JOURNAL OF RARE EARTHS, Vol. 35, No. 8, Aug. 2017, P.

739

A review on the cracking, baking and leaching processes of

rare earth element concentrates
Farzaneh Sadri, Amir Mohammad Nazari, Ahmad Ghahreman*
(Department of Mining Engineering, Queen’s University, 25 Union Street, Kingston, Ontario, K7L 3N6, Canada)

Received 3 October 2016; revised 23 January 2017

Abstract: Rare earth elements (REE) are a set of seventeen chemical elements in the periodic table, which have been found in a vari-
ety classes of minerals in the world. The global demand for REE and their compounds has increased in high-tech applications over the
past decades due to their chemical, catalytic, electrical, magnetic, and optical properties. After mining, comminution and ore benefici-
ation, hydrometallurgical and pyrometallurgical processes are carried out to recover REE compounds. The concentrate cracking is a
process wherein the structure of a REE mineral is modified in order to dissolve REE in a weak acid solution. This would be accom-
plished through various techniques such as alkaline cracking and acid baking. The cracked concentrate is then leached to dissolve
REE in a solution and subsequently recover those via neutralization, precipitation or solvent extraction methods. This paper reviewed
the cracking and leaching methods applied to REE concentrates to produce an intermediate product for further REE separation.
Keywords: rare earth elements; alkaline cracking; acid baking; leaching; separation

Rare earth elements (REE) are a group of 17 elements,
including scandium (Sc), yttrium (Y) and 15 lanthanides
from lanthanum (La, 57) to lutetium (Lu, 71). They show
the similar chemical properties, and tend to occur in the
same mineral deposits[1]. This leads to a major difficulty
in REE separation from an aqueous solution.
Despite the term “rare earth”, REE are relatively plen-
tiful in the earth crust. However, REE scarcely occur in
the concentrated and economically exploitable mineral
deposits. Their abundance in the earth crust is even
higher than that of other commonly used elements such
as platinum group elements. REE often fall into two
categories[2–4]: (i) Cerium (Ce) group including light REE
(LREE) from La to gadolinium (Gd); (ii) Yttrium group
which consists of heavy REE (HREE) from terbium (Tb)
to Lu as well as Y. However, Sc is not included in either
LREE or HREE classification. Sometimes, the rare
earths are divided into three subgroups. In this classifica-
tion, samarium (Sm) to dysprosium (Dy) are referred to
as the middle REE (MREE)[2].
Although few REE-containing minerals could be eco-
nomically mined and processed[5], REE have been identi-
fied in over 250 mineral classes, such as halides, carbon-
ates, oxides, phosphates, silicates. Bastnasite, monazite
and xenotime are the main REE-bearing hard rock min-
erals which have been successfully used as the commer-
cial minerals for REE extraction. Bastnasite
((Ce,La)(CO3)F) is a fluorocarbonate mineral, consists of
Ce, La, praseodymium (Pr) and neodymium (Nd) (ap-
proximately 97.95 wt.% of total rare earth oxide
(REO))[2,3,6]. Monazite, (Ce,La,Nd,Th)PO4, is a phos-
phate mineral which, similarly to bastnasite, possesses
Ce, La, Pr and Nd[7–9]. The REE concentration in the
monazite varies with deposit location, and the total REO
is often between 83 wt.% and 95 wt.%. Monazite mostly
contains 4 wt.%–12 wt.% thorium (Th) and a variable
amount of uranium (U), up to 14 wt.%. Xenotime, YPO4,
is an yttrium phosphate mineral and frequently its Ce, La,
Pr and Nd content is much less than monazite and bast-
nasite. Weathering crust rare earth minerals known as
ion-adsorbed clays are considered as an important source
of HREE (60 wt.% of total REO)[10,11]. They are mainly
in the form of physisorbed ions which have been ad-
sorbed onto the surfaces of the alumina silicate minerals
such as kaolin, feldspar and mica and could be easily re-
covered directly by a hydrometallurgical method such as
ion-exchange (IX) process[12].
The global demand for REE and their compounds has
noticeably increased in many high-tech applications ow-
ing to their chemical, catalytic, electrical, magnetic, and
optical properties. For examples, REE are used in hybrid
cars, wind turbines, compact fluorescent lights, re-
chargeable batteries, catalytic convertors, flat screen
televisions, mobile phones, and disc driver[13–17]. Due to
the global sourcing challenges and volatile price of REE,
some researchers are interested in substitution of REE

Foundation item: Project supported by the Research Initiation Grant of Queen’s University, Canada (#378140) and Ontario Centers of Excellence VIP
fund (#25394)
* Corresponding author: Ahmad Ghahreman (E-mail: ahmad.g@queensu.ca; Tel.: +1-613-533-3294)
DOI: 10.1016/S1002-0721(17)60971-2
740 JOURNAL OF RARE EARTHS, Vol. 35, No. 8, Aug. 2017

