Hydrometallurgy 193 (2020) 105295

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Research progress on leaching technology and theory of weathered crust T

elution-deposited rare earth ore
⁎ ⁎
Wenrui Niea, Rong Zhanga, Zhengyan Hea, Jie Zhoua, Ming Wua, Zhigao Xua, , Ruan Chib, ,
Huifang Yanga,b
a
Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South-Central
University for Nationalities, Wuhan 430074, China
b
Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan 430073, China

A R T I C LE I N FO A B S T R A C T

Keywords: Rare earth (RE) with specific application value has become the relatively important strategic resource for all
Rare earth countries. Weathered crust elution-deposited rare earth ore (WCED-REO) are rich in middle-heavy RE, and its
Weathered crust exploitation restrict the global supply of the middle-heavy RE. The leaching technology directly determines the
Leaching technology leaching efficiency of RE in WCED-REO. The selection and use of the leaching agents are the most important
Leaching agent
parts of the leaching technology. The leaching mechanism is at the core of the leaching technology and also
Leaching mechanism
affects the effective utilization of the leaching agents. The research and development of leaching technologies,
leaching agents, and leaching mechanisms of WCED-REO are discussed in this article. The development pro-
cesses of exiting leaching technologies are introduced. The advantages and disadvantages of barrel leaching,
pool leaching, heap leaching, in-situ leaching, and other leaching technologies are compared. And the new and
practical leaching technologies are put forward. The research progresses of ammonium salt leaching agents,
composite ammonium salt leaching agents, and novel non-ammonium leaching agents in recent years are re-
viewed. The leaching effects of different leaching agents are compared comprehensively to provide guidance for
industrial application and research direction of the best leaching agent in the later period. The leaching basic
theory, as well as the mass transfer process and leaching kinetics of rare earth are introduced. The mass transfer
processes in leaching mechanism are explained from the macroscopic and microscopic perspectives. The further
research directions of the leaching technologies, leaching agents, and leaching mechanism of WCED-REO are put
forward, which provide the theoretical guidance and technical supports for the green and efficient exploitation
of WCED-REO.

1. Introduction 2011).
Rare earth ores (REOs) generally have two types: the mineral type
Rare earth (RE) is an industrial vitamin (Meng, 2011) with high rare earth ores (MT-REOs) and the weathered type rare earth ores (WT-
application value that can significantly improve the performance of REOs). The MT-REOs are rich in light RE and mostly represented by of
materials. RE elements include 15 lanthanides, scandium, and yttrium. bastnaesite and monazite. This type REOs are mainly distributed in
The light RE elements refer to La, Ce, Pr, and Nd. The middle RE ele- China, America, Australia, Canada, and South Africa (Ober, 2016). The
ments refer to Sm, Eu, and Gd. The heavy RE elements refer to Tb, Dy, RE in MT-REOs can be enriched by the conventional physical separation
Ho, Er, Tm, Yb, Lu, and Y (Xu, 2002). Especially, the middle-heavy RE methods such as flotation, magnetic separation, and gravity separation
elements are widely used in the manufacture of permanent magnet (Moldoveanu and Papangelakis, 2012).
materials, luminescent, laser materials, superconducting materials, and Unlike MT-REOs, the WT-REOs are mainly rich in middle-heavy RE,
electronic materials (Moldoveanu and Papangelakis, 2016; Gupta and mostly represented by the weathered crust elution-deposited rare earth
Krishnamurthy, 2015). With the continuous development of science ore (WCED-REO, also known as ion adsorption rare earth ore). WT-
and technology, RE has become the relatively important strategic re- REOs are mainly distributed in the southern provinces of China, such as
source for all countries due to its specific value and low reserves (Chen, Jiangxi, Guangdong, Fujian, Guangxi, Hainan, Hunan, and Yunnan (Chi

⁎
Corresponding authors.
E-mail addresses: xuzhigaotc@126.com (Z. Xu), rac@wit.edu.cn (R. Chi).

https://doi.org/10.1016/j.hydromet.2020.105295
Received 15 November 2019; Received in revised form 18 January 2020; Accepted 15 February 2020
Available online 19 February 2020
0304-386X/ © 2020 Elsevier B.V. All rights reserved.
W. Nie, et al. Hydrometallurgy 193 (2020) 105295

leaching technology for specific ore bodies or mines.

The leaching agent directly relates to the exchange efficiency of
REEs in WCED-REO, the content of impurities in leachate. Whether the
leaching agent meets the environmental requirements is also the hot-
spot for the leaching process of WCED-REO. On the basis of sodium salt
and ammonium salt leaching agents, the RE leaching agents develop
into composite ammonium salt and green non-ammonium leaching
agents (Chi and Liu, 2019). It is believed that ammonium salt leaching
agent is still difficult to be completely replaced in a short period of time.
In this article, the performance of different leaching agents are re-
viewed, which can provide guidance for using and developing green RE
leaching agent with high efficiency.
With the existing leaching technology and leaching agent, the
leaching efficiency of RE has not reached the theoretical maximum. It is
still impossible to leach the RE from the WCED-REO completely.
Because the leaching mechanism has not been thoroughly studied. In
this article, the main methods and achievements in the study of
leaching mechanism for WCED-REO are reviewed, such as the basic ion
Fig. 1. The number of published papers with topics on “Weathered crust elu- exchange theory of leaching, the mass transfer process explained from
tion-deposited rare earth & Ion adsorption rare earth” and “Weathered crust macro and micro perspective, and the leaching kinetics. These are aims
elution-deposited rare earth leaching & Ion adsorption rare earth leaching”, to guide the readers to further study the leaching mechanism, and to
respectively (literature search in the database of Web of Science). further enhance the leaching efficiency of RE.

