Journal of Cleaner Production 165 (2017) 231e242

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Journal of Cleaner Production

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Review

Towards cleaner production of rare earth elements from bastnaesite in

China
Liangshi Wang a, b, *, Xiaowei Huang a, b, Ying Yu a, b, Longsheng Zhao a, b,
Chunmei Wang a, b, Zongyu Feng a, b, Dali Cui a, b, Zhiqi Long a, b
a
National Engineering Research Center for Rare Earth Materials, General Research Institute for Nonferrous Metals, Beijing 100088, China
b
Grirem Advanced Materials Co. Ltd., Beijing 100088, China

a r t i c l e i n f o a b s t r a c t

Article history: Rare earth elements (REEs) play a critical role in numerous high-tech applications owing to their unique
Received 24 March 2016 magnetic, optical, and electrical properties. China is widely recognized by its abundant rare earth re-
Received in revised form sources with the annual output of 100,000e150,000 tonnes, which accounts for over 90% of the world’s
2 April 2017
total production. Bastnaesite is one of the four rare earth minerals in China. With the rapid development
Accepted 15 July 2017
of rare earth industry, resources and environmental issues have attracted more and more public
Available online 17 July 2017
attention around the world. The Chinese government, together with the Chinese researchers, have been
devoted to establish a high standard by proactively addressing resources and environmental issues. This
Keywords:
Cleaner production
review gives an overview of the recent progresses in the environmentally friendly rare earth separation
Bastnaesite and industrial application of bastnaesite in China, including oxidation roasting-acid leaching process,
Rare earths sulfuric acid bake-water leaching process, caustic soda decomposition process, chlorination process,
Separation and purification NH4Cl roasting technique, hyperlink extraction process, equilibrium acidity controlling technique, and
some other improved processes. These progresses have exerted important impacts on the wolrd’s rare
earth industry and futher pointed out the future directions for the technical development of the rare
earth industry in China. Moreover, the recent policies on the cleaner production of rare earth industry
issued by the Chinese government have been briefly discussed, which provides sufficient policy support
for the generalization and application of the advanced cleaner production technologies in the rare earth
industry.
© 2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
2. Bastnaesite processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
2.1. Oxidation roasting-acid leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
2.1.1. Oxidation roasting-hydrochloric acid leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
2.1.2. Oxidation roasting-sulfuric acid leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
2.2. Sulfuric acid bake-water leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.3. Caustic soda decomposition process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.4. Chlorination process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.5. NH4Cl roasting process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3. Separation and purification of the rare earths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
3.1. Progress of hyperlink extraction process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
3.2. Technique for controlling equilibrium acidity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238

* Corresponding author. No. 2 Xinjiekou Wai St., Beijing 100088, China.

E-mail address: wls1657@163.com (L. Wang).

http://dx.doi.org/10.1016/j.jclepro.2017.07.107
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
232 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242

4. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240

1. Introduction Gupta and Krishnamurthy, 2005; Jordens et al., 2013). Another

alternative mineral used as a source of REEs is apatite (Chen and
The term “rare earth” denotes the 17 chemically similar ele- Graedel, 2015; Wang et al., 2010; Beltrami et al., 2014). The occur-
ments, including scandium, yttrium, and the lanthanides with rence of REEs in the main rare earth deposits around the world is
atomic numbers of 57e71. Except for promethium, all the lantha- shown in Table 1.
nides occur in nature. The stunning story of rare earths (Fig. 1) Rare earth ores have been processed in South Africa, India, and
started in 1787. Yttrium was first identified and isolated at the end Brazil in the 1950s. Fig. 3 shows a graphical illustration for the
of 18th Century. A series of investigations eventually led to the history of rare earths production. After the Mountain Pass rare
identification of 15 other rare earth elements (REEs) between 1803 earth deposit was opened in 1952 by Molybdenum Corporation
(cerium) and 1907 (lutetium) along with radioactive promethium (later Molycorp), the rare earths production in the U.S. quickly
synthesized in 1947. The REEs from lanthanum to gadolinium are overtook the global production because of the rare earth metal-
often referred to cerium subgroup or light REEs, whereas those lurgy and catalyzer preparation. During the “Mountain Pass Era”,
from terbium to lutetium, together with yttrium, belong to yttrium Molycorp produced 10,000e20,000 tonnes of rare earth oxide
subgroup or heavy REEs. REEs are also divided into three sub- (REO) per annum, which was higher than the sum of other regions
groups, viz. lanthanum to neodymium are called “light rare earths”, and more than sufficient to meet the global demand. Then, in the
samarium to dysprosium are known as “middle rare earths”, and mid 1980s, China entered into the rare earths market, and rapidly
holmium to lutetium, together with yttrium, are called “heavy rare became the dominant producer around the world. The “Mountain
earths” (Xu, 1995; Gupta and Krishnamurthy, 2005). Pass Era” ended in the mid 1990s since the REO production in China
Generally, the abundance or scarcity of an element is expressed (principally Baotou in Inner Mongolia) began to outstrip that of the
by its crustal abundance, which is defined as the average content in U.S. and other regions. Since the U.S. ceased the rare earths pro-
the earth crust. In terms of inherent abundance in the earth crust, duction in the late 1990s, the trend of rare earths production
REEs are not actually rare because the crustal abundance of REEs became a prime concern in Washington and other capital cities
(220 ppm) is even higher than those of carbon (200 ppm) and many because of China’s nearly total domination of the rare earths
well-known metals, such as copper, lead and zinc (Xu, 1995; Gupta market.
and Krishnamurthy, 2005), as illustrated in Fig. 2. There are four main rare earth deposits in China (Xu, 1995;
The REEs, being chemically similar to one another, invariably Gupta and Krishnamurthy, 2005; Clark and Zheng, 1991),
occur together in many mineral deposits and behave as an entity. including Inner Mongolia deposit, Fuji, Jiangxi-Guangdong,
Typically, REEs in the hard rock and placer deposits occur as car- Guangxi- Hunan deposit, Hubei-Sichuan deposit, and Southeast
bonates, oxides, phosphates and silicates, with notably large re- China beach placer deposit. Each of these deposits has a unique
serves in China, the U.S. and Australia (Xu, 1995; Gupta and type of rare earth mineral. The Inner Mongolia deposit is the
Krishnamurthy, 2005). About 95% of the REEs occurs in only four world’s largest rare earth deposit and contains the Bayan Obo rare
minerals, including bastnaesite, monazite, ion-adsorption clays and earth-iron ore, with the reserves of over 350 million tonnes. The
xenotime, in which bastnaesite is the most common (Xu, 1995; principal minerals are bastnaesite and monazite. The Fuji, Jiangxi-
Guangdong, Guangxi-Hunan deposit occurs along the borders of
these provinces and contains the ion adsorption deposits, which
are located in the lateritic zones containing bastnaesite, synchysite,
and allanite. The Hubei-Sichuan deposit occurs along the borders of
these two provinces and consists of bastnaesite and parisite,