with other more available and cheaper elements. The sulfidizing atmosphere with calcium chloride and cal-
REE price forecast by Alkane for 2020 is shown in Table cium carbonate[24–28]. Table 2 summarizes some of these
1. methods which would be discussed hereunder.
REE are found in 34 countries in 5 continents. Brazil Among the above-mentioned methods, both acid bak-
is one of the countries with a history of REE production ing and alkaline cracking are the most common proc-
since 1884. The most interesting deposit of REE associ- esses, but the alkaline cracking has been used more often
ated with diamond and gold mine is located in Sierra than the acid baking. The preference of the alkaline
Leone[19]. Baotou rare earth deposit in China is the larg- cracking process in industry mostly originates from the
est deposit in the world containing bastnasite and mona- fact that the process removes sulfates and phosphates and
zite with the weight ratio of 7:3, respectively[20]. also simplifies the thorium concentrate purification step.
Generally the extraction process of REE is divided In addition, it is possible to regenerate alkali after the
into three steps: (i) Mining and comminution; (ii) Ore cracking process. Another positive side of the alkaline
beneficiation processes consisting of flotation, gravity cracking is the formation of trisodium phosphate
and magnetic techniques in order to generate REE con- (Na3PO4) as a by-product which is used as a fertil-
centrate; (iii) Hydrometallurgical methods to extract REE izer[7,21,24]. Although acid baking is considered as a ma-
compounds. The latter also falls into three stages: (i) ture technology in China, it is not as common as alkaline
Cracking the REE concentrate; (ii) Leaching, neutraliza- cracking in the western world, particularly due to the
tion and precipitation processes; (iii) Separation and pu- fact that the acid baking process product is a high
rification techniques including solvent extraction (SX) strength pasty mass which dries out inside the rotary kiln,
and IX. or any other baking equipment, and mass transfer inside
This paper reviewed the different techniques of crack- the kiln becomes a technical issue. Among other chal-
ing the REE concentrates, with a focus on two major lenges of acid baking are the evaporation of sulfuric acid
methods, alkaline cracking and acid baking. as well as the selection of proper construction materials
for the kilns, considering the severe corrosive conditions
inside the acid baking kilns. The latter two challenges
1 Cracking the REE concentrate
have been experienced in many pilot plant runs as
There are different methods for processing of mona- well[29].
zite and xenotime including sulfuric acid digestion at
155– 230 ºC[21–23], alkaline cracking with sodium hy- 1.1 Alkaline cracking process
droxide solutions at 140 ºC[24], roasting with sodium 1.1.1 Bastnasite, monazite and xenotime
carbonate at 900 ºC and with sodium carbonate and flux The alkaline cracking process could be carried out in
(sodium fluoride) at 800–825 ºC, roasting with sodium hy- an autoclave containing finely ground monazite or xeno-
droxide at 400–500 ºC, heating under reducing and time and 50 wt.% sodium hydroxide (NaOH) at 150 ºC
where the weight ratio of the solid to liquid (S:L) is ap-
Table 1 Current price range and anticipated 2020 price of
proximately 1:1. The reaction for alkaline cracking is as
REE products by Alkane[18] (reproduced with per-
follows[21]:
mission)
Current price range/ Anticipated
Chemical (1)
Product (US$/kg) 2020 price/
name The process could also be carried out using a more
From To (US$/kg)
Lanthanum oxide La2O3 2 2.5 2
concentrated alkali (~70 wt.% NaOH) in a cast-iron/
Cerium oxide CeO2 2 2.5 2
stainless steel vessel, which is equipped with an agitator
Praseodymium oxide Pr6O11 62 75 80
at a lower temperature (~120 ºC) and ambient pressure[30].
Neodymium oxide Nd2O3 45 50 60
The solution, which contains Na3PO4 and NaOH, is fil-
Samarium oxide Sm2O3 2.5 3.5 3
tered in order to obtain insoluble REE and thorium hy-
Europium oxide Eu2O3 235 325 300
droxide precipitates. The REE hydroxide precipitates are
Gadolinium oxide Gd2O3 15 20 20
subsequently dissolved in a weak acid solution at pH 3.5.
Terbium oxide Tb4O7 550 650 650 Hydrochloric acid (HCl), sulfuric acid (H2SO4) or nitric
Dysprosium oxide Dy2O3 260 310 350 acid (HNO3) could be used to prepare the acidic solution
Holmium oxide Ho2O3 39 40 40 depending on the REE separation process. REE com-
Erbium oxide Er2O3 39 42 40 pounds in the form of REE double sulfate salt or REE
Thulium oxide Tm2O3 NA NA – oxalate are thereafter removed from the solution using
Ytterbium oxide Yb2O3 29 31 30 precipitation method. The final mixed rare earth product
Lutetium oxide Lu2O3 980 990 990 is then further refined using solvent extraction for REE
Yttrium oxide Y2O3 6 8 15 separation[31,32].
Farzaneh Sadri et al., A review on the cracking, baking and leaching processes of rare earth element concentrates 741

Table 2 REE concentrate cracking methods

Process Temperature and resi- Status Remarks Operating plants or Ref.
dence time concentrate origin
Alkaline cracking with 4 h at 150 and 120 ºC Industrial scale - The process could be -Baotou in China [21,22,30–34]
sodium hydroxide where the dosage of carried out in an auto- -Egyptian Rosetta
sodium hydroxide is 50 clave monazite
wt.% and 70 wt.%, re- - REE hydroxides could
spectively be dissolved in either an
acidic solution at pH 3.5
or a carbonate solution
Alkaline cracking with 2.5 h at 150 ºC Laboratory scale -Using ammonium car- -Egyptian mona- [24,35]
sodium hydroxide in a 1 h at 175 ºC bonate-bicarbonate solu- zite
ball mill autoclave tion to selectively sepa-
rate U and Th from hy-
drous oxide cake
Roasting with calcium 977–1187 ºC Laboratory scale -Reducing and sulfidizing -Western Austra- [25]
chloride and calcium car- 0.75–3 h environment lian monazite
bonate -Leaching with 3 wt.% -Chuktukon in
HCl Russia
Mechanical ball milling 12 h Laboratory scale -Under argon atmosphere -Western Austra- [36]
with calcium oxide and 400 ºC lian beach sand
calcium chloride monazite
Acid baking with sulfuric Monazite: 200–250 ºC Industrial scale -93 wt.%–98 wt.% H2SO4 -Bastnasite from [7,21,37]
acid Bastnasite: 400–560 ºC -water leaching Baotou in China
3–4 h -This process yields no
pure product
Roasting in an oxidizing Roasting at 620 ºC -Outdated -calcination in a -Mountain Pass, [38]
atmosphere within 3 h -Laboratory scale multi-layer furnace using California
low-sulfur fuel -Turkish bastna-
-leaching in 30 wt.% HCl site-containing
solution pre-concentrate
Sodium carbonate 80 min -Laboratory scale -Fluorine is washed away – [20,39]
(Na2CO3) roasting and 400–500 ºC with hot water
chlorinating with NH4Cl -MgO treatment prior to
chlorination process to fix
the fluorine in the calcine
Roasting with ammonium – -Laboratory scale -REE chlorides easily – [12]
chloride dissolve in hot water

