration Acid leaching: 2 mol/L HNO3, 1:10 ratio,
1:1.5 49.06%
200rpm
53 % REE,
Alkali Leaching: NaOH 5 M; 100 °C, 120
(Trinch, Kim and from 267
min. Acid leaching: 5 mol/L HCl, 1:10
Lee, 2022) ppm to 556
ratio, 200rpm, 120 min
ppm

6
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