Fig. 2. Crustal abundance of lanthanide elements and some other elements (Xu, 1995;
Fig. 1. Illustration of the history of rare earth elements. Gupta and Krishnamurthy, 2005; Jordens et al., 2013).
 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242 233

Table 1
Occurrence and composition of the rare earth elements in the main rare earths deposits around the world (wt.%) (Xu, 1995).

Country China U.S. Russia Australia

Mineral RE component Mixed RE concentrate (Baotou) Bastnaestie (Sichuan) ion adsorption deposits Bastnaestie Loparite Monazite

A B C

La2O3 25.00 29.81 38.00 27.56 2.81 32.00 25.00 23.90

CeO2 50.07 51.11 3.50 3.23 <1.09 49.00 50.00 46.30
Pr6O11 5.10 4.26 7.41 5.62 1.08 4.40 5.00 5.05
Nd2O3 16.60 12.78 30.18 17.55 3.47 13.50 15.00 17.38
Sm2O3 1.20 1.09 5.32 4.54 2.37 0.50 0.70 2.53
Eu2O3 0.18 0.17 0.51 0.93 <0.37 0.10 0.09 0.05
Gd2O3 0.70 0.45 4.21 5.96 5.69 0.30 0.60 1.49
Tb4O7 <0.1 0.05 0.46 0.68 1.13 0.01 e 0.04
Dy2O3 <0.1 0.06 1.77 3.71 7.48 0.03 0.60 0.69
Ho2O3 <0.1 <0.05 0.27 e e e e e
Er2O3 <0.1 0.034 0.88 2.48 4.26 0.01 0.80 0.21
Tm2O3 <0.1 e 0.13 0.27 0.60 0.02 0.10 0.01
Yb2O3 <0.1 0.018 0.62 1.13 3.34 0.01 0.20 0.12
Lu2O3 <0.1 e 0.13 0.21 0.47 0.01 0.15 0.04
Y2O3 0.43 0.23 10.07 24.26 64.97 0.10 1.30 2.41

occurring in barite and calcite veins associated with alkaline and
carbonatite rocks. The southeast China beach placer deposit occurs
along the coastal areas of west Guangdong Province and Hainan
Island, and contains monazite and xenotime.
The mineral bastnaesite is a fluorocarbonate of the cerium
subgroup, with the REO mass fraction of approximately 70%. Bast-
naesite is a primary source of light rare earths found in the enor-
mous deposit of Bayan Obo in China and Mountain Pass in the U.S.
In addition, bastnaesite is also the main rare earth mineral at
Brockman in Australia, Pocos de Caldas in Brazil, Thor Lake in
Canada, and Karonge in Burundi (Gupta and Krishnamurthy, 2005).
Bastnaesite is chemically susceptible to weathering, which leads to
the dissolution of REO with subsequent combination with available
phosphates.
The REEs are becoming increasingly important in the transition
to a low-carbon, green economy, due to their primary usage in
permanent magnets, optics and lasers, catalysts, wind- and solar-
energy conversion, rechargeable batteries and other green econ-
omy applications (Huang et al., 2015; Dong et al., 2015; Binnemans
et al., 2013, 2015; Shen et al., 2009). With large demands and rapid
development of rare earths, resources and environmental issues in
the rare earth industry have recently attracted more and more
attention, and the development of green processes on the cleaner
production of rare earths will become a trend in the future rare
earth industry. This review gives an overview of the main processes
developed in the past towards greener hydrometallurgy of bast-
naesite in China. Brief descriptions for the main processes for the
treatment of bastnaesite are first presented, and the key feature of
rare earth extraction metallurgy, separation of the REEs from one
another will also be covered. All the important processes, which
have been rated as suitable for industrial operation, have been
concluded in this review.
2. Bastnaesite processing
Bastnaesite is a primary rare earth mineral in the world. Typical
bastnaesite contains 0.2e0.3 wt% thorium and 8e10 wt% fluorine in
addition to the REEs (Wang et al., 2012a, 2013a). During the past
decades, several processes for the treatment of bastnaesite were
developed, including oxidation roasting-acid leaching, sulfuric acid
bake-water leaching, caustic soda decomposition process, chlori-
nation process and NH4Cl roasting process. However, these pro-
cesses are disadvantaged by the discharge of fluorine and
radioactive thorium, which brings serious environmental degra-
dation and largely lower the economical and technical indexes.
Therefore, efficient recovery of REEs, thorium, and fluorine from
bastnaesite is a standing question in rare earth industry.
2.1. Oxidation roasting-acid leaching