For bastnasite, alkaline treatment is accomplished
through a three step process; However, the first step could
be eliminated: (i) Formation of the REE fluoride and chlo-
ride solution by using a mild HCl solution (Eq. (2)); (ii)
Conversion of the REE fluorides to REE hydroxides
through NaOH digestion at 96 ºC (Eq. (3)), and (iii)
Leaching REE hydroxides in the HCl solution (Eq. (4))[37].
REEF3-REE2(CO3)3(s)+9HCl(aq)→REEF3(s)+
2REECl3(aq)+3HCl(aq)+3H2O(l)+3CO2(g) (2)
(3)
(4)
[33]
Mahmoud investigated the treatment of the Egypt
Rosetta monazite concentrate for REE recovery. The
Egypt Rosetta monazite concentrate was initially disin-
tegrated in a 40 wt.% NaOH solution with an S:L ratio of
1:1.5 at 140 ºC for 4 h[33]. In order to recover virtually all
REE from the Th hydroxide precipitate, one way is to
leach the hydroxide cake in a mineral acid such as HCl
or HNO3 and then use sodium carbonate (Na2CO3) solu-
tion to solubilize Th and U as carbonates species, while
REE carbonates are insoluble precipitates (Eqs. (5), (6)
and (7))[22]. The separation process can be practiced via
one of the following two methods: (i) Leaching the hy-
drous oxide cake with a carbonate solution; (ii) Adding
an excess of carbonate salt to the mineral acid solution of
the metal oxide cake. The first method is used to selec-
tively dissolve thorium and uranium in a carbonate solu-
tion as Eqs. (5) and (6). The reactions are reversible and
even the addition of carbon dioxide to the solution does
not improve the recovery of thorium and uranium. The
second method is carried out where the bulk of REE pre-
cipitated out of the solution via Eq. (7) and thorium and
uranium formed soluble complexes, as illustrated in Eqs.
(5) and (6). However, it was shown that the addition of
five-fold excess Na2CO3 led to the precipitation of ap-
proximately all Th and REE out of the solution. Another
technique to separate REE from Th and U is through
co-precipitation of Th and U using hydrogen peroxide
(H2O2) at pH 2, while REE remained soluble in the solu-
tion[22,31]. Nonetheless, the cost of H2O2 is high and con-
sequently makes this process uneconomic.
(5)
742
(6)
(7)
Th and U could selectively be precipitated at pH 5.8
from the hydrous oxide cake solution in HCl and then
leached with an alkali solution of equal concentration of
Na2CO3/NaHCO3. Further separation of U and Th from
the obtained solution would be applied by an ion ex-
change resin[22,31,35].
The REE, Th and U from the hydrous oxide cakes of
the alkaline cracking processes could be leached in a
H2SO4 solution to obtain a sulfate liquor of REE (Eq. (8)).
The Na3PO4 by-product is crystallized via the digestion
of filtrate at 60 ºC. Amer et al. reported that the dissolu-
tion efficiencies of U, Th and REE were 99%, 96.1% and
97.2%, respectively[31].
2RE(OH)3(s)+UO2(OH)2(s)+Th(OH)4(s)+6H2SO4(aq)→
RE2(SO4)3(aq)+UO2(SO4)(aq)+Th(SO4)2(aq)+12H2O(l) (8)
Mixed REE and Th are then precipitated as oxalates
by addition of 30 wt.% oxalic acid (H2C2O4) solution at
60 ºC. The oxalic precipitation process could precipitate
99% of the REE and 98% of the Th via the following re-
actions[31]:
(9)
(10)
Unlike REE and Th, U in the solution reacts with ox-
alic acid and forms a soluble oxalic species. The reaction
between U and oxalic acid is as follows:
(11)
At 60 ºC and pH 0.7, uranium oxalate re-oxidizes to its
hexavalent state and forms sulfate which could be pre-
cipitated at pH 7 by ammonia (NH4OH) addition[31]:
(12)
The concentration of U in the sulfate liquor is in-
creased by evaporation of the filtrate (sulfate liquor) and
reduction of its volume after REE oxalate precipitation
step. Then, U is precipitated out of the solution as am-
monium diuranate (NH4)2U2O7 by the addition of
NH4OH. The U precipitation reaction is as follows[31]:
(13)
Afterwards, the U precipitate is calcined at 850 ºC for
1 h to produce a high purity of UO3. Next step for the
formation of highly pure mixed REE is to separate Th
from the Th-REE oxalate precipitate. Th could be selec-
tively separated from the oxalate precipitate using a
mixed solution of sodium carbonate and bicarbonate[35].
Amer et al.[31] reported that 99.5% of Th was effectively
dissolved in a carbonate/bicarbonate solution
(Na2CO3:NaHCO3 weight ratio of 3:1 and total Na2CO3
and NaHCO3 concentration of 150 g/L) with an S:L ratio
of 1:6 at 75 ºC for 2 h (Eq. (14))[31].
Th(C2O4)2(s)+4Na2CO3(aq)+2NaHCO3(aq)→
JOURNAL OF RARE EARTHS, Vol. 35, No. 8, Aug. 2017
Na6Th(CO3)5(aq)+2Na2C2O4(aq)+H2O(l)+CO2(g) (14)
The REE oxalate cake from this process is then cal-
cined to produce 97 wt.% REO, 2.17 wt.% Th and 0.83
wt.% U. Fig. 1 shows the working flowsheet for this
process[31]. The filtrate of the process, i.e. Th-containing
carbonate-oxalate solution, is subsequently acidified by
HCl addition to pH 2.3, to precipitate Th as Th hydroxide.
The Th hydroxide precipitate is frequently calcined to
produce a Th product with a purity above 97%.
The other method proposed for monazite leaching,
which is applied on digestion process to enhance its effi-
ciency, is to use a ball milling autoclave to grind and leach
the monazite concentrate simultaneously[35]. This process
was applied on Egyptian monazite by Abdel-Rehim[24]. In
this study the alkaline digestion of monazite was tested in
a ball milling autoclave followed by a selective separation
of U and Th from the hydrous cake of lanthanides using
ammonium carbonate-bicarbonate ((NH4)2CO3/NH4HCO3)
solution. The U and Th separation process was also con-
ducted in an autoclave. The favorable digestion conditions
to leach 99.8% monazite are: 150 to 175 ºC within 2.5 h
(for lower temperatures) and 1 h (for higher temperatures),
using 150% stoichiometric requirement of NaOH at the
concentration of 500 g/L. The application of steel balls
re-generates the fresh monazite surfaces by removing the
hydroxide layer which forms on the partially reacted
monazite particles surfaces, thus accelerates monazite
digestion. The obtained hydrous cake from the autoclave
process is then treated with (NH4)2CO3/NH4HCO3 solu-
tion (Eqs. (12) to (14)) to form insoluble ammo-
nium-thorium and uranyl carbonate complexes (Eqs. (15)
and (16)), and soluble ammonium-REE double carbon-
ates (Eq. (17))[24]:
(15)
(16)
(17)
The (NH4)2CO3 reactant in Eqs. (15) to (17) is gener-
ated via contacting NH4HCO3 with ammonium hydrox-
ide (NH4OH) solutions (Eq. (18))[24]:
(18)
The leaching solution is then diluted with 3 wt.%
(NH4)2CO3 solution to hinder the hydrolysis of Th and U
complexes[24].
Merrit[25] used calcium chloride (CaCl2) and calcium
carbonate (CaCO3) in order to treat western Australian
monazite concentrate under reducing and sulfidizing en-
vironment at 977–1187 ºC. As presented in Fig. 2, the
reaction products were REE oxy-sulfides and oxychlo-
rides, thorium-rich oxide solid solution and calcium
chlorophosphate (chlorapatite). The products were then
