minerals

Review
A Comprehensive Review of Rare Earth Elements
Recovery from Coal-Related Materials
Wencai Zhang 1, *, Aaron Noble 1 , Xinbo Yang 2 and Rick Honaker 2
1 Department of Mining and Minerals Engineering, Virginia Polytechnic Institute and State University,
Blacksburg, VA 24061, USA; aaron.noble@vt.edu
2 Department of Mining Engineering, University of Kentucky, Lexington, KY 40506, USA;
xinbo.yang@uky.edu (X.Y.); rick.honaker@uky.edu (R.H.)
* Correspondence: wencaizhang@vt.edu




Received: 22 April 2020; Accepted: 14 May 2020; Published: 17 May 2020


Abstract: Many studies have been published in recent years focusing on the recovery of rare earth
elements (REEs) from coal-related materials, including coal, coal refuse, coal mine drainage, and coal
combustion byproducts particularly fly ash. The scientific basis and technology development
have been supported by coal geologists and extractive metallurgists, and through these efforts,
the concept has progressed from feasibility assessment to pilot-scale production over the last five
years. Physical beneficiation, acid leaching, ion-exchange leaching, bio-leaching, thermal treatment,
alkali treatment, solvent extraction, and other recovery technologies have been evaluated with varying
degrees of success depending on the feedstock properties. In general, physical beneficiation can be a
suitable low-cost option for preliminary upgrading; however, most studies showed exceedingly low
recovery values unless ultrafine grinding was first performed. This finding is largely attributed to the
combination of small RE-bearing mineral particle size and complex REE mineralogy in coal-based
resources. Alternatively, direct chemical extraction by acid was able to produce moderate recovery
values, and the inclusion of leaching additives, alkaline pretreatment, and/or thermal pretreatment
considerably improved the process performance. The studies reviewed in this article revealed two
major pilot plants where these processes have been successfully deployed along with suitable solution
purification technologies to continuously produce high-grade mixed rare earth products (as high as
+95%) from coal-based resources. This article presents a systematic review of the recovery methods,
testing outcomes, and separation mechanisms that are involved in REE extraction from coal-related
materials. The most recent findings regarding the modes of occurrence of REEs in coal-related
materials are also included.

Keywords: rare earth elements; recovery; coal; acid mine drainage; coal combustion byproducts

1. Introduction
Rare earth elements (REEs) including the 15 lanthanides plus yttrium and scandium have been
identified as critical commodities by several international agencies and national governments due to
their crucial roles in clean energy, high tech, and national defense industries [1–3]. REEs scarcely form
natural ore depositsthat are economically recoverable. As a result, only a few commercial deposits
are currently being extracted worldwide. This combination of restricted supply and critical need has
prompted many public and private entities to evaluate alternative REE sources. Coal-related materials,
including coal refuse, coal fly ash, and coal mine drainage have been identified as a potentially
promising resource. The average REE contents in lignite and bituminous coals as well as lignite
and bituminous coal ashes worldwide have been estimated to be around 69, 72, 378, and 469 ppm,
respectively [4]. Many coal deposits with elevated REE contents have been found and reported in the

Minerals 2020, 10, 451; doi:10.3390/min10050451 www.mdpi.com/journal/minerals

Minerals 2020, 10, 451 2 of 28

literature [5–8]. REE concentration in coal mine drainage varies from site-to-site, ranging from several
ppb to ppm levels [9,10].
Recovering REEs from coal-related materials has several advantages over commercial rare earth
ores: (1) coal-related materials contain more heavy and critical REEs (HREEs and CREEs) relative to the
light REEs (LREEs) [5,10]; (2) the mining costs are negligible since REEs can be produced as byproducts
from the coal production and utilization processes [11]; (3) coal-based materials, particularly coal
mine drainage, tend to have lower concentrations of radionuclide (e.g., U and Th) when compared to
traditional ore deposits [12]; and (4) REE recovery from coal materials has the potential to mitigate
or eliminate legacy environmental issues [13]. The concept has been discussed in several review
articles [5,14–16]; however, these articles have primarily addressed geologic considerations, such as
depositional settings and resource characteristics.
To this end, the U.S. Department of Energy initiated research and development efforts in 2014 to
evaluate the technical and economicviability of extracting REEs from coal-related materials with a
particular focus on technology maturation and process development [17]. During the last five years,
the extraction of REEs from coal-related materials has progressed through feasibility assessment,
field sampling and characterization, bench-scale REE separation, and pilot-scale REE production stages.
During this period, many innovative findings concerning the recovery of REEs from coal-related
materials have been published, which significantly contributed to the scientific knowledge in this
area [11,12,18–26]. A review article focused on promising methods for REE recovery from coal and
coal byproducts was published by the authors of [27] in 2015. However, experimental results and
findings were limited at that time. Considerable developments in this area since 2015 led to a need for
another review in order to cover the latest findings.
This review article summarizes technical information regarding process flowsheets, metallurgical
performance, and economical metrics of the various methods that have been developed for REE
extraction from coal-related materials. This review will provide comparative data to prompt further
study and analysis in this area. The review is divided into three sections based on the types of the
coal-related materials that were investigated as reported in the literature, i.e., coal and coal refuse,
coal combustion ash, and acid mine drainage. Recent findings regarding the modes of occurrence of
REEs in coal-related materials and how these findings inform process design are also covered.

2. REEs in Coal and Coal Refuse

The geological aspects such as accumulation mechanisms and modes of occurrence of REEs in
coal and coal refuse have been extensively investigated by coal geologists, and these topics have been
systematically reviewed in several prior publications [5,14,15,28,29]. Therefore, this article only focuses
on the recovery aspect of REEs from coal and coal refuse.

2.1. Physical Beneficiation of REEs from Coal and Coal Refuse

Several studies have been performed to concentrate rare earth (RE)-bearing mineral particles from
coal and coal refuse using physical beneficiation techniques such as gravity, magnetic, and flotation
separations [11,20,30–34]. Table 1 summarizes some of the beneficiation performances. It is worth
noting that decarbonization is normally conducted prior to REE beneficiation, which enables the
production of clean coal. A systematic study was performed by Honaker et al. [35] to evaluate the
viability of using physical separation methods (riffle table, multi-gravity, and wet high intensity
magnetic separations as well as froth flotation) to concentrate rare earth minerals from coal and coal
refuse, and representative test results are shown in Table 1. With respect to gravity-based separations,
the REEs were only enriched by a factor of 1.1 using a riffle table, and the separation performance
was still unsatisfactory when using a multi-gravity separator. This finding has been corroborated
by a separate study performed by another group of researchers [24]. Physical separations (size,
density, and magnetic) performed on a clean coal sample collected from Kentucky, USA showed that a
Minerals 2020, 10, 451 3 of 28

maximum enrichment ratio of 1.21 was obtained. As such, a high degree of enrichment of rare earth
minerals from coal and coal refuse is difficult using physical separation methods.

Table 1. A summary of physical beneficiation of rare earth minerals from coal and coal refuse.

Separation REE Re
Sample Sources Separation Method ER Reference
Method (ppm) (%)
Coarse refuse (28 × 100
Fire Clay Riffle table 252 w 1.1 16.8
mesh fraction)
Coarse refuse (28 × 100 Eagle
Riffle table 213 w 1.1 16.1 [35]
mesh fraction) Seam
Coarse refuse (28 × 100 Fire Clay
Riffle table 234 w 1.1 24.75
Gravity mesh fraction) Rider
Separation Coarse refuse (<100 Eagle
Multi-gravity separation 257 a 1.2 90
mesh fraction) Seam
Coarse refuse (<100
Fire Clay Multi-gravity separation 290 a 1.2 85
mesh fraction)
Coarse refuse (<100 Fire Clay
Multi-gravity separation 254 a 1.1 87
mesh fraction) Rider
Multi-stage flotation
Decarbonized thickener using a conventional cell
Fire Clay 2300 a 5.3 <5
underflow with sodium oleate as [33]
the collector
Multi-stage flotation
Decarbonized thickener using a column with
Fire Clay 4700 a 10.9 <5
underflow sodium oleate as
the collector
Single-stage conventional
Flotation Decarbonized thickener
Fire Clay cell flotation using oleic 386 w 1.4 23
underflow
acid as the collector [35]
Single-stage flotation
Decarbonized thickener Eagle using a conventional cell
367 w 1.8 31
underflow Seam with oleic acid as
the collector
Single-stage conventional
Decarbonized thickener Fire Clay
cell flotation using oleic 377 w 1.3 13
underflow Rider
acid as the collector
Potassium
octylhydroxamate and
Decarbonized thickener
HHS Fire Clay sorbitan monooleate were 17,428 a 53 5.9 [11]
underflow
used as the
hydrophobizing agent
Three-stage wet high
Magnetic
Decarbonized middling Fire Clay intensity magnetic 7000 w 14 <5 [20]
Separation
separation (1.4 T)
Note: w and a represent dry whole sample basis and dry ash basis, respectively; ER and Re represent enrichment
ratio and recovery, respectively.

Froth flotation is normally utilized to treat fine particles based on their varying degrees of surface
hydrophobicity. Rare earth mineral particles present in decarbonized thickener underflows of coal
preparation plants can be selectivily recovered by froth flotation. As shown in Table 1, concentrates
containing 2300 and 4700 ppm of REEs were obtained by using multiple treatment stages involving
conventional flotation cells and column flotation, respectively. A limited concentration was also
obtained when using a single-stage of flotation. For example, REEs in the decarbonized thickener
underflow derived from treating Eagle seam coal was concentated by nearly two times with the
flotation product containing 367 ppm of REEs on a dry whole sample basis (see Table 1). Oleic acid
was used as the collector for the flotation test results shown in Table 1, which has been widely used to
recover rare earth minerals (e.g., monazite and xenotime) from heavy mineral sands [36,37].
Minerals 2020, 10, 451 4 of 28

As an alternative to flotation, the hydrophobic–hydrophilic separation (HHS) process is a novel

ultrafine particle concentrator that provides improved recovery of micron-size material while also
providing a dewatered product [38]. The process uses hydrocarbon oils to agglomerate hydrophobic
particles and recover the particles through a phase separation. As shown in Table 1, a concentrate
containing 17,428 ppm of REEs was obtained from the Fire Clay decarbonized thickener underflow
using HHS. Octylhydroxamate was used as the collector, which is another commonly used reagent for
rare earth mineral beneficiation [39,40]. The enrichment ratio of the HHS test reached as high as 53:1.
In addition to the aforementioned gravity separation and flotation studies, a concentrate containing
7,000 ppm of REEs was also obtained from the decarbonzied Fire Clay middlings using high-intensity
magnetic separation [20].
Overall, rare earth minerals in the decarbonized materials can be concentrated by using flotation,
HHS, and magnetic separations. However, the recovery values obtained using these technologies are
often too low to be economically viable. One explanation for this consistent finding is that RE-bearing
particles in coal and coal refuse are extremely fine and often interlocked within the host-particles.
SEM characterizations showed that RE-enriched particles occurring in coal refuse and middlings
normally have a particle size of <10 µm [20,33]. In this case, extensive grinding is required to liberate the
encapsulated rare earth particles, thereby making the operating process cost prohibitive [23]. However,
physical separations without significant size reduction can be employed to generate a higher-grade
feedstock for downstream recovery and purification processes.