and Wang, 2014). With the continuous deepening of mine exploration 2. Leaching technology of weathered crust elution-deposited rare
degree, the WT-REOs have been also discovered in Laos (Sanematsu earth ore
et al., 2009), Thailand (Sanematsu et al., 2013, 2015), Indonesia
(Maulana et al., 2014), Madagascar (Berger et al., 2014), Philippines The leaching technology of WCED-REO has gone through three
(Padrones et al., 2017), America (Bern et al., 2017), and other countries stages: barrel leaching and pool leaching technology, heap leaching
in recent years. The WT-REOs are mainly composed of clay minerals, technology, and in-situ leaching technology (Chi and Liu, 2019; Huang
quartz sand, and rock-forming mineral feldspar. The contents of clay et al., 2005).
minerals range from 40 to 70% and its main mineral compositions are
kaolinite, halloysite, illite, and montmorillonite (Chi and Wang, 2014). 2.1. Barrel leaching and pool leaching technology
Rare earth ions (REEs) adsorbed on these clay minerals are mainly in
the forms of hydrated or hydroxyl hydrated ions (Chi and Wang, 2014; The barrel leaching technology was developed in the early 1970s.
Tian et al., 2010a). According to the specific occurrence states of RE in The screened rare earth ore was placed inside wooden barrels, and REEs
WCED-REO, the RE can be easily recovered through ion exchange. That were leached by sodium chloride solution. Due to the small production
is to say, the REEs in the RE raw ore can be exchanged into the solution scale, low output, and high cost, the barrel leaching technology was
by electrolytes leaching. The accompanying impurity ions are also rapidly replaced by the pool leaching technology in the mid-1970s.
being exchanged into the solution, the impurities mainly contain iron During the pool leaching, the screened REOs were firstly placed in
and aluminum, but also calcium and barium. the cement leaching pool with a certain angle tilted bottom, which
The recovery of RE from the WCED-REO is highly dependent on the facilitate the outflow of the RE leachate. The pool leaching technology,
leaching processes. Fig. 1 displays the numbers of published papers on as well as the leaching facilities, is simple and lack of further protec-
the topics of “Weathered crust elution-deposited rare earth & Ion ad- tions, thereby has caused serious environmental pollution. For instance,
sorption rare earth” and “Weathered crust elution-deposited rare earth the vegetation restoration on polluted sites is difficult to achieve.
leaching & Ion adsorption rare earth leaching” from 2010 to 2019. The Moreover, the low recovery efficiency of RE also restricted its further
number of published papers on RE leaching has grown rapidly in the applications. As a consequence, sodium chloride was replaced by am-
past decades, which indicates that this scientific area has become a monium sulfate in the early 1980s. In contrast, ammonium sulfate
research hot spot and has attracted more researchers in this filed. leaching has the lower dosage, higher RE leaching efficiency, and
Recently, the review articles of RE leaching for WCED-REO are brings purer RE products (Chi and Tian, 2008).
limited. Moreover, the existing review publications are mainly focus on In order to further achieve higher exploitation efficiency of WCED-
introducing the mining and leaching processes of REOs. These papers REO, new leaching technologies were developed, such as the heap
do not summarize the latest leaching technologies, and rarely discuss leaching technology and in-situ leaching technology.
the development and application trend of leaching agents, nor do they
explain the leaching mechanism and research methods of REOs. 2.2. Heap leaching technology
The leaching technology directly determines the leaching efficiency
of RE in WCED-REO. Incorrect leaching technology or improper For heap leaching, a clean heap leaching field is required. Junction
leaching process operation (such as liquid injection and liquid collec- canals surrounded with flood protection ditches are designed at the
tion) may lead to serious groundwater pollution or geological disasters lower side of the heap, and the leakproof layer are covered. Meanwhile,
such as landslides while failing to achieve ideal RE leaching efficiency. sludge settling tanks are set to link the junction canals, so that the
In this article, the development of the leaching technologies from barrel leachate can be clarified. Then the REOs are placed on the heap
leaching and pool leaching (Chi and Wang, 2014), heap leaching leaching field. The leaching agent solution is injected to the top of the
technology to in-situ leaching and other leaching technologies are in- heap, then naturally penetrate downward, and therefore leach REEs
troduced. And the new and practical leaching technologies are in- (Deng and Yang, 2016). The flowsheet of the heap leaching technology
troduced. The advantages & disadvantages for different leaching tech- is shown in Fig. 2. Compared with the pool leaching technology, heap
nologies are discussed, in order to guide the selection of a suitable leaching technology can effectively control the solid-liquid ratio of the
leaching process by changing the height of the ore heap (Li, 2014). The

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humus layer. In order to reduce the content of impurities in RE leachate

in heap leaching technology, Chi et al. (2014) stripped the humus layer
and only piled the REOs of the completely weathered layer and partly
weathered layer for heap leaching. Use this method to leach could help
improve the purity of RE leachate, so as to obtain purer RE products,
and reduce the cost of subsequent recovery.

2.3. In-situ leaching technology

In-situ leaching technology include mine prospecting, injection

system, collection system, and some follow-up work. For in-situ
leaching, the mine should be prospected first, to make sure the orebody
has false floor, non-fissure and high permeability (Li, 2014). If these
geological conditions are lacked, a large amount of RE enrichment fluid
will be lost, or the leaching efficiency will be very low. And even worse,
the underground water will be seriously polluted by the leakage of
leaching agent. At this point, it is necessary to replace in-situ leaching
technology with heap leaching technology.
After geological prospecting, the leaching agents are allowed to be
vertically injected into the orebody through injection holes drilled at
the top of the RE mine. RE leachate is collected from deflector holes and
collection ditches at the foot of the mountain, anti-seepage measures
were applied in the collection ditches and drainage ditches to avoid the
loss of RE enrichment fluid (Deng and Yang, 2016). The flowsheet of
the in-situ leaching technology is shown in Fig. 3. Compared with pool
leaching and heap leaching technologies, in-situ leaching technology
does not dig topsoil or ore. There are no damages to the mountains and
vegetation, little destruction of mine surroundings, less workload, and
lower production cost in the in-situ leaching technology. These obvious
advantages make in-situ leaching technology widely used.
In-situ leaching technology is not perfect. Collapse of the injection
hole or leakage of the leachate is usually appeared during the leaching
process, which is easy to cause landslides, environmental damages and
reduce the recovery efficiency of RE. To a certain extent, these pro-
blems can be improved by optimizing injection and collection tech-
nology.