2.1.1. Oxidation roasting-hydrochloric acid leaching

Exploitation of bastnaesite in China started in the early 1980s
(Huang et al., 2005). At present, industrial bastnaesite processing
Chinese Era involves oxidation roasting, hydrochloric acid (HCl) leaching, and
solvent extraction, as shown in Fig. 4. Bastnaesite concentrates are
typically roasted to decompose the fluorocarbonate and oxidize the
cerium to a tetravalent state (Eq. (1)) before being leached with HCl.
To minimize the separation costs, the cerium, which comprises
about 50% of the total REEs in the bastnaesite, is oxidized to CeO2
Mountain Pass Era during oxidation roasting so that little cerium is dissolved in HCl
since the presence of cerium dramatically reduces the solvent
extraction capacity in selective separation of individual rare earths.
Placer Era The calcined bastnaesite is then treated with HCl to dissolve the
non-cerium rare earths (Eq. (2)), yielding a marketable cerium
concentrate containing 65e70 wt% REO and 55e60 wt% CeO2. The
obtained leaching solution is further processed using solvent
extraction for the recovery of single rare earths. The cerium
concentrate, which is composed of CeO2 and mixed rare earth
Fig. 3. World’s REO production trends (Long, 2011; U.S. Geological Survey, 2014). fluorides, is then digested with caustic soda to form soluble alkali
234 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242

Bastnaesite

Oxidative
Off gas
roasting

Hydrochloric
acid leaching

Ce-Th
Filtration RECl3
concentrate

Caustic Neutralization Solid waste

conversion

wastewater with high

F-bearing Removal of F Solvent extraction
ammonium-nitrogen
wastewater by washing with P507
content or salinity
wastewater with oxalic acid,
Acid Precipitation high ammonium-nitrogen
dissolution content or salinity

Ce-rich slag Calcination

Fe-Si alloys Reductive

leaching REO
smelting

Th-bearing CeO2 product

slag (97%-98%)

Fig. 4. Bastnaesite treatment by oxidation roasting, hydrochloric acid leaching, and caustic conversion.

fluoride and rare earth hydroxides (Eq. (3)). The rare earth hy-
droxides are then leached with HCl prior to solvent extraction of
single rare earths. The traditional hydrometallurgical process for
rare earths in industrial practice also involves removal of thorium
and fluorine as impurities from the acid leaching solution through
precipitation using magnesium/calcium salts. This process suffers
from many problems, such as low REEs recovery, disposal of solid
waste and wastewater, and pollution arising from the storage of
radioactive solid waste and fluorine-containing wastewater.
[CeFx]4x and [AlFx]3x coordination reactions on the precipitation
and dissolution of rare earths fluoride were investigated inten-
sively. The leaching of non-cerium rare earths was nearly 93%, and
the mass ratio of CeO2/TREO in the leach residue almost reached
94% under optimal conditions. Additionally, citric acid, boric acid
and Al3þ were added as complexing agents during the acid leaching
using HCl or HNO3 to increase the rare earths concentration of the
leaching solution (Bian et al., 2010, 2011a; Zhang et al., 2013; Liu
et al., 2012; Li et al., 2014).