2.2. Chemical Extraction

Given the low recovery and subsequent high production costs associated with physical
beneficiation, direct chemical extraction of REEs from coal refuse has been evaluated by a number
of researchers [11,20,21,25,41–43]. Moreover, thermal and alkaline treatments prior to acid leaching
have also been used to improve the REE leachability [21,44–47]. These technologies have included
acid leaching, salt/ion exchange leaching, and leaching with pretreatment, which are reviewed in the
following sections.

2.2.1. Salt and Acid Leaching

In the commerical production of REEs from ion-adsorbed clays, ammonium sulfate is commonly
used as a salt lixiviant due to the relatively low hydration energy of ammonium ions. Rozelle et al. [48]
collected two high-ash content samples from the overlying strata of the Upper Kittanning bed.
The samples were crushed and screened to obtain the 595 µm × 150 µm fraction for salt leaching
tests. It was found that around 80% of the total REEs were extracted from the solid, which provided
promise as an economically viable option. However, in subsequent investigations performed by other
researchers, only a small fraction (e.g., 10%) of the total REEs were determined to be ion-exchangeable in
the components of the other coal deposits [41,49]. Given these disparate findings, successful extraction
of REEs from coal and coal refuse using salt leaching largely depends on the nature of coal deposit.
REEs can be efficiently extracted using acid solutions of relatively low concentration from some
coal sources. Laudal et al. successfully extracted nearly 90% of total REEs from a lignite using
0.5 M H2 SO4 [25]. The high recovery was explained by the fact that the REEs in the lignite are
primarily complexed with organic acids, and the complexation can be destroyed under mild acidic
conditions. For bituminous coals, sytematic acid leaching studies have been condcuted on decarbonized
middlings, fine refuse, and coarse refuse produced from the treatment of coals originating from different
seams [11,20,43,50,51]. It was found that REEs in the mineral matter of coal middlings obtained by
grinding and flotation were more leachable than those in coal refuse. For example, nearly 83% of
REEs were leached from the decarbonized Fire Clay middlings using a nitric acid solution of pH 0 at
75 ◦ C, whereas less than 30% of REEs were extracted under the same conditions from the decarbonized
thickener underflow [11]. However, liberation of the mineral matter from coal middlings consumes a
significant amount of energy, which requires consideration for determining economic viability [23].
Minerals 2020, 10, 451 5 of 28

Improvements in the REE leaching efficiency from coal refuse have been achieved by optimizing
the operation parameters such as particle size, temperature, and leaching duration. REE recovery
values were relatively low (<30%) for most of the investigated sources [11]. A summary of salt and acid
leaching of REEs from coal and coal refuse is shown in Table 2. Overall, direct leaching with salt or acid
failed to provide satisfactory recovery from high-rank coal and coal refuse, whereas, direct leaching
is a promising choice for recovering REEs from low-rank coal. Therefore, thermal and/or alkaline
pretreatment has been utilized in subsequent studies to improve the leaching performance.

Table 2. A summary of salt and acid leaching of rare earth elements (REEs) from coal and coal refuse.

Sample Coal Seam Extraction Condition Leaching Recovery Reference

Around 10% of total REEs, 7% of
Decarbonized 0.1 M (NH4 )2 SO4 , pH 5
LREEs, and 18% of HREEs
thickener West Kentucky No. 13 [41]
underflow Around 12% of total REEs, 10%
0.1 M (NH4 )2 SO4 , pH 3
of LREEs, and 21% of HREEs
1 M (NH4 )2 SO4 , Nearly 90% of the total REEs
Roof material,
Upper Kittanning 1/2 solid/solution mass were extracted after 1 h [48]
595 µm × 150 µm
ratio, room temperature of reaction
Lignite Fort Union 0.5 M H2 SO4 , 40 ◦ C, 48 h Nearly 90% of the total REEs [25]
Nitric acid solution of 83% of total REEs, 86% of
Fire Clay
pH 0 at 75 ◦ C LREEs, and 69% of HREEs

Decarbonized Nitric acid solution of 15% of La, 21% of Ce, 31% of Nd,
West Kentucky No. 13
middlings pH 0 at 75 ◦ C 45% of Y
Nitric acid solution of
Lower Kittanning 41% of total REEs
pH 0 at 75 ◦ C
[11]
Nitric acid solution of 31% of La, 26% of Ce, 40% of Nd,
Fire Clay
pH 0 at 75 ◦ C 36% of Y
Decarbonized Nitric acid solution of 6% of La, 5% of Ce, 16% of Nd,
thickener West Kentucky No. 13
pH 0 at 75 ◦ C 34% of Y
underflow
Nitric acid solution of 2% of La, 5% of Ce, 8% of Nd,
Lower Kittanning
pH 0 at 75 ◦ C 25% of Y

2.2.2. Alkali and Thermal Pretreatment

Alkali and thermal pretreatments of coal and coal refuse have been applied to enhance the acid
leaching recoveries of REEs from coal and coal refuse [21,41,44,47,52,53]. A summary of the relevant
studies reported in the literature is provided in Table 3. Yang et al. used an 8 M NaOH solution
to treat decarbonized fine refuse at 75 ◦ C for two hours prior to acid leaching [41]. It was found
that the recovery of REEs was significantly increased from 22% to 75% due to the positive impact
on the leachability of the light REEs. Under the same experimental conditions, a small incremental
increase in recovery was achieved for the HREEs (38% to 48%). Kuppusamy et al. conducted a
study of simultaneous production of clean coal and REEs by alkali-acid leaching of a coal fine refuse
material [52]. The ash content of the material was reduced from 46.21% to 14.17% after treatment with a
NaOH solution (30 wt.%) at 190 ◦ C for 30 min followed by an HCl solution (7.5 wt.%) at 50 ◦ C for 30 min.
Simultaneously, 97% of the LREEs and 76% of the HREEs occurring in the material were extracted.
The enhanced leaching efficiency of REEs resulting from alkali treatment was explained by
two mechanisms: (1) Difficult-to-leach rare earth minerals such as monazite were converted to more
leachable forms [27,41] and (2) Crystal structures of the dominant minerals such as clays were destroyed
resulting in liberation of the encapsulated rare earth minerals [52]. The reactions are as follows:

REEPO4(s) + 3NaOH(aq) → REE(OH)3(s) + Na3 PO4(aq) (1)

Al2 O3 ·2SiO2 ·2H2 O(s) + 6NaOH(aq)

(2)
→ 2Na2 SiO3(aq) + 2NaAlO2(aq) + 5H2 O(aq)
 REEPO ( ) + 3NaOH( ) → REE(OH) ( ) + Na PO ( ) (1)
Al O ∙ 2SiO ∙ 2H O( ) + 6NaOH( )
(2)
Minerals 2020, 10, 451 → 2Na SiO ( ) + 2NaAlO ( ) + 5H O( ) 6 of 28

A schematic diagram incorporating the use of the alkali-acid leaching process to extract REEs
A schematic diagram incorporating the use of the alkali-acid leaching process to extract REEs
from coal and coal refuse is shown in Figure 1. A negative aspect of the alkali leaching step is the
from coal and coal refuse is shown in Figure 1. A negative aspect of the alkali leaching step is the
considerable amount of contaminants dissolved into solution along with the REEs, which complicates
considerable amount of contaminants dissolved into solution along with the REEs, which complicates
the downstream purification process. Another negative aspect is the chemical cost, which will likely
the downstream purification process. Another negative aspect is the chemical cost, which will likely be
be prohibitively high given the relatively low content of REEs in coal-based feedstock. Additional
prohibitively high given the relatively low content of REEs in coal-based feedstock. Additional studies
studies need to be performed to investigate the possibility of selectively increasing the REE
need to be performed to investigate the possibility of selectively increasing the REE leachability using
leachability using diluted alkaline solutions and/or weak alkalis.
diluted alkaline solutions and/or weak alkalis.

Figure 1. Schematic diagram of the alkaline-acid leaching process to extract REEs from coal and coal
Figure 1. Schematic diagram of the alkaline-acid leaching process to extract REEs from coal and coal
refuse [52].
refuse [52].
Another scenario to enhance the REE leachability from coal and coal refuse is thermal activation,
Another scenario to enhance the REE leachability from coal and coal refuse is thermal activation,
also known as calcination or roasting [21,41,44,46,47,54]. As reported by Zhang et al., after thermal
also known as calcination or roasting [21,41,44,46,47,54]. As reported by Zhang et al., after thermal
activation of a coal gangue material at 700 ◦ C for 30 min, 88.6% of the total REEs were leached
activation of a coal gangue material at 700 °C for 30 min, 88.6% of the total REEs were leached using
using 25% HCl at room temperature [46]. The impact of thermal activation on REE leachability has
25% HCl at room temperature [46]. The impact of thermal activation on REE leachability has been
been systematically studied [21,47,54]. As shown in Table 3, for both the clean coal and coal refuse,
systematically studied◦ [21,47,54]. As shown in Table 3, for both the clean coal and coal refuse,
calcination under 600 C in static atmosphere without adding any additives significantly improved the
calcination under 600 °C in static atmosphere without adding any additives significantly improved
REE leaching recovery. For example, the total REE recovery from Pocahontas No. 3 coarse refuse was
the REE leaching recovery. For example, the total REE recovery from Pocahontas No. 3 coarse refuse
increased from 14% to 81% by thermal activation using 1.2 M HCl as a lixiviant. In addition, moderate
was increased from 14% to 81% by thermal activation using 1.2 M HCl as a lixiviant. In addition,
recovery values were also obtained when using mildly acidic conditions. Reducing the acidity by
moderate recovery values were also obtained when using mildly acidic conditions. Reducing the
twenty times, i.e., 1.2 M HCl to 0.06 M HCl, resulted in a relatively small drop in REE recovery for
acidity by twenty times, i.e., 1.2 M HCl to 0.06 M HCl, resulted in a relatively small drop in REE
thermally activated Pocahontas No. 3 coarse refuse to around 60% [21]. As such, acid consumption is
recovery for thermally activated Pocahontas No. 3 coarse refuse to around 60% [21]. As such, acid
significantly reduced, which is typically the highest cost component of a rare earth extraction process.
consumption is significantly reduced, which is typically the highest cost component of a rare earth
Another advantage of thermal activation is that fewer contaminants are dissolved relative to the
extraction process.
REEs. During the calcination process, pyrite began to decompose and was converted to iron oxide
Another advantage of thermal activation is that fewer contaminants are dissolved relative to the
(primarily hematite) in the temperature range of 400–500 ◦ C. The crystallinity of hematite increased
REEs. During the calcination process, pyrite began to decompose and was converted to iron oxide
with the elevation in calcination temperature [21,55,56]. When calcined under high temperature,
(primarily hematite) in the temperature range of 400–500 °C. The crystallinity of hematite increased
inter-layered structures of clay minerals, especially kaolinite, were destroyed due to dehydration,
with the elevation in calcination temperature [21,55,56]. When calcined under high temperature,
resulting in disintegration into thin slices and an increase in surface area [21,57,58]. The overall impact
inter-layered structures of clay minerals, especially kaolinite, were destroyed due to dehydration,
of the mineralogical changes was that Al leachability was noticeably increased, while Fe leachability
resulting in disintegration into thin slices and an increase in surface area [21,57,58]. The overall impact
was slightly increased (see Figure 2). However, as shown in Figure 2 the leaching duration can be
of the mineralogical changes was that Al leachability was noticeably increased, while Fe leachability
shortened to less than 15 min, within which the REE leaching reaction is nearly completed while
was slightly increased (see Figure 2). However, as shown in Figure 2 the leaching duration can be
leaching of Al and Fe is minimal. Therefore, a pregnant leaching solution (PLS) containing relatively
higher concentrations of REEs can be produced using the thermal activation-mild acid leaching process.
The aforementioned process has been installed and is currently under testing in a rare earth pilot
plant funded by the U.S. Department of Energy [59]. A schematic diagram of the process used in the
plant is shown in Figure 3. During the testing process, it was found that organic matter associated
with the coal refuse helped maintain a constant temperature in the roaster, thus, significantly reducing
the energy costs associated with the roaster. In addition to REEs, recent studies [54,60] showed that
leaching recovery of other critical metals such as lithium from coal refuse was also positively impacted
by calcination. Therefore, given the aforementioned benefits, pre-leach calcination combined with mild
acid leaching is one of the most promising approaches for recovering REEs from coal-related materials.
Several mechanisms have been proposed for the positive impacts of thermal activation on REE
extraction from coal, i.e.,: (1) Surface area increase resulting from clay dehydration, which liberates
some rare earth minerals; (2) Decomposition of the difficult-to-leach rare earth minerals; and (3) Release
 leaching of Al and Fe is minimal. Therefore, a pregnant leaching solution (PLS) containing relatively
higher Minerals
concentrations
2020, 10, 451 of REEs can be produced using the thermal activation-mild acid leaching 7 of 30