2.3.1. Injection technologies

Injection technology is the first step of in-situ leaching technology.
In the traditional injection technology, the leaching agent is injected
directly into the ore body through the injection holes, the drilled holes
enlarge contact areas so that enhance the ore leaching. But there are
some problems, such as the poor stability of injection holes, the over-
topping of leaching liquid in injection holes, and the increase of land-
slides probability. In order to overcome these issues, the injection
technology has been optimized. Zhang et al. (2016a) proposed a new
Fig. 2. Flowsheet of heap leaching technology of the weathered crust elution- injection technology. In this technology, the circular injection holes
deposited rare earth ore. with a diameter of 0.16 m were drilled vertically downward along the
mountain surface. The downcomers were placed into the holes, the
leaching agents can be used more effectively, and the technology has space between the hole and the downcomers were filled with fillings,
higher recovery efficiency so that result in lower costs. which could withstand the mountain surface pressure. The marker
The RE leaching efficiency is affected by the permeation of leaching poles were placed into the downcomer to monitor liquid level heights.
solution in ore (Zhou et al., 2019). High permeability is beneficial to the This method not only guarantees the effective utilization rate of injec-
leaching efficiency of RE. However, orebody of some WCED-REO are tion holes, but also reduces the occurrence of safety accidents and
weak in permeability. In this case, Wei et al. (2016) found that adopting improved the recovery efficiency of RE. Wang et al. (2017a) designed a
the heap leaching technology could have a shorter leaching period and device to promote the permeability of the ore, this was also a new type
higher RE recovery efficiency. At the same time, it could mitigate the of injection tube. It was comprised of the inner tube, the outer tube with
anti-adsorption phenomenon of RE as well as the influence of the cli- seepage holes, and cavity with the sealed bottom. The cavity was filled
matic conditions. Mei et al. (2017) effectively improved the perme- with porous anticorrosive medium. This device can reduce the depth
ability of solution in ore and the leaching efficiency of RE by optimizing and quantity of the injection holes, therefore enhance the stability of
the conditions and parameters of heap site constructions. These op- the injection holes. Zhang et al. (2016b) controlled the height of the
timum proposals include a set bottom pad inclination angle in the heap liquid level in the injection holes by adjusting the flow rates of liquid
site, a reduced heap height, adopted heap construction in sections and injection, so that the leaching agent only contacted with the completely
layers, and added permeators within the ore heap. and partly weathered layer with more ionic phase RE and less im-
Most of the main impurity aluminum in RE leachate came from the purities, and avoided contacting with humus layer with few ionic phase
RE and more impurities. This method can not only decrease the content

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W. Nie, et al. Hydrometallurgy 193 (2020) 105295

2.3.2. Collection technologies

The collection technology is the key to ensure the recovery effi-
ciency of RE and prevent pollution diffusion. Traditional collection
technology not only has low RE recovery efficiency, but also has the
hidden danger of leaching liquid leakage. In the meanwhile, the col-
lection ditch built by cement can also pollute the mountain environ-
ment. For these reasons, new collection technologies have been put
forward one after another. Hu et al. (2015) proposed a new method to
improve RE leachate recovery efficiency. In this technology, the de-
flector roadways in mine were opened between the completely
weathered layer and partly weathered layer. The deflector holes had
been increased from 1 to 2 rows, and were located at the side of the
partly weathered layer, near the slight weathered layer. The horizontal
inclination angle, distance of deflection holes, and row spacing of de-
flection holes were improved. This technology can avoid the loss of RE
resources in the completely weathered layer and the loss of RE en-
richment fluid in leachate by means of opening the combination of
deflector roadways and deflector holes. Aimed at the WCED-REO with
complex orebody, Yuan et al. (2017) proposed a new interception and
collection technology to improve RE leachate recovery efficiency. The
technology included four processes: collecting roadways, deflector
holes, cutting grooves and anti-seepage treatment. The most important
point was that the deflector hole and the groove could form a manual
interception plate, which could intercept more than 90% of the
leaching fluid flowing through the area. In order to effectively reduce
the leakage of the leachate, Chi et al. (2018) designed multi-stage in-
tercept pools according to the high terrain to low terrain, which were
built in the catchment water at the foot of the mine. According to the
content of RE in the interception pool, the dosage of leaching agent
could be controlled precisely to reduce the extra consumption of
leaching agent, thus reduced the costs and the corresponding pollution.
Zou et al. (2016) invented an aquifer water collection device. The de-
vices were connected with the collection ditches and were placed sur-
round REOs. This device effectively improves the collection efficiency
of leachate, therefore avoided the loss of RE enrichment solution and
reduced the recovery costs.

2.4. Other leaching technologies

In the leaching process of WCED-REO, some external conditions can

be applied, such as heating (Moldoveanu and Papangelakis, 2015),
electric field (Zuo et al., 2007), magnetic field (Qiu et al., 2008), and
ultrasound (Yin et al., 2018). The techniques mentioned above can
change the physicochemical properties of the surface of mineral parti-
Fig. 3. Flowsheet of in-situ leaching technology of the weathered crust elution- cles, enhance the diffusion rate of the ions between the solid-liquid
deposited rare earth ore. interface, therefore improve the leaching efficiency of RE (Wang et al.,
2018). However, these auxiliary conditions are difficult to be applied in
of the impurity ions in the leachate from the source, but also reduce the the practical industrial exploitation, and only keep the laboratory ex-
geological disasters such as the landslide caused by the water swelling ploration stage.
of clay minerals in the humus layer. Gui et al. (2017a,b) calculated the
total amount of liquid injection and steady seepage flow of the single- 2.5. Comparison of different leaching technologies
hole injection during in-situ leaching by determining relationship be-
tween the leaching efficiency of RE and the saturation of the hole In order to comprehensively evaluate the above-mentioned leaching
bottom. Based on these, a design method of network hole parameters technologies, the advantages and disadvantages of which are illustrated
for in-situ leaching was proposed to reduce the no-control rates of in Table 1 (Li, 2014). It can be seen that in-situ leaching technology is
leaching ore and landslide incidence. the best and most promising technology at present, but it is easy to

Table 1
Advantages and disadvantages of above-mentioned leaching technologies.
Comparison item Heap leaching technology In-situ leaching technology Other leaching technologies