REFCO3 / REOF þ CeO2 þ CO2[
3REOF þ 6HCl / 2RECl3 þ REF3Y þ 3H2O
REF3 þ 3NaOH ¼ RE(OH)3 þ 3NaF
Another process for the preparation of cerium concentrate from
bastnaesite by two-step HCl leaching has been proposed by Dr. Chi
(Chi et al., 2006). Bastnaesite is roasted with sodium carbonate to
form rare earth oxides, in which most of the cerium exists as CeO2
and cannot be dissolved with dilute HCl, while non-cerium rare
earths existed as trivalent state can be leached out easily. The
roasted bastnaesite was first leached with dilute HCl to form a
sludge containing cerium concentrate. In concentrated HCl, Ce(IV)
is a strong oxidant, so it can be easily reduced to Ce(III) using
hydrogen peroxide (H2O2) as a reducing agent. The sludge is further
leached with concentrated HCl, adding H2O2 as a reducing agent to
form CeCl3.
The presence of fluorine has been widely considered as a
fundamental cause of environmental pollution and wastage of re-
sources during the treatment of bastnaesite, and as such, a new low
temperature roasting-coordination leaching process has been
developed to recover the fluorine from bastnaesite as CeF3 by
product and to enhance the REEs leaching, especially the non-
cerium rare earths (Wang et al., 2013b, 2012b, 2015). The effect of
(1) 2.1.2. Oxidation roasting-sulfuric acid leaching
After the oxidation roasting (Eq. (1)), most of the cerium in
(2) bastnaesite exists as CeO2, which cannot be further dissolved in
dilute HCl. In order to enhance the REEs recovery, sulfuric acid
(3) (H2SO4) was employed to treat the roasted bastnaesite (Eq. (4)), and
the effect of thiourea addition on the H2SO4 leaching of the roasted
bastnaesite was studied. Experimental data revealed that the
addition of thiourea induced the dissolution of REEs in the roasted
bastnaesite because of the reduction of Ce(IV) to Ce(III) by thiourea
(Yo€ rükog
lu et al., 2003). Virtually all the RE(III), Ce(IV), Th(IV), and
F(I) in the roasted bastnaesite could be leached out (Wang et al.,
2012a, 2013a).
2REOF þ CeO2 þ 4H2SO4 / RE2(SO4)3 þ CeF2SO4 þ 4H2O (4)
According to the Ministry of Environmental Protection of the
People’s Republic of China, rare earths plants must meet stricter
environmental emission standards (China Ministry of Environ-
mental Protection, 2011), which provides the impetus to develop
cleaner processes. Thorium is a promising element in nuclear in-
dustry (Kimura, 1995), and fluorine exhaust from bastnaesite cau-
ses environmental degradation and worses the economical indexes
of the proposed process. Hence, efficient recovery of REEs, thorium,
and fluorine from bastnaesite is of great importance in rare earths
metallurgy.
 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242
To ensure comprehensive utilization of cerium, thorium, and
fluorine from bastnaesite, Li developed a new technology for
simultaneous extraction of Ce(IV), F(I), and radioactive Th(IV) from
Panxi bastnaesite concentrate (Zhang et al., 2008, 2010; Li et al.,
2004; Lu et al., 1998). However, Cyanex 923 used in this process
is more expensive than other commercial extractants such as
D2EHPA and HEH(EHP). Fluorine was recovered as CeF3 nano-
particles using reductive stripping, and the precipitation of CeF3 in
the mixer-settler caused loss of the organic phase, which largely
increased the complexity and the total cost of the process. Thus, it is
still necessary to develop a more efficient and environmentally
friendly process.
A new process for the recovery of thorium and fluorine from
bastnaesite with less waste has been developed and put into in-
dustrial practice (Wang et al., 2012b; Wang et al., 2014a, 2015;
Zhang et al., 2012), as shown in Fig. 5. This process includes
oxidation roasting, H2SO4 leaching, and solvent extraction of REEs,
fluorine, and thorium using HEH(EHP). After oxidation, virtually all
RE(III), Ce(IV), Th(IV), and F(I) can be leached out. F(I) in the
leaching solution coordinates with Ce(IV) and Th(IV) to form
[CeFx]4x and [ThFx]4x, respectively, which can be easily extracted
by HEH(EHP) and separated from RE(III). The F(I)-loaded organic
phase was then stripped using Al3þ to produce cryolite. After
removal of F(I), Ce(IV) was reductively stripped using H2O2 and HCl
to produce CeO2 with purity of 99.95% while Th(IV) remained in the
organic phase. Finally, Th(IV) was stripped with H2SO4 to produce
ThO2 with purity of 99.5%. This process can prevent pollution
caused by dumping of thorium and fluorine as hazardous industrial
wastes.
2.2. Sulfuric acid bake-water leaching
To enhance the REEs recovery, the bastnaesite concentrates
containing a small amount of monazite are digested with concen-
trated H2SO4 at >300  C to ensure the complete decomposition of
the monazite (Huang et al., 2015). Fig. 6 shows the third generation
of sulfuric acid process for the treatment of Baotou mixed rare earth
ore. More than 90% of the Baotou mixed rare earth ore, containing
bastnaesite and monazite, is treated using the sulfuric acid process
because of its flexibility in the ore grade and low production cost.
This process has caused a boost in the rare earth industry.The flu-
orocarbonate matrix is first digested with H2SO4 to form rare earth
sulfates (RE2(SO4)3) and release hydrogen fluoride (HF) and carbon
dioxide (Eq. (5)). The baking product is then leached with water,
with subsequent impurities removal using magnesia and filtration
to form a purified leaching solution. The leaching solution is finally
subjected to solvent extraction; alternatively, the leaching solution
is treated with ammonium bicarbonate to precipitate the REEs,
which is then dissolved with HCl to produce a mixed rare earth
chloride solution. However, radioactive thorium is precipitated to
form radioactive leach residue, which cannot be economically
Leaching
H2SO4
solution
HEH(EHP)
Solvent RE(III) F(I)
extraction Scrubbing scrubbing
RE(III) Recovered as Na3AlF6
Fig. 5. Extraction and separation process of REE from bastnaesite using a leaching solution.
235
recovered, resulting in thorium loss and potential environmental
hazards. Sulfur dioxide (SO2) is also found in the volatiles during
acid bake, and large amounts of water or alkaline solutions were
necessary for the removal of SO2, resulting in discharge of acidic
wastewater. Thus, the environmental issues still remain to be
concerned.
2REFCO3 þ 3H2SO4 / RE2(SO4)3 þ 2HF[ þ 2CO2[ þ 2H2O[ (5)
An alternative route involves mixing with H2SO4, heating the
mixture at 40e180  C for 2e4 h, and acid baking of the mixture at
150e330  C (Xie et al., 2014). This method suppresses the H2SO4
digestion, resulting in a higher partial pressure of HF in the gas
phase, which can be recovered as solid ammonium fluoride (NH4F)
by reacting with (NH4)2CO3 in the off-gas pipe. Thorium can also be
recovered from the leaching solution.
2.3. Caustic soda decomposition process
Liquid alkali decomposition is an important technique for the
treatment of the bastnaesite concentrates (Xu, 1995; Gupta and
Krishnamurthy, 2005), as shown in Fig. 7. The bastnaesite concen-
trates are first digested with caustic soda (NaOH) to convert the
fluorides to hydroxides (Eq. (6)). Then, the digested product is
dissolved in HCl to produce a rare earth chloride solution, which is
further used for the recovery of individual rare earths. Despite it is
relatively cleaner compared to sulfuric acid bake process, the
caustic soda decomposition process is still disadvantaged in in-
dustrial practice by batch operation and two-step solid-liquid re-
action. More unfortunately, an additional step for calcium removal
of the feed by acid pickling is inevitable since the calcium content in
the feed should be lower than 0.2%. Higher calcium content in the
feed will worsen the caustic digestion and the following acid
leaching processes. Several other disadvantages of this process
include high alkali consumption and dispersive distribution of
radioactive thorium (Xu et al., 2012).
REFCO3 þ 3NaOH / RE(OH)3 þ NaF þ Na2CO3 (6)
Another new process is mechanochemical treatment for the
REEs recovery from bastnaesite (Zhang and Saito, 1998). The bast-
naesite is first mixed with NaOH powders, and then milled to
produce RE(OH)3 and soluble sodium salts. After removing the
sodium salts by water washing, more than 90% of the REEs in the
bastnaesite can be leached out with dilute HCl. This method has
only been studied in a laboratory scale.
2.4. Chlorination process
In the early 1960s, a direct chlorination process was developed
to produce anhydrous rare earth chlorides from bastnaesite (Gupta
H2O2+HCl
Al(III) H2SO4
Ce(IV) Th(IV)
regeneration
stripping stipping
CeO2 ThO2
236 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242