process.
shortened to less than 15 min, within which the REE leaching reaction is nearly completed while
The aforementioned process has been installed and is currently under testing in a rare earth pilot
leaching of Al and Fe is minimal. Therefore, a pregnant leaching solution (PLS) containing relatively
plant funded
higher by the U.S. Department
concentrations of REEs can ofbe
Energy
produced[59].using
A schematic diagram
the thermal of the process
activation-mild used in the
acid leaching
Minerals 2020, 10, 451 7 of 28
plant isprocess.
shown in Figure 3. During the testing process, it was found that organic matter associated
with the coal refuse helped process
The aforementioned maintain a constant
has been installedtemperature
and is currently inunder
the roaster,
testing in thus, significantly
a rare earth pilot
of a portion of the REEs that were originally associated with the organic matter, which was[54,60]
reducingplantthe energy
funded by costs
the associated
U.S. Department with
of the
Energy roaster.
[59]. A In addition
schematic to
diagram REEs,
of therecent
process studies
used in the
removed
showed plant is shown
that leaching in Figure
recovery 3. During the
of 4other testing
critical process, it was
metals such as found that organic
lithiumparticles matter
from coaland associated
refuse was also
after calcination [21,42,53]. Figure shows the disintegrated kaolinite a REE-enriched
with impacted
positively the coal refuse helped maintain
by calcination. a constant
Therefore, temperature
given in the roaster, thus,
the aforementioned significantly
benefits, pre-leach
particle present in
reducing the
aenergy
thermally
costs
activated
associated
coalthe
with
refuse sample.
roaster. In
Sequential
addition to REEs,
chemical
recent
extraction
studies [54,60]
tests
calcination
have been combined
performed with
on mild
the acid leaching
calcination is
products one of
of the
clean most promising
coals of West approaches
Kentucky for
No. recovering
13, Fire Clay,
showed that leaching recovery of other critical metals such as lithium from coal refuse was also
REEs from coal-related materials.
and Illinois No. 6 impacted
positively [47]. It was by found that aTherefore,
calcination. significant fraction
given of REEs (50% benefits,
the aforementioned for the West Kentucky
pre-leach
calcinationexisted
No. 13 material) combined aswith
metalmildoxides,
acid leaching
which is one of the most
originated promising
from approaches
the removal for recovering
of the organic matter
present inREEs
thefromclean coal-related
coals andmaterials.
the decomposition of the difficult-to-leach rare earth minerals.
80
600˚C-calcined; REE
80 600˚C-calcined; Al
Recovery (%)

60 600˚C-calcined; Fe
600˚C-calcined;REE
None-calcined; REE
600˚C-calcined; Al
None-calcined; Al
Recovery (%)

60 600˚C-calcined; Fe
None-calcined; Fe
40 None-calcined; REE
None-calcined; Al
None-calcined; Fe
40
20
20
0
00 100 200 300
0 100 200
Leaching Duration (min) 300
Leaching Duration (min)
Figure 2. Effects of calcination on the leaching kinetics of REEs, Al, and Fe from Pocahontas No. 3
Effects
Figure 2.Figure of calcination
2. Effects on the
of calcination leaching
on the leachingkinetics
kinetics of REEs,Al,
of REEs, Al,and
and
Fe Fe from
from Pocahontas
Pocahontas No. 3 No. 3
coarse refuse. (Data were extracted from [21]).
coarse refuse. (Data were extracted from [21]).
coarse refuse. (Data were extracted from [21]).

A simplified
Figure 3.Figure block diagram of the REE recovery process used in a REE pilot plant located in
3. A simplified block diagram of the REE recovery process used in a REE pilot plant located in
Figure
west 3. A simplified block diagram of the REE recovery process used in a REE pilot plant located in
Kentucky.
west Kentucky.
west Kentucky.
Minerals 2020, 10, 451 8 of 30
DespiteSeveral
the aforementioned
mechanisms haveadvantages,
been proposedafor few thetechnical and fundamental
positive impacts problems
of thermal activation on REE must be
Several mechanisms
Despite
extraction the
from coal, have
aforementioned
i.e.,: been
(1) proposed
advantages,
Surface area for
a
increasethe
few positive
technical
resulting impacts
and
from of thermal
fundamental
clay
resolved to fully validate the approach. As shown in Table 3, the improvements in the HREE recoveries dehydration, activation
problems
which must on
be
liberates REE
extraction
some from
resolved to
rare coal,
fully
earth i.e.,: (1)
validate
minerals; Surface
the
(2) area
approach. increase
Decomposition As shown
of resulting
the in Tablefrom3, clay
the
difficult-to-leach
are much smaller than those of the LREEs and elevating the calcination temperature did not enhance dehydration,
improvements
rare earth which
in the
minerals; liberates
HREE
and (3)
some recoveries
Release
rare ofare
earth much smaller
aminerals;
portion of (2) than that
those
the Decomposition
REEs of the
were LREEs
originally and elevating
associated with thethe
calcination
organic temperature
matter, which did was (3)
the recovery due to the sintering of aluminumofsilicates
the difficult-to-leach
[21]. In addition, rare earth minerals;
mineralogical and
changes of
not enhance
removed the
after recovery
calcination due to the
[21,42,53]. sintering
Figure 4 of aluminum
shows the silicates
disintegrated [21].
Release of a portion of the REEs that were originally associated with the organic matter, which was In addition,
kaolinite mineralogical
particles and a REE-
the REEs during
changes calcination isinstill unclear.activated
Previous studies only listed some possible mechanisms,
removed afterofcalcination
enriched the REEs
particle during
present acalcination
[21,42,53]. Figureis4still
thermally unclear.
shows coal Previous
therefuse studies
sample.
disintegrated only
Sequential
kaolinitelisted someextraction
chemical
particles possible
and a REE-
whereasmechanisms,
the direct
tests have beenevidence
whereas
performed in supporting
the direct evidence
on the the conclusions
in supporting
calcination productsthe has not
conclusions
of clean been
coals of has obtained
not Kentucky
West to
been obtaineddate.
No. to13,date.
Fire
enriched particle present in a thermally activated coal refuse sample. Sequential chemical extraction
Clay, and Illinois No. 6 [47]. It was found that a significant fraction of REEs (50% for the West
tests have been performed on the calcination products of clean coals of West Kentucky No. 13, Fire
Kentucky No. 13 material) existed as metal oxides, which originated from the removal of the organic
Clay, and (A) Illinois
matter present No. 6 [47].
in the clean It wasand
coals found that a significant
the decomposition fraction of REEs
of the difficult-to-leach rare(50%
earth for the West
(B)
minerals.
Kentucky No. 13 material) existed as metal oxides, which originated from the removal of the organic
matter present in the clean coals and the decomposition of the difficult-to-leach rare earth minerals.

3 µm 1 µm

Figure 4. SEM-EDX
Figure images
4. SEM-EDX of aofcoal
images coarse
a coal coarserefuse
refuse sample afterthermal
sample after thermal activation:
activation: (A) Disintegrated
(A) Disintegrated
kaolinitekaolinite particles;
particles; (B) A(B) A REE-enriched
REE-enriched particle.[21].
particle. [21].
Minerals 2020, 10, 451 8 of 28

Table 3. Summary of the thermal and alkaline pretreatment effects on the leaching recoveries of REEs from coal and coal refuse.