Industry technology policy Less widely used leaching technology Popularized leaching technology Experimental leaching technology
Mine condition Orebody with weak permeability, fissure, and non-false Orebody needs false floor or flat land, non-fissure No leaching in the field.
floor or the flat land. and high permeability.
Vegetation Suffer great damage No damage
RE leaching efficiency About 90% 90%–95% 89.52%–99.62%

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W. Nie, et al. Hydrometallurgy 193 (2020) 105295

cause geological problems due to improper technical treatment or WCED-REO.

management. Therefore, more attention should pay for the ore geology
prospecting before using in-situ leaching technology, and improving the
3.1. Composite ammonium salt leaching agents
injection technologies. More attention should also be payed to the im-
provement of the collection technologies, because which not only affect
The common ammonium salt leaching agents are (NH4)2SO4,
the leaching efficiency of RE, but also affect the pollution degree of
NH4Cl, and NH4NO3. The cation exchangeability and permeability of
surface water and groundwater. It is important to point out that, for the
NH4NO3 and NH4Cl are better than (NH4)2SO4 (He et al., 2017).
orebody with weak permeability, fissure, and non-false floor or the flat
NH4NO3 as a dual‑nitrogen fertilizer provides more available nitrogen
land, the heap leaching technology is particularly recommend. It can
during leaching, which will aggravate ammonia nitrogen pollution in
realize the high recovery efficiency of RE and avoid the leakage of the
mining areas. Although NH4Cl is more available and inexpensive, its
RE leachate to pollute the water body (Chi and Liu, 2019). Also, ve-
poor selectivity performance lead to more remained impurity ions in
getation removed during heap leaching also needs to be handled
the leachate. (NH4)2SO4 as the leaching agent can obtain the leachate
properly. Other novel leaching technologies need to take the actual
with fewer impurity ions, but the leaching efficiency of RE is slightly
situation into account, otherwise it is an armchair strategist.
lower and the anti-swelling effect is worse (He et al., 2016). Compre-
hensive evaluation shows that the leaching effect of (NH4)2SO4 is better
3. Leaching agent of weathered crust elution-deposited rare earth than that of NH4Cl and NH4NO3. In order to optimize the performance
ore of single ammonium salt leaching agent, some methods are proposed,
like compounding ammonium salts or adding additives (e.g. inorganic
The initial leaching agent of WCED-REO was NaCl solution (6–8 wt or organic agents) into the leaching agents (Li, 2014).
%). However, NaCl leaching agent gets low RE leaching efficiency and Zhang et al. (2013) and (2014) compounded NH4Cl, NH4NO3, and
high impurity in leachate. What's more, it would produce a large (NH4)2SO4 with a mass ratio of 4: 5: 6, NH4Cl and NH4NO3 were
number of high-salt wastewater, improper treatment or disposal will compounded with a mass ratio of 8: 2, respectively. Compared with
lead to soil salinization and eventually damage the ecological en- single ammonium salt leaching agents, composite ammonium salt
vironment. (NH4)2SO4 as the leaching agent, by contrast, can not only leaching agents could maintain high RE leaching efficiency. Besides,
decrease the concentration and consumption volume of the leaching they could effectively reduce the linear expansion rate of clay minerals,
agent, but also improve the leaching efficiency of RE and reduce the the linear expansion rates were both lower than 2.8%. As an assistant
leaching of impurities (eg. calcium and barium) by forming the in- leaching agent, the addition of some quaternary ammonium salt sur-
soluble sulfate to stagnate in ore body. Thus, (NH4)2SO4 (1–4 wt%) factants can also play an anti-swelling role (Wang et al., 2018). The
replaced NaCl as the main leaching agent in the exploitation of WCED- geological disasters like landslides caused by the swelling of clay mi-
REO, and are widely used at present. nerals after adsorption of water (Zhang et al., 2018) could be reduced in
In addition, (NH4)2SO4 leaching agent can also be injected in stages the leaching process.
with different concentration. For the WCED-REO with high muddy, Tian et al. (2013a) and Tang et al. (2013) found that when 0.03%
Kong (2018) suggested that the leaching process could be divided into sesbania gum (SG) was added with 3% (NH4)2SO4, the leaching effi-
two stages to improve the permeability coefficient of the muddy ores ciency of RE could be increased by 7.12%. Also, the concentration of
and shorten the production cycle. In the earlier stage, the leaching leaching agent decreased from 4% to 3%. Then Tian et al. (2013b)
agent was 4% (NH4)2SO4, and the concentration of (NH4)2SO4 was modified SG with carboxymethyl to obtain carboxymethyl sesbania
decreased to 2% in the later stage. High concentration of (NH4)2SO4 in gum (CSG), which was added into (NH4)2SO4 to further improve the
the earlier stage had high acidity, which could dissolve alkaline mi- leaching efficiency of RE, and reduced the concentration of (NH4)2SO4
nerals or colloids of micro particles in mineral soil and expand pores in to 2.5%.
mineral soil, the permeability of ores was improved. The dosage of Qiu et al. (2014a) found that the composite leaching agent of 0.1%
leaching agent could be reduced by reducing the concentration in later of the impurity inhibitor LG-01 (organic agents containing hydroxyl
stage. and carboxyl groups) and 4% (NH4)2SO4 could obtain a high RE
In order to further improve leaching effect (e.g. RE leaching effi- leaching efficiency and up to 92% of the impurities removal efficiency.
ciency, impurity removal efficiency, and environmental impact and so Qiu et al. (2014b) found that adding YZJ-01 (organic impurity in-
on.), many scholars tried to optimize leaching agents or develop novel hibitor) to (NH4)2SO4 leaching agent could make RE leaching efficiency
leaching agents such as composite ammonium salt, magnesium salt, and up to 98% under the best conditions. At the same time, the leaching of
aluminum salt leaching agents (Wang et al., 2018; Yang et al., 2019). impurities such as aluminum and iron are greatly inhibited. Subse-
Applying more advanced leaching agents could help realize a green, quently many novel leaching agents with ammonium salts were also
higher efficiency, low impurity, and low consumption exploitation of proposed, and the main leaching agents were listed in Table 2.