Mixed rare earths

concentrate

Sprayed Off gas containing

H2SO4 roast
wastewater F and S

Th-bearing
Neutralization
solid waste

A Rare earths B
sulfate solution
Ammonium Group separation by
Precipitation
-nitrogen wastewater P507

Filtration &
washing Rare earths sulfate
Sm-Eu-Gd solution with little Sm
concentrate
Acid dissolution
Group separation by Acidic
Wastewater with high wastewater
Group separation P204
ammonium-nitrogen
by saponified P507
content or salinity

RECl3 (La, Ce, Pr, Nd)

Wastewater with high
Solvent extraction ammonium-nitrogen
content or salinity
Wastewater with oxalic acid,
Precipitation high ammonium-nitrogen
content or salinity

Calcination

REO

Fig. 6. The sulfuric acid process.

and Krishnamurthy, 2005; Brugger and Greinacher, 1967), and a
special furnace was used for chlorination. The bastnaesite is first
mixed with amorphous carbon, and then reacted with gaseous
chlorine to form chlorides (Eqs. (7)e(9)), which were then sepa-
rated according to the differences in volatility (Brugger and
Greinacher, 1967; Zhang et al., 2004, 2007a, 2007b; Wang and
Liu, 1996; Wang et al., 2002; Zhang et al., 2002; Ozaki et al.,
1996; Murase et al., 1996). To ensure complete chlorination, the
temperature in the reaction zone of the furnace should be
1000e1200  C. The rare earth chlorides, along with alkali chlo-
rides and alkaline earth chlorides, were collected from the bottom
of the furnace periodically as a nonvolatile fluid melt, while the
other volatile chlorides were carried off by the off gases. The
collected fluid melt was then allowed to solidify to form rare
earth chlorides. This process was also found to be suitable
for the treatment of monazite and xenotime. Nevertheless,
this process is no longer in industrial use due to high fluorine
content and radioactive thorium contamination in the rare earth
chlorides products (Gupta and Krishnamurthy, 2005; Zhang et al.,
2007a).
REFCO3 / REOF þ CO2
3REOF þ 3C þ 6Cl2 / 2RECl3 þ 3CO þ REF3
REOF þ C þ 2Cl2 / RECl3 þ CO þ ClF
A stepwise carbochlorination-oxidation process was developed
for the REEs recovery from bastnaesite and mixed bastnaesite-
monazite concentrate using carbon as reductant, chlorine gas as
chlorination agent, SiCl4 gas as defluorinating agent, and O2 þ H2O
mixed gas as oxidant (Eq. (10)) (Zhang et al., 2007a). Carbo-
chlorination mechanism has also been investigated for the REEs
recovery from mixed bastnaesitemonazite concentrate using
AlCl3 as defluorinating agent (Yu et al., 2008). The relationship
between vapor pressure and temperature for different chlorides is
presented in Fig. 8.
4REOF þ 4C þ 4Cl2 þ SiCl4 / 4RECl3 þ 4CO þ SiF4 (10)
2.5. NH4Cl roasting process
Although effective for the REEs recovery, sulfuric acid bake
process is a complex process and requires highly corrosion-
resistant equipments. Futher, this process produces large
amounts of wastewater and toxic gases like HF, which are difficult
(7)
to be recovered in an economically feasible way. Therefore, some
modified processes have recently been proposed, for example by
(8)
adding Magnesium oxide (MgO) or CaO-NaCl to stabilize the fluo-
rine in the leach residue other than exhausted as waste gases
(9)
(Wang and Liu, 1996; Wu et al., 2002; Wu et al., 2006, 2007; Bian
 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242 237