Recovery
Sample Coal Seam Pre-Leach Treatment Leach Conditions Reference
TREE LREE HREE
Coarse refuse (2.2 SG float, 1.2 M HCl; 75 ◦ C, 1% (w/v)
Pocahontas No. 3 None 14% 12% 23%
crushed to below 177 µm) solid concentration, 5 h
Coarse refuse (2.2 SG float, Calcination at 600 ◦ C for 2 h 1.2 M HCl; 75 ◦ C, 1% (w/v)
Pocahontas No. 3 81% 89% 27%
crushed to below 177 µm) without adding any additives solid concentration, 5 h
[21]
Middlings (crushed to 1.2 M HCl; 75 ◦ C, 1% (w/v)
Pocahontas No. 3 None 28% 31% 19%
below 177 µm) solid concentration, 5 h
Middlings (crushed to Calcination at 600 ◦ C for 2 h 1.2 M HCl; 75 ◦ C, 1% (w/v)
Pocahontas No. 3 76% 80% 57%
below 177 µm) without adding any additives solid concentration, 5 h
Plant feed (2.2 SG sink, 1.2 M HCl; 75 ◦ C, 1% (w/v)
West Kentucky No. 13 None 24% 21% 36%
crushed to below 177 µm) solid concentration, 5 h
Plant feed (2.2 SG sink, Calcination at 600 ◦ C for 2 h 1.2 M HCl; 75 ◦ C, 1% (w/v)
West Kentucky No. 13 79% 87% 41%
crushed to below 177 µm) without adding any additives solid concentration, 5 h
Plant feed (2.2 SG sink, 1.2 M HCl; 75 ◦ C, 1% (w/v)
Fire Clay None 43% 43% 38%
crushed to below 177 µm) solid concentration, 5 h
[54]
Plant feed (2.2 SG sink, Calcination at 600 ◦ C for 2 h 1.2 M HCl; 75 ◦ C, 1% (w/v)
Fire Clay 62% 68% 33%
crushed to below 177 µm) without adding any additives solid concentration, 5 h
Plant feed (2.2 SG sink, 1.2 M HCl; 75 ◦ C, 1% (w/v)
Illinois No. 6 None 32% 31% 37%
crushed to below 177 µm) solid concentration, 5 h
Plant feed (1.4 SG float, Calcination at 600 ◦ C for 2 h 1.2 M HCl; 75 ◦ C, 1% (w/v)
Illinois No. 6 65% 73% 41%
crushed to below 177 µm) without adding any additives solid concentration, 5 h
Plant feed (1.4 SG float, 1.2 M HCl; 75 ◦ C, 1% (w/v)
West Kentucky No. 13 None 25% 30% 15%
crushed to below 177 µm) solid concentration, 5 h
Plant feed (1.4 SG float, Calcination at 600 ◦ C for 2 h 1.2 M HCl; 75 ◦ C, 1% (w/v)
West Kentucky No. 13 86% 88% 82%
crushed to below 177 µm) without adding any additives solid concentration, 5 h
Plant feed (1.4 SG float, 1.2 M HCl; 75 ◦ C, 1% (w/v)
Fire Clay None 41% 47% 20%
crushed to below 177 µm) solid concentration, 5 h
[53]
Plant feed (1.4 SG float, Calcination at 600 ◦ C for 2 h 1.2 M HCl; 75 ◦ C, 1% (w/v)
Fire Clay 84% 87% 75%
crushed to below 177 µm) without adding any additives solid concentration, 5 h
Minerals 2020, 10, 451 9 of 28

Table 3. Cont.

Recovery
Sample Coal Seam Pre-Leach Treatment Leach Conditions Reference
TREE LREE HREE
Plant feed (1.4 SG float, 1.2 M HCl; 75 ◦ C, 1% (w/v)
Illinois No. 6 None 34% 43% 10%
crushed to below 177 µm) solid concentration, 5 h
Plant feed (1.4 SG float, Calcination at 600 ◦ C for 2 h 1.2 M HCl; 75 ◦ C, 1% (w/v)
Illinois No. 6 75% 74% 75%
crushed to below 177 µm) without adding any additives solid concentration, 5 h
Middlings (crushed to Calcination at 750 ◦ C for 2 h 1.2 M H2 SO4 ; 75 ◦ C, 1%
West Kentucky No. 13 41% 81% 40%
below 177 µm) without adding any additives (w/v) solid concentration, 5 h
Middlings (crushed to 1.2 M H2 SO4 ; 75 ◦ C, 1%
West Kentucky No. 13 None 29% 23% 47%
below 177 µm) (w/v) solid concentration, 5 h
Pre-leach using 8 M NaOH [41]
1.2 M H2 SO4 ; 75 ◦ C, 1% Unpublished
Fine refuse West Kentucky No. 13 solution at a solid/liquid ratio of 75% 82% 48%
(w/v) solid concentration, 5 h data
1/10 (w/v) and 75 ◦ C for 2 h
1.2 M H2 SO4 ; 75 ◦ C, 1%
Fine refuse West Kentucky No. 13 None 23% 21% 38%
(w/v) solid concentration, 5 h
Pre-leach using 30 wt.% NaOH
solution at 20% solid
Flotation Tailings (<500 µm) East Kootenay 7.5 wt.% HCl, 50 ◦ C, 30 min >85% 97% 76% [52]
concentration and 190 ◦ C for
30 min
Coal refuse (ground to D50 Calcination at 600 ◦ C for 30 min
Junggar coalfield 25% HCl at 25 ◦ C 88.6% NA NA [46]
= 3.78 µm) without adding any additives
Calcination at 600 ◦ C for 2 h 6 M HCl, 1/5 solid/liquid
Coarse refuse NA NA NA NA [44]
without adding any additives ratio, 85–90 ◦ C, 4 h
Minerals 2020, 10, 451 10 of 28

3. REE Recovery from Coal Combustion Byproducts

3.1. Modes of Occurrence of REEs in Coal Combustion Ash

Coal combustion fly ash is composed of both amorphous and crystalline phases. The amorphous
phases account for 60–90% of bulk fly ash composition, while crystalline material accounts for
the remainder [61]. The crystalline phases mainly include quartz, mullite, hematite, magnetite,
ferrite spinels, anhydrite, melilite, merwinite, periclase, tricalcium aluminate, and lime [62–64].
Until recently, researchers have found limited success in characterizing the amorphous phases of
fly ash due to its disordered nature and heterogeneity [61]. This characteristic along with the low
concentration and dispersed nature of REEs have caused difficulties in characterizing the modes
of occurrence of REEs in fly ash using traditional approaches. However, many recent studies have
addressed this challenge using advanced characterization tools, such as X-ray Absorption Near Edge
Structure (XANES), micro-X-Ray Absorption Near Edge Structure (µ-XANES), laser ablation inductively
coupled plasma mass spectroscopy (LA-ICP-MS), multimodal image analysis, and sensitive high
resolution ion microprobe–reverse geometry SHRIMP-RG [65–70]. In addition, systematic SEM-EDX,
TEM-EDX, and sequential chemical extraction (SCE) studies have been performed on coal combustion
ashes, which also provided valuable information regarding the REE occurrence modes and potential
processing routes [71–78].
Sequential chemical extraction (SCE) tests performed on several class F-type fly ash [79] samples
(SiO2 % + Al2 O3 % + Fe2 O3 % > 70%) showed that the majority of REEs were associated with silicates
and aluminosilicates (quartz, glass, mullite, zircon, etc.), indicating that REEs are dispersed in the
glassy phases and/or associated with the Al–Si–oxide phases [76–78]. Chemical composition analysis
of the different size fractions of a class F-type fly ash showed that a strong positive correlation existed
between the REEs and the Al plus Si contents [77], which corroborates the above conclusion. In class F
fly ashes, REEs associating with carbonates and metal oxides, such as CaCO3 and CaO, accounted for
less than 10% of the total REEs, whereas, 50–60% of the total REEs present in class C-type fly ashes
produces from Powder River basin coal occurred as carbonates and metal oxides [66,76–78]. Liu et al.
combined acid leaching results and solution chemistry modelling findings to predict the percentage
of the total REEs that occurred as monazite and hematite in a fly ash sample [66]. It was found
that 10–20% of REEs were leached in the pH range of 0–1.5, which corresponds to the range where
monazite and hematite dissolve based on solution chemistry modelling. Therefore, 10–20% of the
total REEs were reported to exist as monazite and hematite forms. However, many studies have
shown that monazite is thermally and chemically stable, and acid cracking or roasting is required to
efficiently dissolve monazite [80,81]. Therefore, the solution chemistry modelling findings indicating
that monazite and hematite dissolve in solutions having a pH in the range of 0–1.5 is questionable.
Furthermore, the conclusion that 10–20% of the total REEs occur as monazite and hematite needs to be
re-assessed in further investigations.
The association of REEs with silicates and aluminosilicates has been further proven by SEM-EDX,
TEM-EDX, and LA-ICP-MS analyses. Thompson et al. found that, during laser ablation of a
REE-enriched fly ash grain, the ion intensities of Al and Si were consistent, whereas the intensities of
REEs changed in different ablation periods [70]. This finding indicated that REEs tend to be localized
in small grains within fly ash. Using SEM-EDX, some monazite grains within Al–Si cenospheres and
aluminosilicate glass particles were found, and particle size of the grains was less than 10 µm [70].
Moreover, several other SEM-EDX studies also showed the dispersion of REE enriched grains within
aluminosilicates [66,67,71–73,75,78]. Associations of REEs with the other phases present in fly ash
such as iron oxide, zircon, Ca/Fe-rich aluminosilicates, and lime have also been reported [65,66,82].
In addition to associations with the major phases, discrete REE enriched grains such as apatite
(Ca, LREE, and P) and monazite (LREE and P) were also found in fly ash [66,70].
Overall, many RE-bearing minerals such as monazite, xenotime, rhabdophane, zircon, ilmenite,
lime, and calcite have been found in fly ash, and those minerals have complex association characteristics
Minerals 2020, 10, 451 11 of 28

with the major phases [66,67,70,73,75]. Taggart et al. tested both the bulk and micro speciation of
yttrium (Y) in fly ashes using bulk and micro XANES [69]. Bulk XANES analysis indicated that Y
coordination states in the fly ashes resembled a combination of Y-oxide, Y-carbonate, and Y-doped
glass. However, using micro XANES, some “hotspots” of Y were observed including different mineral
forms (e.g., Y-phosphate), which were not observed in the bulk measurements. This result indicated
the heterogeneity of REEs in fly ash, and microscale analysis may be unable to represent the REEs
in bulk fly ash. Hower et al. reported that the distribution of REEs in a coal ash sample seemed
to be in the form of nanoscale crystalline minerals with additional distributions corresponding to
overlapping ultra-fine minerals as well as atomic dispersion within the fly ash glass [71]. Therefore,
the heterogeneity of REEs in fly ash occurs in nano- and atomic-scales.

3.2. Physical Beneficiation of REEs from Coal Combustion Ash

Coal fly ash particles can be separated into different fractions based on their contrasts in physical
characteristics such as density, particle size, magnetism, and surface hydrophobicity [19,24,83–87].
Rather than processing the bulk ash material, REE extraction from certain fractions that are relatively
more enriched in REEs will make the overall recovery more economically viable. REEs in fly ash
are more concentrated in the finer fractions relative to the entire bulk material [19,24,74,83–86].
Size fractionation analyses of REEs in fly ashes collected from power plants of various countries (China,
USA, United Kingdom, Poland) showed that REE contents gradually increased with a decrease in
particle size [19,74,83,85]. For example, the minus 500 mesh fraction of a fly ash sample that was
collected from the Jungar power plant [74] contained 648 ppm of total REEs, which is more than two
times higher than the plus 120 mesh fraction (277 ppm). Several explanations have been suggested
for this phenomenon: (1) The finer fractions in fly ash usually contain more glass phase relative to
the coarser fractions, while REEs are preferentially associated with the glass phase in fly ash [85];
(2) The organic-bound REEs partially volatize and deposit on the fine particles of fly ash [84,88];
and (3) REEs associated with organic matter may form extremely small particles when the organic
matter is combusted and such small particles tend to enrich in the finer fractions of fly ash [84].
Fly ash particles can also be partitioned into different fractions using magnetic separation. Dai et al.
analyzed the magnetic, non-magnetic, and glassy fractions of a fly ash and discovered that the magnetic
fraction contained less REEs relative to the bulk fly ash (202 ppm versus 261 ppm) [84]. Blissett et al.
obtained a magnetic fraction containing 270 ppm of rare earth oxide from a fly ash with 505 ppm of
rare earth oxide [83]. Lin et al. separated a fly ash into five fractions by using different magnetic field
intensities [24]. It was found that REEs were more enriched in the weak- and non-magnetic fractions.
For example, the non-magnetic fraction of a fly ash sample contained more than 600 ppm of REEs,
whereas the strongest magnetic fraction only contained around 200 ppm of REEs. Therefore, based on
these studies, it can be concluded that REEs are preferentially enriched in the non-magnetic fraction of
fly ash.
Fractionation of REEs was also observed in gravity and flotation separations [24,27,83]. In one
of our prior studies [19], a float-sink test was performed on a fly ash sample at a density cut point of
1.8 specific gravity (SG). It was found that the 1.8 SG sink fraction contained more REEs than the 1.8 SG
float fraction (521 ppm versus 376 ppm). Flotation tests using different collectors and collector dosages
also produced a series of products with different REE contents varying from 400 to 650 ppm. Lin et al.
performed density fractionation tests on two fly ash samples and it was found that maximum REE
contents occurred in the medium density fractions (2.71–2.95 SG and 2.45–2.71 SG) [24].
Given these results, physical separation can be used to pre-concentrate REEs from coal
combustion ash, thereby providing a higher-grade feed material to the downstream extraction
processes (e.g., acid leaching), resulting in a reduction in the overall recovery cost ($/kg of rare earth
oxide). In the patents [89,90], magnetic separation was used to produce a feed material for the
subsequent acid leaching process. Two physical beneficiation processes are shown in Figure 5. In
both circuits, magnetic separation is performed prior to size fractionation, whereas in another study
Minerals 2020, 10, 451 12 of 28