leached using 3 wt.% HCl and the insoluble parti-
Farzaneh Sadri et al., A review on the cracking, baking and leaching processes of rare earth element concentrates
Fig. 1 Working flowsheet for processing of Rosetta monazite concentrate (reproduced with permission)
Fig. 2 Working flowsheet for alkaline cracking of REE concen-
trate with CaCl2 and CaCO3
cles containing gangue minerals and thorium-rich oxide
were separated from REE-bearing solution. It is worth
mentioning that the use of 3 wt.% HCl was reported as
an optimum concentration to establish a balance between
stabilizing REE in the solution and preventing thorium
oxide from solubilisation into the REE solution. Merrit[25]
743
claimed that this monazite treatment method has three
advantages over other caustic digestion techniques: (i)
The monazite is decomposed in a shorter time than caus-
tic digestion; (ii) No fine grinding is required – in other
techniques, the preferred grind size is <50 µm; (iii) The
leach residue is more stable against acid attack than that
of the caustic digestion process, which results in an im-
proved filterability of the insoluble particles.
Zhang and Lincoln[36] conducted mechanical ball
milling process in the presence of calcium oxide (CaO)
and CaCl2 to decompose monazite under argon (Ar) at-
mosphere and produce chlorine oxygen compound, tho-
rium oxide (ThO2) and fluorapatite (Ca5F(PO4)3)[34]. The
ratio of monazite:CaO:CaCl2 was set at 3:3:2 and 10%
stoichiometric reagents CaO and CaCl2 were used. In this
study, the milling of the Western Australian beach sand
monazite with/without CaO and CaCl2 addition was
tested under both air and Ar atmosphere. It was con-
cluded that the monazite milling without additives would
not make any chemical or structural change in the mona-
zite lattice. Inversely, monazite gradually reacts to form
744
new REE oxychloride and calcium chlorapatite through
milling with CaO and CaCl2 addition for 12 h under Ar
atmosphere. The same experiments were conducted un-
der air atmosphere to study the effect of oxygen on the
process. It was observed that the oxygen presence af-
fected the reaction rate, where a longer time of 24 h or
more was required for complete monazite decomposition
and more REE converted to oxides. An interesting ob-
servation of the study was that opening the vial during
the milling process under air changed the products par-
ticularly, because more oxygen entered the vial and con-
sequently more REE converted to REO[36].
1.1.2 Mixed bastnasite and monazite
Mixed bastnasite and monazite minerals are the im-
portant rare earth resources, accounting for 40% of the
world’s REE ores. An example of such ore source is the
Baotou mine in China[20,34]. The mixed bastnasite and
monazite minerals are among the difficult-to-treat ores,
due to the presence of monazite. Both H2SO4 cracking
and alkali decomposition methods could be used to de-
compose these mixed ores. In the H2SO4 baking process,
the sulfur dioxide (SO2) and hydrogen fluoride (HF)
off-gasses are produced which are difficult to recycle and
serious actions should be taken to strip those gasses in
order to prevent environmental pollutions. The liquid al-
kali decomposition process, by the application of alkali
metal compounds such as NaOH, magnesium oxide
(MgO) and CaO, is often applied to decompose the
mixed REE concentrates[25]. This process is relatively
cleaner than H2SO4 baking method. As this process in-
volves solid-liquid contact, the fluorine element dissolves
into the washing fluid as sodium fluoride (NaF) and it
does not produce fluorine waste gas[34]. Therefore, fluo-
rine could be recovered in this process. On the negative
side, this process involves two steps of solid-liquid reac-
tions, which both are followed by water wash processes.
In addition, an extra calcium (Ca) removal step by acid
pickling is needed in this process, to reduce the amount
of Ca to about 0.2% (a high Ca fraction would negatively
affect the decomposition and leaching of REE). Thus,
this process is not the most favorable process for
large-scale REE concentrate processing. The direct de-
composition of the mixed bastnasite and monazite con-
centrates by alkali liquid has also been investigated. Xu
et al.[42] carried out a series of alkaline cracking experi-
ments using a NaOH solution at a pH range between 8–9.
REE hydroxide precipitates were washed with water and
then leached in a HCl solution. It was demonstrated that
in the presence of alkali, the decomposing rate was high
at 200 ºC because of the slow evaporation of water which
led to a long solid-liquid reaction; however, increasing
the temperature to 250 ºC decreased the decomposition
rate of the bastnasite and monazite due to the rapid
evaporation of water and shorter time of solid-liquid re-
action[42]. Increasing the temperature to 300 ºC and above
JOURNAL OF RARE EARTHS, Vol. 35, No. 8, Aug. 2017
increased the decomposition rate once again, which
made the reaction between solid NaOH and mixed
monazite and bastnasite possible and produced
acid-soluble products[42]. It was reported that most of the
fluorine (F) ions were present in the wash water and a
trace of F remained in the alkali cake. No F was detected
in the exhaust gas. It was also shown that the oxidation
rate of Ce increased with the elevation of the temperature
and reached 91.75% at 300 ºC and 96.40% at 400 ºC;
then, mixed REE chloride with low Ce content was ob-
tained after acid leaching which facilitated the subse-
quent REE extraction[42].
The above-mentioned process was applied to different
grades of Baotou mixed REE concentrates (50%–60%)
and the reported decomposition rates of all REE were
always above 93%[42].
1.2 Acid baking techniques
1.2.1 Monazite and xenotime
Acid baking process is a method of treating REE con-
centrates, particularly monazite and xenotime ores and
concentrates with H2SO4. In the acid baking process, a
highly concentrated acid, such as 93 wt.%–98 wt.%
H2SO4, is contacted with the REE ore or concentrate at
the elevated temperatures (200–250 ºC). The acid to
concentrate ratio is commonly in the range of 1–2.5 and
the process could be virtually completed within 3–4
h[7,21,43,44]. The process reaction starts with a fast kinetics
in the initial 15 min; however, the gray insoluble solid
product coats the monazite grains and then the reaction
kinetics slows down. The acid baking reactions depicted
in Eqs. (19), (20) and (21), are exothermic in na-
ture[7,21,45,46].
2REEPO4(s)+3H2SO4(aq)→REE2(SO4)3(s)+6H+(aq)+2PO3–4(aq)
(19)
Th3(PO4)4(s)+6H2SO4(aq)→3Th(SO4)2(s)+12H+(aq)+4PO3–4(aq)
(20)
(21)
After completion of the reactions, the resultant
acid-digested mass which often contains Th, U, lantha-
nide sulfates and other unreacted minerals and impurities
are leached in water. As a result, Th, U and REE sulfates
solubilize into water, leaving behind silica, rutile ilmenite,