Mixed
Mixed rare
rare earths
earths
concentrate
concentrate

Acidic
Acidic waste
waste calcium removal
water
water by acid pickling

Caustic soda NaOH

NaOH
decomposition

Filtration Recovery of wastewater

NaOH &Na3PO4 containing F & Th

RE(OH)
RE((OH))33

Acid ThRE-bearing
ThRE-bearingg Sulfuric acid
dissolution residue
residue roasting

RECl
RECl33

wastewater with high

Solvent extraction
ammonium-nitrogen
with P507
content or salinity
wastewater with oxalic acid,
Precipitation high ammonium-nitrogen
content or salinity

Calcination

REO

Fig. 7. The caustic soda decomposition process.

et al., 2011b). MgO was used to deactivate the fluorine in the
bastnaesite to minimize the formation of rare earth fluorides,
thereby significantly facilitating the REEs leaching.
Recently, a new process for the REEs recovery from bastnaesite
by ammonium chloride (NH4Cl) roasting has been developed (Zhu
et al., 2003; Chi et al., 2004, 2005; Zhu et al., 2000; Zhu et al., 2002).
In this process, the bastnaesite is roasted with MgO at 500e650  C
to deactivate the fluorine in the form of insoluble magnesium
fluoride (MgF2) while transforming the rare earth fluorocarbonate
to rare earth oxides (Eq. (11)). Then, the roasted bastnaesite is
mixed with NH4Cl and transformed to soluble rare earth chlorides
in the second stage roasting (Eq. (12)). Unlike the traditional pro-
cess, the new process uses ammonium salt to decompose bast-
naesite instead of acid and alkali, which largely increases the
selectivity, resulting in considerable reduction in the chemical
materials consumption. Moreover, the process is largely simplified
with the REEs recovery increased. However, the recovery of the
fluorine and thorium has not been taken into consideration in this
process yet.
2REFCO3 þ MgO / RE2O3 þ MgF2 þ 2CO2 (11)

RE2O3 þ 6NH4Cl / 2RECl3 þ 6NH3[ þ 3H2O (12)