by Pan et al. [87], the sequence is reversed. Therefore, no fixed strategy has been proposed
Minerals 2020, 10, 451
for the
13 of 30
physical beneficiation process. The selection of pre-concentration strategy for a specific ash sample
physical
should be basedbeneficiation process. The laboratory
on a comprehensive selection of evaluation
pre-concentration
of thestrategy for a specific
REE partitioning ash sample
characteristics.
should be based on a comprehensive laboratory evaluation of the REE partitioning characteristics.

(A) (B)

Figure
Figure 5. Flowsheet
5. Flowsheet reported
reported in in theliterature
the literaturefor
for REE
REE pre-concentration
pre-concentration using physical
using methods:
physical (A) (A)
methods:
reported by [83] and (B) reported by
reported by [83] and (B) reported by [76]. [76].

3.3. Chemical
3.3. Chemical Extraction
Extraction of REEs
of REEs fromCoal
from CoalCombustion
Combustion Ash
Ash
ManyMany studies
studies havehave
beenbeen published
published in recent
in recent years
years focused
focused onon the
the chemicalextraction
chemical extractionof
ofREEs
REEs from
from coal combustion ashes [26,53,76,88,89,91–101]. As shown in Table 4, acid leaching
coal combustion ashes [26,53,76,88,89,91–101]. As shown in Table 4, acid leaching has been extensivelyhas been
extensively exploited to extract REEs from coal combustion ash, and often the ash materials must be
exploited to extract REEs from coal combustion ash, and often the ash materials must be chemically
chemically and/or thermally treated prior to acid leaching to achieve better extraction performance.
and/or thermally treated prior to acid leaching to achieve better extraction performance. Chemical and
Chemical and physical characteristics of coal combustion ash change significantly relative to the raw
physical characteristics
materials of coal combustion
after pretreatment ash change
[26,96,98]. Therefore, significantly
the leaching relative
mechanisms aretodistinct.
the raw materials after
pretreatment [26,96,98]. Therefore, the leaching mechanisms are distinct.
3.3.1. Acid Leaching of REEs from Coal Combustion Ashes
3.3.1. Acid Leaching of REEs from Coal Combustion Ashes
Satisfactory recoveries of REEs from some coal combustion ash produced from conventional
Satisfactory
boilers has been recoveries
achievedof byREEs
using from some coal
acid leaching combustion
alone. For example, ash produced
Taggart et al. from conventional
extracted more
than
boilers has70% of achieved
been the total REEs fromacid
by using fly ashes of the
leaching Powder
alone. ForRiver basinTaggart
example, using 15etMal. HNO 3 at 85–90
extracted more°C than
70% of[102].
the Nearly
total REEs100%fromrecovery was of
fly ashes obtained
the Powderfrom theRiver samples
basin using
using 12 15 MM HCl
HNOat3 85 °C, and
at 85–90 ◦ Ca[102].

Nearlyconsiderable
100% recovery amount of REEs
was (71%)from
obtained weretheextracted
samples from a fly12
using ashMsample
HCl atof85the same
◦ C, andsource even
a considerable
under much weaker acidity (1 M HCl). Cao et al. conducted a parametric study to optimize the
amount of REEs (71%) were extracted from a fly ash sample of the same source even under much
leaching recovery of REEs from a fly ash sample that was collected from a power plant located in
weaker acidity (1 M HCl). Cao et al. conducted a parametric study to optimize the leaching recovery
Guizhou, China [91]. It was found that 71.9% of La, 66.0% of Ce, and 61.9% of Nd were leached using
of REEs
3 Mfrom
HCl ata 60
fly°C.
ashHowever,
sample that was
due to thecollected from
fact that most ofathepower
REEs plant located in in
are encapsulated Guizhou, China [91].
the amorphous
It wasstructures
found that 71.9% of La, 66.0% of Ce, and 61.9% of Nd were leached
of fly ash generated by combusting pulverized coal under high temperature (~1400 °C),using 3 M HCl at 60 ◦ C.
However, due low
relatively to the fact thatwere
recoveries mostusually
of the achieved
REEs areusing encapsulated in the
acid leaching amorphous
alone. As shownstructures
in Table 4,of35–fly ash
generated by combusting pulverized coalextracted
under high ◦
43% and 40–57% of total REEs were fromtemperature
fly ashes of (~1400
Illinois andC), relatively
Appalachian lowbasins,
recoveries
were respectively, using strong
usually achieved usingacidity at high temperature
acid leaching alone. As shown(12 M HCl at 85 °C;
in Table 4, [96]).
35–43% and 40–57% of total
REEs were Several studies
extracted prepared
from coal ash
fly ashes samples and
of Illinois by combusting
Appalachian coalsbasins,
in muffle furnaces, which
respectively, usingwerestrong
used to simulate fly ash and bottom
acidity at high temperature (12 M HCl at 85 C; [96]). ash◦ produced from pulverized coal-fired boilers [97,103].
Relatively high leaching recoveries were achieved from artificially prepared coal ashes. However, the
Several studies prepared coal ash samples by combusting coals in muffle furnaces, which were used
temperatures used were much lower than the typical temperatures used in conventional pulverized
to simulate fly ash and bottom ash produced from pulverized coal-fired boilers [97,103]. Relatively high
coal boilers. For example, Kumari et al. burned a coal at 450 °C for 8 h and treated the material as coal
leaching recoveries
bottom ash [97]. were achieved
Acid leaching from artificially
optimization showedprepared
that 90% of coal
Ce ashes.
and NdHowever,
as well as 35%the of
temperatures
Y were
used extracted
were much lower than the typical temperatures used in conventional
using 4 M HCl at 90 °C. It has been realized that mineral matter in coal may oxidize, pulverized coal boilers.
For example, Kumari et al. burned a coal at 450 ◦ C for 8 h and treated the material as coal bottom
ash [97]. Acid leaching optimization showed that 90% of Ce and Nd as well as 35% of Y were extracted
Minerals 2020, 10, 451 13 of 28

using 4 M HCl at 90 ◦ C. It has been realized that mineral matter in coal may oxidize, decompose,
Minerals 2020, 10, 451 14 of 30
fuse, disintegrate, or agglomerate under temperatures as high as 1400 ◦ C, and rapid cooling in the
post-combustion
decompose, fuse, zonedisintegrate,
in boilers results in the formation
or agglomerate of spherical,
under temperatures as amorphous
high as 1400 particles [104,105].
°C, and rapid
However,
coolingwhen
in thecombusting in a muffle
post-combustion zone furnace
in boilersatresults
a temperature lower than
in the formation 900 ◦ C, no
of spherical, glassy phases
amorphous
were particles
detected[104,105].
[21,47,53,57]. Therefore,
However, REEs in the
when combusting in laboratory prepared
a muffle furnace ash material
at a temperature are than
lower more900 readily
°C, no glassy phases were detected [21,47,53,57]. Therefore,
leached compared with the REEs in ashes produced in pulverized coal-fired boilers.REEs in the laboratory prepared ash
material are more
Leachabilities readilyfrom
of REEs leached compared
fly ash producedwith in
thefluidized
REEs in ashes produced in (FBC)
bed combustion pulverized coal- have
systems
fired boilers.
also been evaluated [53,101]. REEs present in FBC ash are more leachable than ashes produced from
Leachabilities of REEs from fly ash produced in fluidized bed combustion (FBC) systems have
pulverized coal-fired boilers. Tuan et al. extracted 62.1% Y, 55.5% Nd, and 65.2% Dy from a FBC bottom
also been evaluated [53,101]. REEs present in FBC ash are more leachable than ashes produced from
ash using 2 M HCl at 80 ◦ C [101]. Honaker et al. achieved around 80% of total REE recovery from
pulverized coal-fired boilers. Tuan et al. extracted 62.1% Y, 55.5% Nd, and 65.2% Dy from a FBC
an FBC bottom
bottom ash ash
using using 1.2 M
2 M HCl HCl
at 80 °Cat 75 ◦Honaker
[101]. C [53]. Relatively lowaround
et al. achieved burning 80% temperatures (750–900 ◦ C)
of total REE recovery
are typically
from an FBCutilized
bottomin FBC units1.2
ash using [106].
M HCl Therefore, glassy
at 75 °C [53]. phaseslow
Relatively areburning
less likely formed during
temperatures (750– the
combustion and cooling processes in FBC, which contribute to the higher REE
900 °C) are typically utilized in FBC units [106]. Therefore, glassy phases are less likely formed during leaching efficiency.
As shown in Figureand
the combustion 6, the FBCprocesses
cooling ash samples maintained
in FBC, good crystallization
which contribute to the higher REE and no noticeable
leaching efficiency. glassy
Aswere
phases shownfound.
in Figure 6, the FBC ash
Furthermore, samples
similar tomaintained
the thermal good crystallization
activation of REEs andpresent
no noticeable
in coalglassy
and coal
phases
refuse were3.3.2),
(Section found.combustion
Furthermore,insimilar
a FBCtosystem
the thermal
may activation
enhance the of REEs
REEpresent
leachingin coal and coal
efficiency due to
refuse (Section 3.3.2), combustion in a FBC system may enhance the REE
dehydration of the clays, decomposition of the hard-to-leach rare earth minerals, and removal leaching efficiency due toof the
dehydration of the clays, decomposition of the hard-to-leach rare earth minerals, and removal of the
organic matters [21,47,53].
organic matters [21,47,53].