Table 2
The main novel leaching agent with ammonium salts.
Ammonium salts Additives Effects Literature sources

2.0% of (NH4)2SO4 and NH4NO3 with molar ratio of 0.05% CH3COONH4 The leaching efficiency of RE exceeded 80%. Yang and Zhang (2015)
4:1 The removal efficiency of Al in the leachate exceeded 80%.
4% (NH4)2SO4 0.1% C14H12O8 The leaching efficiency of RE increased by 8.38%. Luo et al. (2015)
The concentration of (NH4)2SO4 was reduced by 25%.
3% (NH4)2SO4 1% of impurity inhibitor 2# The leaching efficiency of RE exceeded 92%. Peng et al. (2016)
The concentration of Al in the leachate was less than 1 mg/L.
2% (NH4)2SO4 2% QZX-02 The leaching efficiency of RE increased to 97.58%. Yan et al. (2018)
The concentration of Al in the leachate was 0.016 g/L.
3% (NH4)2SO4 0.35% C4H6O6 The leaching efficiency of RE exceeded 98%. Fang et al. (2018)
The removal efficiency of Al and Fe in the leachate exceeded
90%.
0.1 mol/L (NH4)2SO4 0.032 mol/L HCOONH4 The leaching efficiency of RE was 92.97%. Feng et al. (2018)
The leaching efficiency of Al was 37.79%.

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3.2. Novel non-ammonium leaching agent alternative green leaching agent is the magnesium salt, proposed by
academician Huang Xiaowei (Huang et al., 2016; Xiao et al., 2016a),
Composite ammonium salt leaching agents still contain NH4+ or which has been widely used in REOs.
NO3−, which will produce ammonia‑nitrogen wastewater. Thus, de- Besides, the colloidal sedimentary phase of RE also accounts for a
veloping novel green non-ammonium leaching agents, to replace the certain proportion of RE in ore. Although the currently used leaching
ammonium salt leaching agents, have become a research hotspot. agents can leach more RE in the colloidal sedimentary phase, the
Xiao et al. (2015a, 2015b) found that the use of 0.20 mol/L MgSO4 leaching efficiency has not reach theoretical maximum, which is what
could obtain a low leaching efficiency of impurity aluminum and above we should pay attention to develop new leaching agent and research the
93% of RE can be leached out. The leaching effect of MgSO4 was nearly leaching mechanism.
the same as that of (NH4)2SO4. It indicated that ammonia nitrogen
pollution could be avoided by using the non-ammonium leaching agent. 4. Leaching mechanism of weathered crust elution-deposited rare
Due to its pollution-free and relatively high leaching efficiency, MgSO4 earth ore
has been added into the leaching agents and used in industry. In order
to further improve the leaching performance and greenization of The leaching mechanism is benefit to enrich the theoretical basis of
MgSO4, MgSO4 was mixed with NH4Cl and CaCl2 at a molar ratio of WCED-REO, and provide theoretical guidance for the development of
15:25:60 to obtain a new composite leaching agent. The leaching effi- novel leaching agents so that help optimize the leaching technologies.
ciency of RE could be increased to above 94%, while that of aluminum The leaching mechanism of WCED-REO is introduced from the fol-
could be reduced to 49.2% (Xiao et al., 2016a). This novel composite lowing three aspects: leaching basic theory of rare earth, mass transfer
magnesium salt leaching agent makes the ratio of exchangeable calcium process, and leaching kinetics.
to magnesium in soil meet the requirement of soil nutrient ratio, and
solves the problem of ammonia nitrogen pollution from the source, so it 4.1. Leaching basic theory of rare earth
has been applied in industry.
The mechanism of the leaching agents mentioned above is mainly The main mineral constituent of WCED-REO is clay minerals, which
leaching of ionic phase RE instead of the colloidal sedimentary phase are aluminosilicate and can be seen as a natural inorganic ion exchange
RE. Xiao et al., 2016b tried to leach the colloidal sedimentary phase RE agent. When rare earths adsorbed on the clay minerals meet the am-
(mainly CeO2/Ce(OH)4) using FeSO4 as leaching agent by the re- monium salt solution, the ion exchange reaction is shown as Eq. (1):
ductivity of Fe2+. To some extent, the leaching efficiency of RE could
reach about 102%, but the content of impurity ions in the leachate was [Al 4 (Si4 O10 )(OH )8 ]m ∙nRE 3 +(s) + 3nNH4+(aq) ⇌ [Al 4 (Si4 O10 )(OH )8 ]m
also greatly increased, it was not conducive to the impurity removal. ∙3n [NH4+(s) ] + nRE 3 +(aq) (1)
Whereupon, the dissolution of CeO2/Ce(OH)4 became easier by adding
ascorbic acid with a strong reductivity to MgSO4 in the leaching pro- where: s is solid phase; aq is liquid phase.
cess, then Ce3+ could be acquired (Xiao et al., 2017). This novel The ion exchange reaction is a reversible heterogeneous reaction,
compound leaching agent could improve the leaching efficiency of which is the theoretical basis of chemical leach of RE from WCED-REO.
colloid sediment phase RE, reduce greatly the leaching efficiency of Therefore, the RE leaching basis theory is to inquire the adsorption
impurities (Al and Fe) and decrease the dosage of MgSO4 (Lai et al., sites, solution ion strength, solution acidity, ion complexation, and
2018a, 2018b). surface electrical properties of clay minerals in WCED-REO. It will be
Beside the leaching agents of magnesium salts, Yang et al. (2018) conducive to reveal the internal influencing factors of RE leaching ef-
put forward aluminum salt as the novel leaching agent. The leaching ficiency.
efficiency of RE for Al2(SO4)3 solution in 0.128 mol/L could reach Xu et al. (2018) considered that except the surface of clay minerals,
98.25%, higher than that of the ammonium salts and magnesium salts. the REEs also adsorbed on the interlamination and marginal fracture
Because of the low zeta potential of Al2(SO4)3, the repulsion force be- structures of clay minerals and the colloidal particles of iron, manga-
tween mineral particles during leaching is the least and the anti-swel- nese, and aluminum with strong adsorption to REEs. Among the ad-
ling effect is the best, which can reduce the risk of landslide (Zhang sorbed sites, the interlayer of clay minerals was the most difficult for
et al., 2018; Yang et al., 2018). Thus, Yang et al. (2019) used Al2(SO4)3 the RE desorption. Sun et al. (2017) thought that the leaching process of
in multi-stage leaching ore process. (NH4)2SO4 was used as the leaching WCED-REO by the low concentration of (NH4)2SO4 belonged to two-
agent in the first stage, 0.02 mol/L Al2(SO4)3 was used as the leaching stage inter-diffusion process. This reflected that the adsorption sites of
agent in the second stage. Due to the addition of Al2(SO4)3, the residual REEs on clay minerals are different, one is adsorbed on the surface, the
ammonium in tailing decreased from 11.2% to 0.6%, the absolute value other is adsorbed on the interlamination. In the first stage, the leaching
of zeta potential of the tailings decreased and approached 1.5, the re- efficiency of RE was fast and the ion exchange reaction main occurred
quired amount of lime in subsequent treatment decreased, which led to on the surface of the clay minerals. In the second stage, the leaching
the low cost and low environmental impact. However, the effect of efficiency of RE was slow and the ion exchange reaction main occurred
impurity content in leachate was not considered when Al2(SO4)3 was among the interlamination of the clay minerals.
used as the leaching agent, so it is only proposed in the experimental Moldoveanu and Papangelakis (2012) believed that under the
stage, and has not been applied in industry. condition of low ion strength and slightly acidic/neutral, it was easy for
the cation exchange to be occurred in the permanent charge position
3.3. Comparison of different leaching agents inside clay particles. The ions complexed on the surface or edge of clay
minerals were easily affected by the pH, so the appropriate increase of
Generally, the development of leaching agent has been gradually on solution acidity was conducive to the leaching of RE. Alshameri et al.
the road of green and pollution-free development. Table 3 illustrates (2019) also found that at pH > 5, the permanent chemical adsorption
advantages and disadvantages of various leaching agents to compre- could occur on montmorillonite and muscovite white mica. Then the
hensively evaluate each leaching agent. The more plus signs (+), the availability of ion-exchangeable between NH4+ with RE3+ adsorbed on
better leaching effect would be gets. Obviously, the leaching agent the clay minerals was reduced, when using (NH4)2SO4 as the leaching
containing ammonium salt is more efficient. It may be inevitable that agent. Moreover, when the pH is higher than 5, the adsorption of rare
there are leaching agents containing ammonium salt in the future. earth ions at amphoteric edge surface sites could be reduced (Sinitsyn
Thus, more attention should be payed to the development of additives et al., 2000; Moldoveanu and Papangelakis, 2013). So the increase of
to reduce ammonia nitrogen pollution. At present, the most promising pH value reduced the leaching efficiency of RE. Wang et al. (2017b)