zircon and undigested monazite residues. The water
leaching reactions occur as Eqs. (22) and (23)[30]:
(REE)2(SO4)3·nH2O(s)→2REE(aq)3++3SO2–4(aq)+nH2O(l) (22)
Th(SO4)2(s)→Th(aq)4++2SO2–4(aq) (23)
In an Outotec process, the calcine from the acid baking
process (250 ºC) is treated at 700 ºC to recover SO2 gas
and subsequently convert SO2 to H2SO4 and reuse in the
process. For this purpose, the fluidized bed technology
has become state-of-the-art technology for processing
sulfur bearing materials. The fluidized bed systems could
be combined with the efficient heat recovery stages and
off-gas treatment which make it possible to convert the
Farzaneh Sadri et al., A review on the cracking, baking and leaching processes of rare earth element concentrates
off-gas to H2SO4. This process, Lurgi Circulating Fluid
Bed (CFB), was originally developed by Lurgi Metal-
lurgy in Germany (now part of Outotec Company)[47,48].
Search Minerals Inc., a Vancouver, Canada based
company, has developed a process which involves
crushing and acid baking of the ore. In this technology,
only a simple coarse crushing is applied on the ore in-
stead of the fine crushing, grinding and physical separa-
tion, to reduce energy consumption of the process which
is mainly related to the beneficiation stage. Then, the ore
is treated with H2SO4 at 200 ºC to render the REE water
soluble. Afterwards, the remaining acid is neutralized
with magnesium carbonate (MgCO3), and then Na2CO3
is added to precipitate REE as REE carbonate concen-
trate. The REE carbonate concentrate is then re-leached
in HCl. The solution pH is adjusted to reject the impuri-
ties and REE are precipitated by an oxalic acid solution.
The resulting REE precipitates are subsequently cal-
cined to produce a high grade of REO product. The fi-
nal product has 98.99 wt.% total rare earth oxides
(TREO)[49].
Chuktukon ores in Russia contain REE mainly as
monazite and florensite (phosphates). The ores contain
40 wt.%–70 wt.% Fe2O3, 1 wt.%–20 wt.% MnO and 1
wt.%–2 wt.% P in the form of REE phosphates and apa-
tite[49]. Ore with a high iron content consumes a large
amount of H2SO4, so sulfuric acid treatment does not suit
this type of ores[17,50,51]. Direct acid leaching with HNO3
is a suitable route for acid treatment of apatites (phos-
phorites) containing monazite. Nitric acid treatment has
some advantages over sulfuric acid method: (i) Less acid
consumption; (ii) Higher rate of REE recovery; (iii) Ni-
trate solutions are more preferable for extraction and
separation of REE; and (iv) Niobium (Nb) minerals,
which were initially locked in the ore structure, are freely
exposed. Therefore, they could be further processed to
produce Nb products[52]. The nitric acid treatment is car-
ried out at the elevated temperature (180–220 ºC) due to
the instability of ferric compounds, which reduces the
HNO3 consumption as a result of iron(III) nitrate hy-
drolysis and increase the REE recovery[50,53]. Kuzmin et
al.[54] proposed a technique in order to dephosphorize the
solution, which is accomplished in two stages: (i) Alka-
line and acidic treatment; and (ii) Preliminary reduction
treatment and iron removal from the Nb containing resi-
due by magnetic separation[54]. The REE phosphates are
initially decomposed by NaOH to produce the REE hy-
droxides and Na3PO4 by-product. The REE hydroxides
are then dissolved in a HNO3 solution. This method has
some drawbacks, which result in a low Ce and REE re-
covery in the HNO3 solution: (i) In the alkaline cracking
process, manganese (Mn)(V) oxidizes Ce (III) to Ce(IV)
as ceria species (CeO2), which is insoluble in the HNO3
solution; and (ii) Soluble Mn(V) is formed in the solution,
because a disproportionation reaction occurred between
745
Mn(III) and Mn(IV) oxides in the strong alkaline me-
dium. Hence, in order to fix the impediments associated
with this method, a preliminary magnetizing roasting of
the ore was carried out to convert the iron oxides and
hydroxides to magnetite. This significantly hindered Ce
oxidation and subsequently increased the REE recovery.
Whereas, a poorly filterable alkaline pulp was produced
in the alkaline treatment stage. In addition, when the iron
oxides are removed by magnetic separation, it prevents
complete release of the pyrochlore or producing a rich
concentrate[54]. Kuzmin et al.[50] also suggested another
process to treat a high iron-bearing REE ore which was
based on the direct decomposition of REE mineral using
HNO3 as shown in Eq. (24).
REE(PO4)(s)+3HNO3(l)→REE(aq)3++3NO–3(aq)+H3PO4(aq)
(24)
Although, this method simplified the process due to the
elimination of the alkaline treatment stage and subse-
quently alkaline pulp filtration, it possessed two disad-
vantages: (i) REE recovery from phosphate solutions was
a significant challenge; (ii) A significant portion of iron
oxides and hydroxides was dissolved in the solution.
This process is possible to be carried out in a way that the
iron and phosphorus become poorly soluble in HNO3 and
remain in the solid phase. This would occur through the
formation of hydroxyl ferric phosphates as shown in Eq.
(25)[50]:
REEPO4(s)+5/8Fe2O3(s)+3HNO3(aq)→REE(NO3)3(aq)+
1/4Fe5(PO4)4(OH)3·2H2O(s)+5/8H2O(l) (25)
At the elevated temperature (180–220 ºC), phosphoric
acid (H3PO4) present in the HNO3 solution
co-precipitates with the iron(III) oxide and/or is adsorbed
on it, due to the substitution of OH– ions in hydroxyl fer-
ric phosphate by H2PO4– and HPO42–[45,50]. This results in
the elimination of H3PO4 from REE nitrate solution. In
addition, in the above mentioned range of temperature,
some other metal nitrates become unstable, which facili-
tate the HNO3 recycling. Also, the leaching residue could
further be processed to generate Nb concentrate. Figs. 3
and 4 show the principle technological scheme for pro-
ducing REE products and Nb concentrate, respectively,
from Chuktukon REE ore[50].
1.2.2 Bastnasite
Bastnasite could be decomposed into REO and REE
fluoride oxides by oxidation roasting in a temperature
range of 400–600 ºC, followed by sulfuric, nitric or hy-
drochloric acid leaching at ambient temperature[6,56]. This
process was used to produce mixed REE sulfate from
bastnasite originated from KIGMA, Korea[57]. Roasting
the concentrate at 600 ºC for 4 h converted the carbonate
REE of the ore into soluble oxide form as is presented in
Eq. (26). The roasted solid is then leached with H2SO4
solution at 60 ºC for 4 h to obtain REE sulfate (Eq. (27)).
After filtration, double sulfate REE can be precipitated
out of the solution[57].
746
Fig. 3 Principle technological scheme for the breakdown of
Chuktukon rare earth ore (reproduced with permission)
Fig. 4 Principle technological flowsheet for niobium concen-
trate producing from the leach residue of nitric acid
breakdown of the Chuktukon rare earth ore (reproduced
with permission)
(26)
(27)
The conventional methods for cracking bastnasite