Figure 6. XRD
Figure patterns
6. XRD patternsof the fluidized
of the fluidizedbed
bedcombustion (FBC)ash
combustion (FBC) ashsamples:
samples: A, anhydrite;
A, anhydrite; C, calcite;
C, calcite;
H, hematite; I, illite; L, Lime; and Q, Quartz [53].
H, hematite; I, illite; L, Lime; and Q, Quartz. [53].

Parametric
Parametric studies have
studies havebeen
beenperformed
performed to optimizethe
to optimize theleaching
leaching recovery
recovery of REEs
of REEs fromfromcoal coal
combustion
combustion ash.ash.
Kumari
Kumari et et
al.al.performed
performed leaching testson
leaching tests ona acoal
coal ashash using
using three
three different
different typestypes
of of
acids,acids,
i.e., hydrochloric
i.e., hydrochloric acid, nitric
acid, nitricacid,
acid,and
and sulfuric acid,under
sulfuric acid, underthe thesame
same conditions
conditions [97].[97].
It wasIt was
foundfound thatleaching
that the the leaching recoveries
recoveries followthe
follow theorder
orderof HCl >>HNO
of HCl HNO3 3> H > 2H
SO2 4. However,
SO 4 . to
However, thetoauthors’
the authors’
knowledge,
knowledge, sulfuric
sulfuric acid
acid is less
is less volatileand
volatile and more
more cost-effective
cost-effectivecompared
compared with the the
with other two acids.
other two acids.
Tuan et al. did not observe a significant difference among the three mineral acids in terms of REE
Tuan et al. did not observe a significant difference among the three mineral acids in terms of REE
extraction from FBC bottom ashes [101]. Despite the inconsistent findings, hydrochloric acid is the
extraction from FBC bottom ashes [101]. Despite the inconsistent findings, hydrochloric acid is the
most commonly used lixiviant per literature (see Table 4). Sulfuric acid is expected to provide the
mostworst
commonly used lixiviant per literature (see Table 4). Sulfuric acid is expected to provide the
efficiency since the large amount of calcium present in coal combustion ash will complex with
worstsulfate
efficiency since
to form gypsum,the large
and amount
some REEs of calcium present in coal
will be incorporated combustion
into the ash willand
gypsum structure complex
lost to with
sulfate
thetoprecipitate
form gypsum, and some
[107]. Leaching REEs will
recovery be incorporated
of REEs into the gypsum
is sensitive to liquid/solid structure
ratio, acid and lost to
concentration,
the precipitate
temperature, [107]. Leaching
and leaching recovery
duration of REEsLeaching
[91,97,100]. is sensitive to liquid/solid
recoveries of La, Ce, andratio,
Ndacid
fromconcentration,
a coal fly
ash were and
temperature, nearly doubledduration
leaching when increasing the liquid/solid
[91,97,100]. Leaching ratio from 5/1
recoveries of to
La, 20/1
Ce,orand
prolonging
Nd from thea coal
reaction time from 30 to 180 min [91].
fly ash were nearly doubled when increasing the liquid/solid ratio from 5/1 to 20/1 or prolonging the
Two from
reaction time flowsheets
30 to that were[91].
180 min reported in the literature for recovering REEs from coal combustion
ash using acid leaching are shown in Figure 7. Solvent extraction was used in both circuits. In the first
Two flowsheets that were reported in the literature for recovering REEs from coal combustion
circuit (Figure 7A), tris-2-ethylhexyl amine (TEHA) was used to complex hydrogen ions in the solvent
ash using acid leaching are shown in Figure 7. Solvent extraction was used in both circuits. In the
Minerals 2020, 10, 451 14 of 28

first circuit (Figure

Minerals 7A), tris-2-ethylhexyl amine (TEHA) was used to complex hydrogen
2020, 10, 451 ions
15 of 30 in the
solvent extraction step, and acid regenerated in the stripping step, which reduced the chemical cost.
REEs were extraction step, and
recovered fromacid
theregenerated in solvent
raffinate of the stripping step, which
extraction usingreduced the chemical
precipitation. cost.second
In the REEs circuit
were recovered from the raffinate of solvent extraction using precipitation. In the second circuit
(Figure 7B), fly ash and bed ash produced from FBC combustors are leached using diluted acid
(Figure 7B), fly ash and bed ash produced from FBC combustors are leached using diluted acid (e.g.,
(e.g., 1.21.2MMhydrochloric acid). REEs in the pregnant leach solution are extracted using a three-stage
hydrochloric acid). REEs in the pregnant leach solution are extracted using a three-stage
counter-current solvent
counter-current extraction
solvent (SX)
extraction (SX)system. Finally,a aconcentrated
system. Finally, concentrated solution
solution of containing
of REEs REEs containing
minimal contaminants
minimal contaminants is produced
is producedfrom
fromthe
theSX-stripping stage.
SX-stripping stage. High-purity
High-purity REE concentrates
REE concentrates are are
produced by selective precipitation using oxalic acid as
produced by selective precipitation using oxalic acid as the precipitant.the precipitant.

Figure 7. Flowsheets
Figure reported
7. Flowsheets in in
reported thethe
literature
literature for recovering
for recovering REEs
REEs from
from coal coal combustion
combustion ash using
ash using
acid leaching: (A) reported by [97] and (B) reported by [53].
acid leaching: (A) reported by [97] and (B) reported by [53].

Overall, REE REE

Overall, recovery
recoveryfrom
from coal combustion
coal combustion ashesashes
using using direct
direct acid acidis leaching
leaching is inefficient.
inefficient. Harsh
leaching conditions
Harsh leaching conditions withwith
concentrated acid solutions
concentrated at higher temperatures
acid solutions are normally required
at higher temperatures are normally
requiredtoto
achieve satisfactory
achieve recovery.
satisfactory In addition
recovery. to the direct
In addition to theacid leaching,
direct REE extraction
acid leaching, REE from fly ashfrom fly
extraction
using bioleaching was also reported [108]. Three microbial strains, Candida bombicola, Phanerochaete
ash using bioleaching was also reported [108]. Three microbial strains, Candida bombicola, Phanerochaete
chrysosporium, and Cryptococcus curvatus, were tested by Park and Liang in terms of REE extraction
chrysosporium,
from fly ash. Cryptococcus
andCandida bombicolacurvatus,
providedwere testedresults
the optimal by Parkwithand
63%Liang in terms
Sc, 62.2% Y, 67.7% ofYb,
REE extraction
64.4%
from flyEr, 60%Candida
ash. Dy, and bombicola provided
51.9% Gd being theatoptimal
extracted 28 °C forresults with 63% Sc, 62.2% Y, 67.7% Yb, 64.4% Er,
6 h [108].
60% Dy, and 51.9% Gd being extracted at 28 ◦ C for 6 h [108].
3.3.2. Chemical/Thermal Pretreatment
3.3.2. Chemical/Thermal Pretreatment
Coal combustion ash was chemically and/or thermally pretreated prior to acid leaching to
achieve high REE recoveries [18,26,76,98,100,109]. Lin et al. performed hydrothermal treatment on a
Coal combustion ash was chemically and/or thermally pretreated prior to acid leaching to achieve
coal fly ash and found that 21.3% of the material was dissolved by using 5 M NaOH with a
high REE recoveries [18,26,76,98,100,109]. Lin et al. performed hydrothermal treatment on a coal
solid/liquid ratio of 1/20 at 100 °C for 120 min [76]. REE content in the solid material was increased
fly ash from
and found
366 to that
803 ppm21.3% of the
after material was
hydrothermal dissolved
treatment, whichby using 5
indicates M REEs
that NaOH with in
present a solid/liquid
coal
ratio ofcombustion
1/20 at 100ash ◦ C for 120 min [76]. REE content in the solid material was increased from 366 to
remain with the solid residue after the hydrothermal treatment. Wang et al. used an
803 ppm 8 Mafter
HCl solution to leach atreatment,
hydrothermal hydrothermally treated
which fly ash and
indicates achieved
that REEsapresent
total REEinrecovery of 88.15%
coal combustion ash
[18]. As shown in Figure 8A, Si, Ga, and Al were also recovered from the fly ash alongside
remain with the solid residue after the hydrothermal treatment. Wang et al. used an 8 M HCl solution REEs. Ma
et al. proposed an alternative NaOH–HCl leaching process, which extracted 55% of REEs, 63% of Si,
to leach a hydrothermally treated fly ash and achieved a total REE recovery of 88.15% [18]. As shown
72% of Ga, and 78% of Al from the fly ash (see Figure 8B) [98]. Unfortunately, none of the studies
in Figure 8A, Si, Ga,
produced and Alfinal
high-grade were also
rare recovered
earth products.from the fly ash alongside REEs. Ma et al. proposed an
alternative NaOH–HCl leaching
In the hydrothermal process,
treatment whichNaOH
process, extracted 55%
reacts ofthe
with REEs,
major 63% of Si, 72%ofofflyGa,
components ashand 78%
of Al from the fly
according to ash (see Figure
the following 8B) [98].
reactions Unfortunately, none of the studies produced high-grade
[110,111]:
final rare earth products.
In the hydrothermal treatment process, NaOH reacts with the major components of fly ash
according to the following reactions [110,111]:

SiO2 + 2NaOH → Na2 SiO3 + H2 O (3)

 Minerals 2020, 10, 451 16 of 30

Minerals 2020, 10, 451 15 of 28

SiO + 2NaOH → Na SiO + H O (3)
3Al O ∙ 2SiO + 10NaOH → 6NaAlO + 2Na SiO + 5H O (4)
3Al2 O3 ·2SiO2 + 10NaOH → 6NaAlO2 + 2Na2 SiO3 + 5H2 O (4)
Al O + 2NaOH → 2NaAlO + H O (5)
Al2 O3 + 2NaOH → 2NaAlO2 + H2 O (5)
The above
The above reactions
reactions destroy
destroy the the amorphous
amorphous glassy
glassy structure
structure of fly
of fly ashash
andand liberate
liberate thethe RE-
RE-bearing
bearing
particles, particles,
which which are dissolved
are dissolved in the
in the acid acid leaching
leaching step. Instep. In addition,
addition, hydrothermal
hydrothermal treatmentusing
treatment
NaOH using NaOH
is also is also
able able to convert
to convert hard-to-dissolve
hard-to-dissolve rarerare earthminerals
earth minerals into
intosoluble forms
soluble (Equation
forms (1)). (1)).
(Equation
All of the above reactions contribute to the extraction of REEs from coal combustion ash.
All of the above reactions contribute to the extraction of REEs from coal combustion ash.