6
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Table 3
Advantages and disadvantages of various leaching agents.
Main leaching agents Additives Leaching Linear expansion rate Removal efficiency of Impurity content Ce partition in Environmental impact Literature sources
efficiency of RE of clay minerals impurity Al3+/Fe3+ in leachate leachate

10 g/L of NH4Cl, NH4NO3 and No ++++ ++ Ammonia nitrogen pollution, the Zhang et al. (2013)
(NH4)2SO4 with a mass ratio of lower probability geological hazard.
4:5:6
3% (NH4)2SO4 0.03% SG +++ Ammonia nitrogen pollution. Tian et al. (2013a)
2.5% (NH4)2SO4 0.03% CSG ++++ Ammonia nitrogen pollution. Tian et al. (2013b)
10 g/L of NH4Cl and NH4NO3 with a No ++++ + Ammonia nitrogen pollution, the Zhang et al. (2014)
mass ratio of 8:2 lower probability geological hazard.
4% (NH4)2SO4 0.1% LG-01 ++++ +++ Ammonia nitrogen pollution. Qiu et al. (2014a)
0.3 mol/L (NH4)2SO4 0.018 mol/L YZJ-01 ++++ +++ Ammonia nitrogen pollution. Qiu et al. (2014b)
2.0% of (NH4)2SO4 and NH4NO3 with 0.05% CH3COONH4 + +++ Ammonia nitrogen pollution. Yang and Zhang
molar ratio of 4:1 (2015)
4% (NH4)2SO4 0.1% C14H12O8 ++++ Ammonia nitrogen pollution. Luo et al. (2015)
0.20 mol/L MgSO4 No +++ ++ Unbalance of soil nutrient elements. Xiao et al. (2015a)

7
3% (NH4)2SO4 1% of impurity +++ ++ Ammonia nitrogen pollution. Peng et al. (2016)
inhibitor 2#
0.20 mol/L of MgSO4, NH4Cl and No +++ + Lower dosage of ammonium, balance Xiao et al. (2016a)
CaCl2 with molar ratio of of soil nutrient elements.
15:25:60
0.20 mol/L FeSO4 No + + ++ – + No ammonia nitrogen pollution Xiao et al. (2016b)
0.20 mol/L MgSO4 0.5 g/L ascorbic acid + + + ++ Unbalance of soil nutrient elements. Xiao et al. (2017)
2%(NH4)2SO4 2% QZX-02 + + ++ ++ Ammonia nitrogen pollution. Yan et al. (2018)
3% (NH4)2SO4 0.35% C4H6O6 + + ++ +++ Ammonia nitrogen pollution. Fang et al. (2018)
0.1 mol/L (NH4)2SO4 0.032 mol/L + + + + Ammonia nitrogen pollution Feng et al. (2018)
HCOONH4
0.15 mol/L MgSO4 1 g/L ascorbic acid ++ + ++ Unbalance of soil nutrient elements. Lai et al. (2018a,
2018b)
0.128 mol/L Al2(SO4)3 No ++++ No ammonia nitrogen pollution, the Yang et al. (2018)
lower probability geological hazard.