3. Separation and purification of the rare earths

Since the chemical properties of an element mainly depend on

Fig. 8. The relationship between vapor pressure and temperature for different chlo-
rides (Zhang et al., 2007b).
the electronic arrangements in the outer shells, the outermost (5s
and 5p) electron shells of REEs are chemically identical, and as such,
the separation factors among REEs show very small differences.
Unlike most other elements, the differences of REEs occur in the
inner 4f shells rather than the outermost electron shells. The 4f
shell of lanthanum has no electron, while that of lutetium has 14
electrons. The variations in the 4f orbital of the REEs, however,
bring subtle differences in the physical properties, which makes it
difficult to separate a single rare earth element from its adjacent
neighbor. The separation of REEs might be the most difficult task in
analytical chemistry. With increasing demands for rare earths
238 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242
HEH(EHP) R1' H2O RECl3
h h h h
1 Ă 5 6 7 Ă 15
R2 R1
Flowmeter
h Gd Concentrate
Fig. 9. Equilibrium acidity-controlled extraction and separation process in a Gd-Tb-HEH(EHP)-Cl system. Note: Fractions of the raffinate (R1) are metered in stage 5 and the required
volume of diluting water was calculated according to the aqueous pH. Stage 6 is a clarification stage. The aqueous phase in stage 6 and 7 was isolated, without circulation, and the
organic phase circulated from stage 6 to stage 7.
compounds, the separation and purification of REEs has gained
considerable attraction in recent years, and many processes, for
example electrolytic reduction, ion exchange, extraction chroma-
tography and solvent extraction, have been successfully developed
(Xu, 1995; Gupta and Krishnamurthy, 2005). Solvent extraction has
been well established and widely used in rare earth industry.
Organophosphorus acids are commonly used extractants (Xu, 1995;
Gupta and Krishnamurthy, 2005; Richelton and Boyle, 1988; Behera
et al., 1994; Sato, 1989; Abbott et al., 2011; Reddy et al., 2004, 2006;
Radhika et al., 2010; Cheng, 2000; Zhu et al., 2011), and various
commercial rare earth compounds with purity of 99%e99.999% are
produced through more than 1000 stages continuous extraction
because of the very small separation factors between the adjacent
REEs.
The solvent extraction of REEs using organophosphorus acids
can be interpreted by ions exchange with hydrogen ion (Hþ). To
facilitate the cation exchange of rare earths, conventional acidic
extractants such as HEH(EHP) need to be saponified by NH3$H2O,
NaOH, or Ca(OH)2. Generally, more than 10 tonnes of acid and base
are consumed to separate per tonne of REO, and as such, large
volume of wastewater containing NHþ þ
4 , Na , or Ca
2þ
was generated,
causing discharge of ammonium nitrogen wastewater or high
salinity wastewater. Generally, evaporative crystallization and va-
por extraction have been used to recover the ammonium nitrogen
from the wastewater. However, these technologies are disadvan-
taged by high energy consumption and cost.
In order to solve the problems of high chemical consumption,
low recovery of REEs and serious pollution arised from “the three
wastes” (gaseous, liquid and solid wastes) in the rare earth industry,
Chinese chemists have recently devoted to developing advanced
separation and purification processes for rare earths, and some
cleaner technologies like hyperlink extraction (Deng and Xu, 2012;
Yan et al., 1997, 2008; Wu et al., 2012; Wu et al., 2004; Jia et al.,
1999a, b, c, 2001; Yan et al., 2006; Yan et al., 1999), calcium
saponification extraction (Yang et al., 2010) and non-saponification
extraction (Huang et al., 2007; Wang et al., 2013c, 2014b; Xiao et al.,
2013; Huang et al., 2008; Zhang et al., 2014) have been developed
and widely used in industrial practice. These new technologies
have significantly reduced the chemical consumption and waste
discharge, bringing out remarkable economic and social benefits.
3.1. Progress of hyperlink extraction process
In 1970s, Xu established a theory of countercurrent extraction
for rare earth separation. This theory, together with its industrial
applications, in complicated system was later further developed by
Yan et al (Liao et al., 2013). In order to reduce the chemical con-
sumption and the discharge of wastewater, a “hyperlink process”
HCl H2O'
h hhh
Ă Ă 29 Ă 38 39 40
99.95% TbCl3
using rare earth loaded organic phase as extractant and aqueous
phase containing rare earth as scrubbing or stripping solution was
developed, and minimum extraction quantity in each segment was
employed to determine the chemical consumption. Experimental
data indicated that the separation of Pr/Nd, Ho/Y and Y/Er were
found to be the key factor to determine the chemical consumption
for the solvent extraction of REEs from the leaching solution of ion
adsorption rare earth ore. To separate each individual lanthanide
using HEH(EHP), the extraction capacity and theoretical minimum
extraction capacity under optimal conditions were 1.38 and 1.2,
respectively. The chemical consumption can be reduced by nearly
30%. Especially, the acid consumption can be reduced by more than
50%.
The non-saponification extraction process and the hyperlink
process have been integrated and then applied in the REEs sepa-
ration using HEH(EHP) and HDEHP in H2SO4 or HCl medium, and a
demonstate line producing 4000 tonnes REO per annum has been
constructed in 2010 (Gansu Rare Earth New Material Limited-
Liability Company, 2012). By using this technique, ammonium ni-
trogen wastewater can be completely eliminated, and the chemical
consumption and the discharge of wastes can also be reduced
significantly.
3.2. Technique for controlling equilibrium acidity
To improve the extraction efficiency and eliminate the discharge
of wastewater, some new extraction systems including non-
saponification extraction, synergistic extraction (Mathur, 1983;
Nayak et al., 2009; Song et al., 2009; Sun et al., 2005, 2006; Wang
et al., 2012c; Xiong et al., 2005), and ionic liquid extraction (Sun
et al., 2011, 2012; Hoogerstraete et al., 2013; Chen et al., 2005; Liu
et al., 2010; Zhang et al., 2015) have been developed recently.
Another new environmentally friendly process for rare earths
separation has also been developed, and pilot experiments for the
separation of Gd from Tb in a HEH(EHP)-HCl system have been
conducted using the equilibrium acidity control technology
without saponification. Experimental data showed that ammonia-
free emissions could be achieved by controlling equilibrium acid-
ity (Fig. 9). The rare earths concentration in the raffinate was lower
than 0.1 g/L, while the rare earths concentration loaded in the
organic phase was approximately 0.16 mol/L, which was almost
equal to the ideal load of continual process (0.17e0.18 mol/L)
(Fig. 10).
Alternatively, a new and clean process for REEs separation by
HEH(EHP) in chloride system was developed which avoided the
generation of wastewater containing NHþ þ 2þ
4 , Na or Ca . To achieve
high rare earths load in the organic phase and eliminate the
saponification of the organic phase, an equilibrium acidity control
 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242
Fig. 10. Equilibrium distribution of the elements in the pilot aqueous and organic
solutions.
method was developed using light rare earth carbonates with a low
purity as the primary product. A rare earths load of 0.17 mol/L and