Figure 8. Flowsheets
Figure reported
8. Flowsheets ininthe
reported theliterature
literature for recoveringREEs
for recovering REEs from
from coal
coal combustion
combustion ash using
ash using
NaOH hydrothermal treatment followed by acid leaching: (A) reported by [18] and (B) reported
NaOH hydrothermal treatment followed by acid leaching: (A) reported by [18] and (B) reported by by [98].
[98].
Several studies have reported that REE recovery from fly ash was improved by alkali roasting
treatmentSeveral
prior to acid have
studies leaching [26,100,112].
reported Taggartfrom
that REE recovery et al.
fly compared the performance
ash was improved of various
by alkali roasting
roasting additives,
treatment prior including Na2 O[26,100,112].
to acid leaching 2 , NaOH, CaO, Na2etCO
Taggart al.3 ,compared
CaSO4 , and the (NH 4 )2 SO4 , by
performance performing
of various
roasting
roasting at 450 ◦ C including
tests additives, on fly ashNa 2O2, NaOH,
samples CaO, Na
originating 2CO3power
from , CaSO4stations
, and (NH in4)the
2SOAppalachian,
4, by performing Illinois,
roasting River
and Powder tests atbasins
450 °C followed
on fly ash samples
by leaching originating
with 1from
M HNOpower[26]. stations
It in the
was Appalachian,
found that NaOH Illinois,
roasting
3
oftenand Powder River
recovered morebasins
than followed
90% of the by leaching with which
total REEs, 1 M HNO [26]. Itefficient
is 3more was found thatthe
than NaOH roasting
other additives.
often recovered more than 90% of the total REEs, which is more efficient than the other additives.
Tang et al. optimized Na2 CO3 roasting on a coal fly ash collected from Guizhou China [100]. Mass ratio
Tang et al. optimized Na2CO3 roasting on a coal fly ash collected from Guizhou China [100]. Mass
of 1/1 (fly ash/ Na2 CO3 ) and roasting temperature of 860 ◦ C provided the maximum total REE recovery
ratio of 1/1 (fly ash/ Na2CO3) and roasting temperature of 860 °C provided the maximum total REE
(~90%) when (~90%)
recovery leaching whenwith 2 M HCl.
leaching withLiu2 M et HCl.
al. proposed
Liu et al.aproposed
flowsheeta to achievetothe
flowsheet simultaneous
achieve the
extraction
simultaneous extraction of REEs, Ga, and Nb from a coal fly ash of the Songzao coalfield, which isfor its
of REEs, Ga, and Nb from a coal fly ash of the Songzao coalfield, which is famous
significant
famousenrichment in trace
for its significant elements in
enrichment [84,112,113].
trace elementsAs [84,112,113].
shown in Figure 9, water
As shown leaching
in Figure was used
9, water
to extract Ga and
leaching was Al
used from the roasting
to extract Ga andproduct,
Al from and REEs were
the roasting recovered
product, fromwere
and REEs the water leaching
recovered from solid
the by
residue water
acidleaching
leaching.solid residue
Ion by acidresin
adsorption leaching.
was Ion
used adsorption
to separate resin
Gawasandused
Al. to separate Ga
Laboratory and
test results
Al. Laboratory test results showed that 68.62% Al, 76.11% Ti, and 80.07%
showed that 68.62% Al, 76.11% Ti, and 80.07% REEs were extracted from the fly ash using the alkali REEs were extracted from
the fly ash using
roasting–water the alkali leaching
leaching–acid roasting–water
method. leaching–acid
The reactionsleaching method.
between The reactions
sodium carbonate between
and fly ash
sodium carbonate and fly ash during roasting are as follows:
during roasting are as follows:

AlAl O ∙ SiO + 2Na CO → Na SiO + 2NaAlO + 2CO

2 O3 ·SiO2 + 2Na2 CO3 → Na2 SiO3 + 2NaAlO2 + 2CO(2()g) (6) (6)
Fe O + Na CO → 2NaFeO + CO ( ) (7)
Fe2 O3 + Na2 CO3 → 2NaFeO2 + CO2(g) (7)
TiO + Na CO → Na TiO + CO ( ) (8)
TiO2 + Na2 CO3 → Na2 TiO3 + CO2(g) (8)
Ga O + Na CO → 2NaGaO + CO ( ) (9)
Ga2 O3 + Na2 CO3 → 2NaGaO2 + CO2(g) (9)

Nb2 O5 + 3Na2 CO3 → 2Na3 NbO4 + 3CO2(g) (10)

REE2 O3 + Na2 CO3 → 2NaREEO2 + CO2(g) (11)

2REEPO4 + 3Na2 CO3 → REE2 O3 + 2Na3 PO4 + 3CO2(g) (12)

Minerals 2020, 10, 451 16 of 28

Table 4. Summary of REE extraction from coal combustion ash using chemical methods.

Sample Source Pretreatment Lixiviant Leaching Condition REE Recovery Reference

50 g/L pulp density, 90 ◦ C, Around 90% for Ce and Nd,
Bottom ash Laboratory prepared None 4 M HCl [97]
120 min and 35% for Y
Around 20% for La, 40% for
Liquid/solid ratio 10/1, 120
Fly ash Guizhou, China None 2 M HCl Ce, 5% for Pr, 20% for Nd,
min
and 10% for Y [100]
Na2 CO3 , 1/1 solid/solid ratio, Liquid/solid ratio 20/1 (v/w),
Fly ash Guizhou, China 3 M HCl 72.78% for total REEs
860 ◦ C 400 rpm stirring speed
Upper, Middle, and
1% solid concentration,
Fly ash Lower Kittanning None 1.2 M HCl Around 60% for total REEs
75 ◦ C, 5 h
seams, United States
[53]
Illinois No.6 seam, 1% solid concentration,
Bottom ash None 1.2 M HCl Around 80% for total REEs
United States 75 ◦ C, 5 h
100 g/L pulp density, 80 ◦ C,
Bottom ash South Korea None 2 M HCl 62.1% Y, 55.5% Nd, 65.2% Dy [101]
12 h
Liquid/solid ratio 10/1 (v/w), 71.9% La, 66.0% Ce,
Fly ash Guizhou, China None 3 M HCl [91]
60 ◦ C, 120 min 61.9% Nd
Fly ash/Bottom ash Sichuan, China None 4% HF 50 g/L, 23–25 ◦ C, 24 h >90% for total REEs
Liquid/solid ratio 40/1(v/w),
Fly ash Sichuan, China None 8 M HCl 32.36% for total REEs
80 ◦ C, 6 h [18]
40% NaOH, 10/1 (v/w) Liquid/solid ratio 30/1 (v/w),
Flay ash Sichuan, China 8 M HCl 88.15% for total REEs
solid/liquid ratio, 150 ◦ C, 2 h 60 ◦ C, 2 h
Acid-alkali based alternate extraction (230 g/L HCl, 200 g/L NaOH, liquid to
Fly ash Shanxi, China 65% for total REEs [98]
solid ratio 5/1 (v/w), 90 ◦ C)
Powder River Basin, Liquid/solid ratio 100/1,
Fly ash None 12 M HCl Neary 100% for total REEs
United States 85 ◦ C, 4 h
Illinois Basin, Liquid/solid ratio 100/1, 35–43% recovery for total
Fly ash None 12 M HCl
United States 85 ◦ C, 4 h REEs
[96]
Appalachian Basin, Liquid/solid ratio 100/1,
Fly ash None 12 M HCl 40–57% for total REEs
United States 85 ◦ C, 4 h
Appalachian Basin, 6.25 M NaOH, liquid/solid
Fly ash 20% HCl NA 48.8–85.9% for total REEs
United States mass ratio 10/1, 85 ◦ C, 4 h
Minerals 2020, 10, 451 17 of 28

Table 4. Cont.

Sample Source Pretreatment Lixiviant Leaching Condition REE Recovery Reference

No experimental tests were
Coal ash Not Available None Super critical CO2 [92]
performed.
5 M NaOH, solid/liquid ratio REE was enriched from 325
Fly ash Ohio, United States None None [76]
1:20, 100 ◦ C, 2 h to 877 ppm
Appalachian, Illinois, NaOH roasting (1:1 100% total REE recovery for
Fly ash and Powder River additive-ash ratio, 450 ◦ C, 2 M HNO3 Room temperature the Powder River Basin, [26]
Basins, United States 30 min) >70% for the other sources
Liquid/ratio of 33/1 (v/w), 90.5% for total REEs and
Coal ash Laboratory prepared None 6 M HNO3 [103]
60 min 90.9% for LREEs
Powder River Basin,
Fly ash None 15 M HNO3 10–50 g/L, 85–90 ◦ C, 4 h 69.9% for total REEs [102]
United States
Coal ash NA Physical beneficiation HNO3 Approximately 90 ◦ C NA [90]
Na2 CO3 roasting (1.5:1
Liquid/solid ratio 20/1 (v/w), Around 80% of total REEs
Fly ash Chongqing, China additive-ash ratio, 860 ◦ C, 6 M HCl [112]
60 ◦ C, 4 h were extracted
30 min)
Liquid/solid ratio 100/1 Around 10–45% of La was
Fly ash Japan None 9.5% H2 SO4 [88]
(v/w), 80 ◦ C, 2 h extracted
Minerals 2020, 10, 451 17 of 30

Nb O + 3Na CO → 2Na NbO + 3CO ( ) (10)

Minerals 2020, 10, 451 REE O + Na CO → 2NaREEO + CO ( ) (11)

18 of 28

2REEPO + 3Na CO → REE O + 2Na PO + 3CO ( ) (12)

Figure9.9.AAflowsheet
Figure flowsheetfor
forrecovering
recoveringREEs,
REEs,Ga,
Ga,Nb,
Nb,and
andAl
Alfrom
fromaafly
flyash
ashusing
usingalkali
alkaliroasting
roasting[112].
[112].

4. REE Recovery from Acid Mine Drainage and Sludge

4.1. REEs in Acid Mine Drainage

The occurrence of REEs in acid coal mine drainage (AMD) is mainly due to the dissolution of
RE-bearing species under acidic conditions created by the natural oxidization of sulfide minerals,
primarily pyrite. When exposed to the natural environment, pyrite is oxidized as described by the
following reactions [114–116]:

+ +
FeS2(s) + 14Fe3(aq )
+ 18H2 O(l) → 15Fe2(aq )
+ 2SO2−
4(aq)
+ 16H+
(aq)
(13)

+
FeS2(s) + 7/2O2(aq) + H2 O(l) → Fe2(aq )
+ 2SO2−
4(aq)
+ 2H+
(aq)
(14)
+
Fe2(aq )
+ 1/4O2(aq) + H+
(aq)
+
→ Fe3(aq )
+ 1/2H2 O(l) (15)

As shown in the above equations, both ferric ions and oxygen serve as oxidants for pyrite.
Moreover, it has been well realized that Fe3+ /S0 -oxidizing microorganisms can significantly accelerate
the reaction [116,117].
Many articles have been published focusing on the characterization of REEs in AMD [9,118–123].
Based on the data drawn from 233 samples collected by the United States Geological Survey (USGS) in
1999 and 2011, Ziemkiewicz et al. found that the total REE concentration increases exponentially with
a decrease in pH [124]. Other studies also observed the same phenomenon [9,121–123]. For example,
Stewart et al. reported that the total REE concentration and solution pH in 18 AMD samples collected
from the Appalachian Basin ranged from 0.29 to 1134 µg/L and 2.8–6.6, respectively, with the higher
concentration occurring in low pH solutions [9]. Total REE concentration in AMD is normally less than
coal and coal refuse, whereas, when reported based on total dissolved solids in AMD, the concentration
is similar to or even higher than coal and coal refuse. For example, Honaker et al. obtained the
dissolved solid from an AMD sample containing 6.7 mg/L total REEs by completely evaporating the
liquid phase [115]. REE content in the dissolved solid was measured to be 380 ppm, which is much
higher than the average content of World coals (68 ppm, [4]). Moreover, AMD samples with more
than 10 mg/L REEs have been reported in the literature [125]. Therefore, AMD can be used as an
alternative resource of REEs. Extremely high concentrations of REEs have been detected in some
sludges generated during the passive treatment process [9,22,124]. For example, 3037 mg/kg of total
Minerals 2020, 10, 451 19 of 28