concentrate are NaOH treatment and H2SO4 roasting.
However, NaOH treatment is not the preferred method
particularly due to its high alkaline consumption rate and
the radioactive Th existence in both leachate and resi-
JOURNAL OF RARE EARTHS, Vol. 35, No. 8, Aug. 2017
due[12,38]. The reaction for the H2SO4 baking of bastnasite
is shown in Eq. (28), where the REE fluorocarbonates
are converted to water soluble sulfates compounds. Wa-
ter leaching is the next step in the bastnasite processing.
(28)
In the most Chinese operations, the bastnasite proc-
essing steps are as follows: (i) Bastnasite ore is concen-
trated to a grade of about 66% REO; (ii) The concentrate
is roasted by H2SO4 at 400–500 ºC for several hours to
decompose the fluorocarbonate matrix and becomes
soluble in the HCl solution[37]; (iii) REE are solubilized
in HCl solution; and (iv) A oxalic acid solution is used to
precipitate REE oxalates. In Mountain Pass process in
California, whose operation was seized in 2015, a hot
flotation process was applied to concentrate bastnasite
minerals. Then the concentrate was leached at pH 1 with
10 wt.% HCl to remove the CaCO3 minerals and further
enrich the bastnasite concentrate to 68 wt.%–72 wt.%
REO. In the next step, the concentrate was calcined in
order to decompose the fluorocarbonates and form REO.
Furtheremore, Ce(III) was oxidized to Ce(IV) as CeO2
(ceric oxide), which is an insoluble compound at the high
acid concentrations. The remainder of CO2 was also
eliminated in this step, yielding a higher grade bastnasite
concentrate (85 wt.%–90 wt.% REO). Calcination proc-
ess was conducted in a multi-layer furnace using a
low-sulfur fuel in an oxidizing medium for 3 h at 620 ºC.
The calcined concentrate was then leached in a 30 wt.%
HCl solution to generate a pregnant leach solution (PLS)
containing REO, while CeO2 and ThO2 remained insolu-
ble in the solution. The PLS contained some impurities
which were subsequently removed by Na2CO3 addition.
Sodium sulfate (Na2SO4) was then added to precipitate
REE insoluble double sulfate salts (NaRE(SO4)2·H2O)
(Eq. (29)). It is worth noticing that the formation of ferric
hydroxide precipitates was inhibited via adjusting solu-
tion pH at 1.5[38].
REE2(SO4)3(s)+Na2SO4(s)+2H2O(l)↔
Na2SO4·REE2(SO4)3·2H2O(s) (29)
The same process was applied to a Turkish bastna-
site-containing pre-concentrate[38]. This process was ca-
pable of extracting 85%–90% REE with a grade above
90% and producing hydrofluoric acid (HF) as a
by-product, as well as eliminating some of the impurities
from the REE salt such as Th, Fe, aluminium (Al) and
Mg by quick precipitation. The Th-rich precipitate was
also a by-product of this process, which was obtained by
adding NaOH to the wastewater after REE double sulfate
precipitation. Fig. 5 shows the working flow sheet for
this operation[38]. The recovered REE double sulfate salt
is an intermediate product, and should be further treated
by sodium hydroxide to convert the REE double sulfate
salt to REE hydroxide. The REE hydroxide could then
Farzaneh Sadri et al., A review on the cracking, baking and leaching processes of rare earth element concentrates
Fig. 5 Working flowsheet for producing RE double sulfate salt and HF from bastnasite concentrate (reproduced with permission)
be dissolved in a HCl solution, leaving behind CeO2 as a
solid residue, and REE could be refined by SX[38].
1.2.3 Mixed bastnasite and monazite
Conventional treatment process for mixed bastnasite
and monazite is a complex process which requires corro-
sion resistant equipments, and generates large quantity of
wastewater, waste acid and alkali or discharges toxic
gases to the environment. Industry has developed a
cleaner process with a simple chemistry and a low cost.
In a newer process, a Na2CO3 roasting is used to de-
fluorinate REE ore and then fluorine in the form of so-
dium fluoride (NaF) is washed away with the hot water.
REE ore is thereafter chlorinated with HCl, where HCl is
formed through decomposition of NH4Cl via Eq. (30).
The chlorination process reactions are shown as Eqs.
(31), (32) and (33). If fluorine is still present in the ore, it
could be treated with MgO prior to chlorination process
to fix the F in the calcine, i.e. Fixing Fluorine Treatment
(FFT). The advantages of the above mentioned process
are: (i) Simplification of the F treatment which would
affect the recovery of REE in the purification and separa-
tion steps. This is particularly because the leachate con-
tains only traces of Fe, silicon (Si), Al and Th; (ii) No
excess acid would remain in the REE leachate. The addi-
tion of MgO results in the formation of insoluble fluorine
compounds, thus eliminating the need for F wash before
chlorination process. The chlorinating roasting step con-
verts REE to the water soluble chlorides which could
further be leached with the hot water[20,39].
(30)
(31)
(32)
(33)
It should be mentioned that the careful dosage of the
747
reagents in the FFT process is important, as excessive
amount of MgO would consume chlorination agent and
would influence the chlorination process.
In Baotou operation in China, a small amount of
monazite is associated with bastnasite. The unit opera-
tions of the process are as follows: (i) Roasting the con-
centrate with the concentrated H2SO4 at an elevated
temperature (>300 ºC) to crack the monazite; (ii) Water
leaching to dissolve REE sulfates and adding magnesia
to neutralize the excess acid; (iii) Solvent extraction
process to separate and purify REE. There are some dis-
advantages for this process: (i) The radioactive thorium
goes to the residue. Th recovery from the residue is not
economic, thus it is disposed of as the hazardous waste
area; (ii) The roasting off-gas contains HF and SO2
which requires a large amount of water or alkaline solu-
tion for scrubbing and a large volume of acidic effluents
would be produced as a result. To modify the process,
MgO or CaO and NaCl have been used to prevent F re-
leasing to the off-gas and stabilize it into the leach resi-
due. Roasting the concentrate with ammonium chloride
(NH4Cl) is another way to modify the process, where
REE chlorides are formed by the decomposition of the
NH4Cl to gaseous HCl (REE chlorides are water soluble
species). Another option is to preheat the concentrate
with H2SO4 at a lower temperature (40–180 ºC) before
the roasting process. Although roasting at a low tem-
perature minimizes H2SO4 decomposition, a large
amount of gaseous HF would be generated, which could
be converted into a solid NH4F through contacting with
(NH4)2CO3 in the off-gas treatment pipes[12]. A new
cleaner technique has been developed to process Bayan
Obo mixed REE concentrate, which is a combination of
oxidative roasting of the bastnasite and alkaline attacking
with wet-air oxidation of monazite. By means of this
748 JOURNAL OF RARE EARTHS, Vol. 35, No. 8, Aug. 2017