fast kinetics with about 5 min for equilibrium can be achieved, and
the purity of the light rare earth carbonates can be improved during
the pre-load of the organic phase and countercurrent extraction.
This new process for rare earths separation is pollution-free, which
are suitable for the application in conventional rare earth
separation.
Magnesia powder was also used to neutralize Hþ arised from
ion exchange reaction during solvent extraction, so as to facilitate
the rare earths extraction. However, magnesia powder can lower
the purity of rare earths products and increase the operating cost
because of the impurities of Fe2O3, Al2O3, and SiO2. Thus, a new
low-carbon, low-salt and ammonia-free technology for the rare
earths separation has been proposed by Huang et al (Huang et al.,
2010; Huang et al., 1314; Feng et al., 2012)., as shown in Fig. 11.
Mg(HCO3)2 solution with high purity was first prepared by
carbonization of magnesite or dolomite using CO2, which was
produced during the organic phase saponification and the calci-
nation of rare earths carbonates. The Mg(HCO3)2 solution was then
used for the leaching of the roasted mixed rare earth ore, the
saponification of the organic phase, and the precipitation of rare
earths carbonates, forming wastewater containing MgCl2, which
could eliminate the ammonium nitrogen pollution. The wastewater
Dolomite/
Limestone
Caustic
conversion
Carbonization
Mg(OH)2
& Purification
CO2
Recovery
&
Recycle
Fig. 11. A new rare earths separation and purification process with low-carbon, low-salt and free of ammonia nitrogen wastewater.
239
was finally recycled and reacted with Ca(OH)2, with subsequent
carbonization to produce Mg(HCO3)2 solution. In this process,
magnesium can be effectively recycled, and the discharge of
wastewater with high salinity can be avoided. The process is
currently conducted to produce 2000 tonnes REO per annum.
Above 90% of the magnesium and CO2 was recycled, with the REEs
recovery up to 99.5%. The rare earths concentration loaded in the
organic phase was higher than 0.17 mol/L. More importantly, the
chemical consumption can be reduced by 35%e50% in comparison
with the traditional saponification process.
4. Conclusions and outlook
While bringing benefits to mankind, the exploitation of rare
earths has also brought serious resources and environmental
problems. The rational utilization of the rare earths resources and
the effective protection of the environment pose great challenges
for the rare earth industry around the world. China is relatively
abundant in rare earth resources, in which the rare earths reserves
account for approximately 23% of the world’s total reserves. In 2011,
China produced 96,900 tonnes of rare earths products, accounting
for more than 90% of the world’s total output.
Recent progresses in the extraction and separation of rare earths
from bastnaesite in China, including oxidation roasting-acid
leaching process, sulfuric acid bake-water leaching process,
caustic soda decomposition process, chlorination process, NH4Cl
roasting process, hyperlink extraction process and equilibrium
acidity controlling technique, have been introduced in detail. These
progresses have exerted important impacts on the wolrd’s rare
earth industry. In order to significantly reduce the consumption of
chemical materials and energy, eliminate the discharge of “the
three wastes”, especially the thorium-bearing radioactive solid
waste, fluorine-bearing wastewater and ammonium nitrogen/high
salinity wastewater, efficient recovery of REEs, thorium, and fluo-
rine from bastnaesite by cleaner technologies with high REEs re-
covery and low cost is of great importance to meet stricter
environmental emission standards in rare earth industry, and
futher point out the future directions for the technical development
of the rare earth industry in China.
Currently, the development of cleaner production processes is of
great importance for the sustainable development of rare earth
industry, and some laws and regulations about the rare earths trade
have been put into effect by the Chinese government for better
coordination between rare earth utilization and environmental
protection. In 2006, the State Council of the People’s Republic of
RECl3
Mg
CO2 Saponification Recovery
process MgCl2
&
Recycle
RE separation
Mg(HCO3)2
& Purification
Precipitation MgCl2
CO2
RE2(CO3)3
CO2 Calcination
REO
240 L. Wang et al. / Journal of Cleaner Production 165 (2017) 231e242
China published ‘Outline of national plan on mid-long term sci-
entific and technological development (2006e2020)’, and the in-
tegrated cleaner production technologies in the heavy pollution
industry are vigorously encouraged to reduce the waste discharge
and improve the recycling of raw materials. In the year of 2011, the
Ministry of Environmental Protection of the People’s Republic of
China published the ‘Emission standard of pollutants for rare earths
industry’ as a norm. Meanwhile, in order to achieve comprehensive
utilization of rare earth resources, reduce the consumption of en-
ergies and chemical materials, and eliminate environmental
pollution, the State Council of the People’s Republic of China pro-
posed ‘several advises on promoting the sustainable and healthy
development of rare earth industry’, in which the recovery of rare
earths from rare earth tailings and rare earth products is encour-
aged. In the year of 2015, the State Council of the People’s Republic
of China issued a notice for the ‘Made in China 2025’ plan.
According to the innovation driven and green development pol-
icies, the generalization and application of energy-saving and
environment-friendly technologies is encouraged to realize cleaner
production, and the circular economy is further developed to
improve the resources recoveries. The Ministry of Industry and
Information Technology of the People’s Republic of China issued the
‘Implementation proposal of cleaner production technologies in
rare earth industry’ in 2014, and published the ‘Plan for the
development of the rare earth industry (2016e2020)’ two years
later, in which rare earth engineering for green upgrading and re-
form has been put forward to speed up the generalization of cleaner
production processes during the exploitation, extraction and sep-
aration of rare earth resources.
At present, the Chinese government has been making efforts to
establish an environmental risk assessment system for the rare
earth industry. The government strives to create a favorable envi-
ronment policy for expediting the cleaner production technological
upgrading, breaking through the resources and environmental
bottlenecks, and providing technological support for sustainable
development of rare earth industry. At the same time, the Chinese
researchers have been devoted to developing cleaner production
technologies for low-carbon and low-salt discharge, synergistic
recovery of associated thorium, comprehensive utilization of fluo-
rine and sulfur in the tail gas, recycling of chemical materials, and
automatic production control, to realize efficient and eco-friendly
extraction and separation of REEs.
Acknowledgements
The authors gratefully acknowledge the financial support from
the following projects: the program of the National Natural Science
Foundation of China (NSFC: 51404035), the National Science and
Technology Support Program of China (2015BAB16B03), and Beijing
Nova Program (Z161100004916108).
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