REEs were estimated from sludge samples from the Saxman Run treatment plant [124]. The same
group later conducted a broad survey of 141 treatment sites in the Northern and Central Appalachian
coal basins and found that more that 20 of the 623 AMD sludge samples had concentrations exceeding
2000 mg/kg on a dry whole mass basis [22]. Northern Appalachian samples tended to have higher
REE concentrations than those from Central Appalachia with statistically significant deviations for all
REEs except Ce, Pr, and Nd.
AMD and AMD sludge typically contain more valuable REEs such as Y relative to La and Ce.
For example, Y in the coarse refuse collected from the West Kentucky No. 13 and Illinois No. 6
seams represented less than 10% of the total REEs; whereas the REEs in AMD generated from the
refuse piles was more than 25% Yttrium. In addition, in the basin comparison study by Vass et al.,
the ratio of critical REEs (defined as Y, Nd, Eu, Tb, and Dy) to total REEs was nearly 50% for the
Northern Appalachian samples [22]. The enrichment of HREEs in AMD, especially the elements located
in the middle of lanthanide series (Sm-Dy, middle REEs), has been well recognized by geologists,
which may be explained by several mechanisms: (1) the abundance and distribution of mineral phases
containing REEs, (2) the stability of RE-bearing mineral phases with respect to the aqueous fluids,
(3) the chemistry of the aqueous fluids, and (4) the immobilizing capacity of minerals, precipitates,
and colloidal materials to REEs [120,122,123,126,127]. Overall, AMD can be used as a potential resource
of REEs due to the relatively high concentration (reported on dissolved solid basis) and the preferential
enrichment in HREEs.

4.2. REE Recovery from Acid Mine Drainage

Many studies have been performed to recover valuable components such as Fe, Al, Cu, Zn,
Ni, and sulfuric acid from acid mine drainage (AMD). The recovery methods can be classified
as precipitation [128–132], adsorption [133,134], diffusion dialysis [135], and ion-exchange [129].
Seo et al. used an oxidation-sequential precipitation method to recover Fe, Al, and Mn from a coal
mine drainage [131]. The laboratory test results showed that 99.2–99.3% of Fe, 70.4–82.2% of Al,
and 37.8–87.5% of Mn were recovered at pH 4.5, 5.5, and 8.5, respectively. Furthermore, Cu and Zn can
be selectively concentrated by collecting the precipitates formed in the pH ranges of 4.49–6.11 and
5.50–7.23, respectively [128]. Instead of artificially adding alkalis, dissolved metals in AMD can also be
precipitated and recovered using OH− produced from electrochemical reactions [136]. Chockalingam
and Subramanian found that rice husk is able to uptake 99% Fe3+ , 98% Fe2+ , 98% Zn2+ , and 95% Cu2+
from an acid mine water, with a concomitant increase in the pH value by two absolute units [133].
Crane and Sapsford reported that nanoscale zerovalent iron (nZVI) selectively adsorbed Cu, Cd, and Al
with more than 99.9% recovery in 1 h [137]. In addition, an acidic pH buffer enabled the formation of
copper–bearing nanoparticles from AMD in presence of nZVI. Magnetite nanoparticles have also been
successfully prepared from AMD [138–140].
Due to the much higher economic values of REEs relative to the major metals such as iron and
aluminum present in AMD, several studies regarding REE recovery from AMD have been reported
recently [9,10,12,22,124,141–144]. In one of our prior studies [10], staged precipitation tests were
performed on a coal mine drainage (6.14 ppm of REEs), and a REE pre-concentrate containing 1.1% of
REEs was produced in the pH range of 4.85–6.11. In addition, the pre-concentrate also contained 17.1%
Al, 1.7% Zn, 1.4% Cu, 1.14% Mn, 0.5% Ni, and 0.2% Co, indicating that multiple valuable components
can be pre-concentrated simultaneously using staged precipitation. By using selective re-dissolution
and oxalic precipitation, a product containing 94% rare earth oxides was finally obtained from the
pre-concentrate. A process flowsheet has been developed in a recent study by the authors [145].
The staged precipitation results also explained the observations in the passive treatment systems of
coal mine drainage, i.e., >90% REEs were sequestered in the treatment solids when pH was raised
above 6.0, and REEs were preferentially retained in the basaluminite (Al4 (SO4 )(OH)10 ·5H2 O) [141,142].
Ramasamy et al. (2018) synthesized N- and O- ligand doped mesoporous silica-chitosan hybrid beads
Minerals 2020, 10, 451 20 of 28

for extracting REEs from AMD and the test results showed that more than 90% of REEs were recovered
in 5 min [143].
According to Vass et al., REEs in AMD treatment sludge can also be economically recovered by
solubilization followed by REE extraction from the solution [22]. Further work by the same group
has led to the design and construction of an acid leaching/solvent extraction mini-pilot plant for the
recovery of REEs from AMD sludge. Leaching data show that high recoveries of REEs (>80%) can
be achieved at a pH value of 1.0 using sulfuric acid. Moreover, the addition of a leaching modifier
increased the leaching recovery from 65% to >95% at a pH of 2.0. Together with the downstream
solvent extraction operation, the continuous pilot process was able to produce high-grade mixed rare
earth oxide products exceeding 80% purity. Techno-economic analysis shows favorable economic
outcomes; however, the authors note that the results are very sensitive to consumable costs [146].
Based on the above discussion, a flowsheet for REE recovery and comprehensive utilization of
AMD is shown in Figure 10. Cost for the staged precipitation step is minimal given the fact that
treatment of AMD is mandated by regulatory agencies. In addition, since only a small quantity
of REE-enriched precipitate is obtained from the staged precipitation step, chemical consumptions
associated with the downstream processes are low. Therefore, AMD can be considered as a promising
Minerals
source 2020, 10, 451
of REEs. 22 of 30

Figure
Figure 10.
10. AAflowsheet
flowsheetfor
formultiple
multiplemetals
metalsrecovery
recoveryfrom
fromacid
acidmine
mine drainage
drainage(AMD)
(AMD)and
andacid
acidmine
mine
drainagesludge.
drainage sludge.

5.Summary
5. Summaryand
andConclusions
Conclusions
Many studies
Many studies have
have been
beenconducted
conductedfor forrecovering
recovering REEs
REEsfrom
fromcoal-related materials,
coal-related primarily
materials, coal
primarily
refuse, coal combustion ash, and acid coal mine drainage. High-purity rare earth
coal refuse, coal combustion ash, and acid coal mine drainage. High-purity rare earth concentratesconcentrates have
been been
have successfully produced
successfully from from
produced coal refuse and acid
coal refuse and coal
acidmine drainage.
coal mine A rare
drainage. A earth pilot plant
rare earth pilot
was constructed and tested, enabling a continuous production of REEs from coal
plant was constructed and tested, enabling a continuous production of REEs from coal refuse. refuse. Reasonable
recovery values
Reasonable also have
recovery valuesbeen
alsoachieved
have beenfrom coal combustion
achieved from coalash. Altogether,
combustion these
ash. findings these
Altogether, show
that significant accomplishments have been made over the past several years in this
findings show that significant accomplishments have been made over the past several years in this area.
area. A summary of the advantages and disadvantages of the methods that have been used for
recovering REEs of
A summary from
thecoal-related
advantages materials is shown in
and disadvantages of Table 5. To achieve
the methods optimum
that have recovery
been used for
performance with minimum cost, process flowsheets integrating various technologies,
recovering REEs from coal-related materials is shown in Table 5. To achieve optimum recovery such as physical
beneficiation,with
performance acid leaching,
minimumpre-leach roasting,
cost, process and hydrothermal
flowsheets integrating pretreatment, need to be designed
various technologies, such as
physical beneficiation, acid leaching, pre-leach roasting, and hydrothermal pretreatment, need to be
designed and tested. More fundamental studies are required to understand the positive impacts
caused by pre-leach calcination on REE recovery from coal refuse. Moreover, this review indicates
that not enough attention has been paid to the extraction behavior of other critical elements as well
as major elements. This deficiency limits the development of multi-element recovery strategies from
Minerals 2020, 10, 451 21 of 28

and tested. More fundamental studies are required to understand the positive impacts caused by
pre-leach calcination on REE recovery from coal refuse. Moreover, this review indicates that not enough
attention has been paid to the extraction behavior of other critical elements as well as major elements.
This deficiency limits the development of multi-element recovery strategies from coal-related materials.
In addition, downstream recovery and purification plans are also ambiguous since the extraction
behavior of major elements such as Al, Fe, and Ca were rarely reported.

Table 5. A summary of the advantages and disadvantages of the methods that have been used for REE
recovery from coal-related materials.

Material Method Advantage Disadvantage

Can be used as a Low recovery; Ultrafine
pre-concentration step to grinding is required if a
Physical beneficiation
generate a higher-grade feed for considerable enrichment ratio
downstream recovery processes. is expected to be achieved.
Leaching performance
Provide relatively higher depends on the nature of
Coal preparation
Direct acid leaching recovery compared with tested samples;
byproducts
physical beneficiation. Acid consumption is
usually high.
Higher REE recovery; Quick
Pre-leach calcination leaching kinetics; Mild leaching Recovery of contaminant ions,
followed by acid leaching conditions; Low chemical such as Al3+ , is also increased.
consumption.
Can be used as a
pre-concentration step to Unable to provide a
Physical beneficiation
generate a higher-grade feed for considerable enrichment.
downstream recovery processes.
Able to transfer a portion of
REEs from solid into solution, Low recovery; High chemical
Coal combustion
Direct acid leaching which can be further recovered cost; Harsh leaching
ashes
and purified using conditions.
other approaches.
High alkali consumption; Low
Alkaline/hydrothermal
High recovery; Quick selectivity and a lot of
treatment followed
leaching kinetics. contaminants are extracted
by leaching
along with REEs
High recovery; Simple process
Staged precipitation flowsheet; Low chemical AMD containing several ppm
Acid coal mine
followed by redissolution consumption; Can be integrated of REEs with a large volume
drainage
and selective precipitation with existing AMD may be difficult to find.
treatment systems.

Author Contributions: Conceptualization, W.Z.; methodology, A.N. and X.Y.; resources, R.H.; writing—original
draft preparation, W.Z. and X.Y.; writing—review and editing, R.H., A.N., and X.Y. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

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