two-step oxidation method, REE, Th, F and phosphorus density of slurry was 1.5 g slag per liter of 0.3 mol/L
(P) can all be recovered effectively. This method uses the H2SO4. It was illustrated that the leaching kinetics could
interactions between Ce(IV), F and P to separate Ce(IV) be described by the shrinking core model and the leach-
from the other REE(III) and recover F, P and Th by ing process occurs in two stages. The rate controlling
complexing F and P through the oxidation of Ce(III) to process of the initial stage was chemical reaction with the
Ce(IV). In the first step of this method, bastnasite is oxi- activation energy of 10.0 kJ/mol. By increasing the
dized by air roasting and sulfuric acid leaching to provide leaching time, the diffusion process through the prod-
a leach liquor containing Ce(IV), F and P. In the second uct/ash layer became the rate controlling process with the
step, monazite is converted into REE hydroxide using activation energy of 24.8 kJ/mol. An increase in the
alkaline cracking, and afterwards Ce(III) in the hydrox- temperature led to a positive effect on the leaching rate
ide cake is oxidized into Ce(IV) by wet-air oxidation. and extent of leaching of lanthanum from the slag.
The hydroxide cake is then leached into sulfuric acid to Feng et al.[61] investigated the H2SO4 leaching kinetics
obtain another leach liquor containing Ce(IV), F and P. of REE from the roasted ore calcines of Dechang bastna-
Primary amine N1923 is used to extract Th, and ThO2 is
recovered as the Th-product. Cyanex923 is used to ob-
tain CeO2, CeF3 and CePO4 based on the complexation
of Ce(IV) with F and P. The overall REE recovery in this
novel process is over 92% and this technique avoids re-
source waste and environment pollution caused by F, P
and Th[58]. The flowsheet of a conventional process for
REE recovery is shown in Fig. 6. This is an example of
an effective process for REE recovery, but there are
some drawbacks which were mentioned above[59]. Fig. 7
shows the flowsheet for the two-step oxidation process of
Bayan Obo mixed ores.