Note: the degree of leaching efficiency of rare earth can be expressed as + + + + (> 95%), + + + (90–95%), + + (85–90%), and +(< 85%). The degree of linear expansion rate of clay minerals can be expressed as
+ + (< 2.5%) and + (2.5–3%). The degree of removal efficiency of impurity can be expressed as + + + (> 90%), + + (80–90%), and + (< 80%). The degree of impurity content in leachate can be expressed as + +
(< 20 mg/L), + (20–40 mg/L),and - (> 40 mg/L). The degree of Ce partition in leachate can be expressed as + + (> 5.5%) and + (< 5.5%).
Hydrometallurgy 193 (2020) 105295
W. Nie, et al. Hydrometallurgy 193 (2020) 105295

pointed out that the relatively high concentration of organic acids could diffusion EDL theory, the model is shown in Fig. 4. In the stern model,
promote the RE desorption and inhibit the RE re-adsorption, due to the EDL is divided into stern layer and diffusion layer. The value of zeta
their complexation ability with RE in the solution (Li, 2014). The dis- potential is very close to the value of the stern layer potential, which
sociation of the relatively low concentration of organic acids could reflects the adsorption capacity of clay mineral surface to metal ions
change the surface charge properties of RE minerals with increasing H+ (Şans et al., 2017). The greater the absolute value of zeta potential is,
absorbed on REOs (Naidu and Harter, 1998; Chiang et al., 2011), de- the stronger the adsorption capacity to metal ions will be. And the
crease the affinity of RE minerals and REEs, thereby organic acids could solute ions in the leaching agent exist in the form of hydration and enter
promote the leaching of RE. Hu et al., 2018a believed that aluminum into the stern layer. The leaching capacity of RE depends on the valence
ions on the surface of kaolin could inhibit the adsorption ability of state and hydration ion radius. On this basis, Xu et al. (2019) and Zhang
kaolin with REEs, and the kaolin would release aluminum ions to affect et al. (2018) found that with the same concentration of the leaching
the adsorption of REEs at a certain acidity. agent, the higher the cation valence state of the leaching agent was, the
easier the cations enter the stern layer and be exchanged by REEs, and
the stronger the leaching capacity of the leaching agent to RE was. Xu
4.2. Mass transfer process et al. (2019) believed that anion in water solution was in the form of a
hydrate state as well, and their adsorption capacity was also determined
The leaching mass transfer process of WCED-REO was once re- by the ion potential or charge density. Compared with chloride ions and
garded as the chromatographic leaching process (MacDonald et al., nitrate ions, hydrated sulfate ions have much higher ionic potential and
2004). The mass transfer of RE leaching could be highly expressed by are more likely to be attached onto the positive charged regions on the
the height equivalent to a theoretical plate (HETP). The mass transfer edge surface of clay mineral particles (Xu et al., 2018), thus making
effect increased with the decrease of HETP (Tian and Yin, 1996). The negatively charged clay mineral surface more negative. Due to the
relation between leaching flowrate and HETP can be described by Van enhanced negative charged surface of clay mineral particles in stern
Deemter equation to determine the optimum flowrate (Tian et al., layer, the cations from leaching agents are more likely to be adsorbed
2010b). This theory can reveal the leaching mechanism of REO from a on the surface so that exchange out the REEs. Therefore, sulfate ions
macro perspective, and guide RE leaching in industry. Meanwhile, ore could improve the exchange rate of REEs. However, in view of this
grade and ore size can largely affect the leaching efficiency. In order to conclusion, some scholars hold opposite perspectives, Zhang et al.
select and use the leaching agent more accurately, it is necessary to (2018) thought that since sulfate ions carry two negative charges, the
study the leaching mechanism from the micro perspective. force between sulfate ions and ammonium ions was stronger than that
For WCED-REO, the REEs are mainly adsorbed on clay minerals in between monovalent anions (eg. Cl− or NO3−) and ammonium ion.
the form of hydrated or hydroxyl hydrated ions (Chi and Wang, 2014; Therefore, compared with the leaching agent of NH4Cl and NH4NO3,
Tian et al., 2010a). Diffusion electric double layer theory can explain ammonium ions and sulfate ions in the leach agent solution are more
the interaction among the cations of clay mineral surface and inter- likely to form “positive and negative ion association”, which reduced
layer, water molecules surrounded the cations and the solution (Gao, the chance for ammonium ions to enter the double electrode layer
2017). At a more microscopic level, the leaching mass transfer process (Raymond et al., 2011; Ermakova et al., 2006). Obviously, the exchange
of REO is actually the ion exchange process of REEs in the diffusion of REEs will also be reduced. The zeta potential of clay minerals in
electric double layer, so the leaching mechanism of WCED-REO can be (NH4)2SO4 is lower than that in NH4Cl and NH4NO3, the anti-swelling
explained by the diffusion electric double layer model. effect is worse. Therefore, NH4Cl instead of (NH4)2SO4 was used as the
According to Poisson Boltzmann equation, Xiao et al. (2018) de- leaching agent in actual mine leaching operation.
duced the relationship between the potential φ(x) and the distance x in In terms of the hydration of hydrated ion in the EDL, Moldoveanu
the electric double layer (EDL). And the potential φ(x) was related to and Papangelakis (2012) thought when the hydrated monovalent ca-
the charge density, temperature, and anti-ion concentration. The higher tion (M+) arrived at the position adsorbed REEs (Ln3+), cations with
these values are, the higher RE leaching efficiency will be obtained. The low ΔHhyd (e.g. < 400 kJ/mol, such as M+) could dehydrate com-
leaching process of WCED-REO was actually a process that a new stable pletely, and adsorbed on the clay minerals surfaces to form a strong
EDL with cations in leaching agent established and the old EDL with electrostatic bond. But cations with high ΔHhyd (e.g. > 3000 kJ/mol,
REEs collapsed. When the potential φ(x) in the new EDL was smaller such as Ln3+) retained at least some of the hydration water, and ad-
than that in the original EDL during the leaching process, the REEs in sorbed on the clay minerals surfaces to form a weaker electrostatic
the diffusion layer will be replaced by the cations from the leaching bond. So, the REEs with high ΔHhyd were easy to be desorbed from the
agents, therefore new EDL clay minerals were formed and REEs were clay minerals by the cations with low ΔHhyd.
exchanged into the leachate. The smaller potential φ(x) in the new EDL
is, the greater RE leaching ability is.
At present, the stern model (Gao, 2017) is widely used in the

Fig. 4. A electric double layer schematic of clay minerals (Xiao et al., 2018).

8
W. Nie, et al. Hydrometallurgy 193 (2020) 105295

particles and its weight ratio had some influence on the dynamic
equilibrium of solvent and solute. The model could not only simulate
the concentration distribution of leaching agents in each area, but also
determine the rate control steps in the leaching process of RE by si-
mulating the main parameters of the leaching kinetics of RE.

5. Conclusion and prospect

In the past 50 years, aimed at the WCED-REO, the leaching tech-

nology obtained a breakthrough. But the RE leaching efficiency and
Fig. 5. Schematic diagram of leaching process. (a is the non-leached mineral environmental pollution still need to be improved further. And most
particle; b is remainder of solid; c is diffusion region of solution). researches on the leaching mechanisms are in the macroscopic aspect,
which needs to be explored in the microscopic aspect.
Through the summary of leaching technologies, leaching agents and
4.3. Leaching kinetics
leaching mechanisms of WCED-REO, it can be seen that the main re-
search directions in the future are as the followings:
In the leaching process of WCED-REO, cations in the leaching agents
will exchange the REEs adsorbed on clay minerals, which is a typical
(1) Optimize the leaching technology of WCED-REO: Enhance the
liquid-solid heterogeneous ion exchange process. At present, the most
prospecting of geological environment information of ore body.
typical leaching reaction model is “shrinking unreactive core model”
Geological environment information such as fault position, plane
(Chi and Tian, 2008), and the schematic diagram is shown in Fig. 5. The
extension direction, and section extension are obtained by means of
leaching process of WCED-REO can be divided into five stages: solute
remote sensing, GIS, and other digital measures, so as to take cor-
ions in the leaching agent diffuse from the solid-liquid interface mem-
rect and effective measurements to reduce the occurrence of geo-
brane to the surface of mineral particles (I External diffusion), solute
logical disasters and environmental pollution caused by leaching. It
ions further diffuse in the mineral particles (II Internal diffusion), solute
is necessary to further optimize the in-situ leaching technology,
ions exchange with REEs on mineral particles (III Chemical reaction),
including injection technologies and collection technologies.
the exchanged REEs then diffuse from the surface of the mineral par-
Eventually realize the greenization, high efficiency, and in-
ticles to the solid-liquid membrane (IV Internal diffusion), the ex-
tellectualization prospecting of WCED-REO.
changed REEs continue to diffuse into the solution (V External diffu-
(2) Develop the leaching agents for WCED-REO: Additives such as
sion). Among the five stages, internal diffusion is the key to control RE
impurity inhibitor, permeability promoter, and swelling inhibitor
leaching efficiency of WCED-REO (Tian et al., 2010b, 2010c). However,
should be developed to make up for the deficiencies of single
the REOs in this model are regarded as the spherical particles, while the
leaching agents. The green and non-pollution novel non-ammonium
shape of the ore particle in the actual leaching process is various, which
leaching agents with better RE leaching performance in ionic or
is also the reason why the model is not rigorous.
colloidal sedimentary phase need more attention and investigation.
Except the shrinking unreactive core model, the Kerr model (Kerr,
(3) Intensify the leaching mechanism of WCED-REO: The ion exchange
1928) proposed by Kerr H W is also a widely used solid-liquid ion ex-
mechanism between REEs and solute ions may be further revealed
change model in edaphology, but the model is rarely used in the
by referring to the solid-liquid ion exchange model commonly used
leaching process of WCED-REO. Hu et al. (2018b) thought that using
in edaphology or digital simulation. The effects of surface charge
the (NH4)2SO4 as the leaching agent to leaching RE, the ion exchange
properties of clay minerals on REEs and impurity ions should be
process between ammonium ions in liquid phase and REEs in solid
investigated from the perspective of microscopic atoms. The ad-
phase could be described accurately by the Kerr model. As shown in Eq.
sorption site and water content of rare earth ions on clay minerals,
(2), the selection coefficient Kk of this model could reflect the adsorp-
and the effects of surface water and interlayer water in clay mi-
tion capacity of clay minerals to NH4+ and RE3+. The larger Kk was, the
nerals on the adsorption and desorption of REEs should be studied
easier the RE3+ in solid phase were exchanged by NH4+ in liquid
with more characterizations. From the aspects of quantum chem-
phase. The optimal concentration of (NH4)2SO4 could be determined by
istry, the exchange forms and modes of REEs/impurity ions need
this model. Long et al. (Long et al., 2019) also used the Kerr model and
further research as well as the solvent cations and the effect of
the convection-dispersion equation to simulate the migration process of
solvent anion on RE leaching.
REEs during column leaching, and found that the optimal concentration
of (NH4)2SO4 leaching agent had a linear relationship with the RE
Declaration of Competing Interest
grade.

[RE 3 +]lq [NH4+]s 3 The authors declare that they have no known competing financial
Kk = interests or personal relationships that could have appeared to influ-
[RE 3 +]s [NH4+]l3 (2)
ence the work reported in this paper.
where [RE3+]lq and [NH4+]l are the molar concentrations of rare earth
ions and ammonium ions in liquid phase, mol/L, respectively. [RE3+]s Acknowledgments
and [NH4+]s are the molar concentrations of rare earth ions and am-
monium ions in solid phase, mol/g, respectively. The work is financially supported by grants from the National
Lattice Boltzmann (LBM) reveals the macroscopic transport reg- Natural Science Foundation of China (No. 51704339 and No.
ularity from the microscopic perspective using the numerical simula- 51734001) and the “Fundamental Research Founds for the Central
tion method (Chen and Doolen, 1998; McNamara and Zanetti, 1988). Universities”, South-Central University for Nationalities (No.
Hence, LBM can be used to simulate the transport process of the solute CZY19033, No. CZP19002, No. YZZ16002, and No. CZQ19016).
in porous media, namely the leaching process of WCED-REO. On this
basis, Qiu et al. (2017) proposed the LBM model with coupled chemical References
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