2 Kinetics of REE leaching

It is necessary to investigate the kinetics of REE-
bearing ore, as they exhibit different characteristics dur-
ing the processing of REE. Kim et al.[60] studied leaching
Fig. 6 Working flowsheet for a conventional process of RE re-
kinetics of lanthanum in H2SO4 from REE slag of reduc-
covery
tion smelting of magnetite ore containing monazite. The

Fig. 7 Working flowsheet for two-step oxidation process of Bayan Obo mixed ores (reproduced with permission)
Farzaneh Sadri et al., A review on the cracking, baking and leaching processes of rare earth element concentrates
site in Sichuan which is associated with celestite. The ore
was roasted in a muffle furnace at 550 ºC for 2 h in the
air atmosphere, and the reported phases in the calcine
were REE2O3, REEOF, CeO2 and SrCO3. 50 g of the
roasted ore was then leached in 400 mL of 1.5 mol/L
H2SO4 with an S:L weight ratio of 1:8. The reactions in-
volved in this leaching process could be written as:
(34)
(35)
(36)
(37)
The model for the leaching process (Fig. 8) includes
four steps[61]: (i) Diffusion of H2SO4 through the liquid
layer; (ii) Diffusion of H2SO4 or liquid products through
the product layer; (iii) Chemical reaction; and (iv) Diffu-
sion of liquid products to the leaching system. The re-
sults demonstrated that the reaction rate of leaching
process is controlled by diffusion through the product/ash
layer with the activation energy of 9.977 kJ/mol which
could be described by shrinking core model. They also
showed that the temperature has a mild effect on the
leaching process while the effects of particle size and
H2S concentration are remarkable and the effect of stir-
ring speed is negligible.
Bian et al.[62] examined the leaching kinetics of bast-
nasite concentrate of Mianning, Sichuan deposit in HCl
solution at atmospheric pressure. It was concluded that
the leaching kinetics of bastnasite concentrate is repre-
sented by shrinking core model and diffusion through the
porous product layer is the rate controlling step. The ac-
tivation energies for the dissolution of REE2(CO3)3 and
REEF3 were 59.39 and 66.13 kJ/mol, respectively.
Fig. 8 Illustrative diagram of leaching process
1–Non-leached particle of REE ore; 2–Product/ash layer; 3–
Diffusion region of solvent (c0: concentration of leaching re-
agent in fluid phase; cs: concentration of leaching reagent on
surface of particle; cs: concentration of leaching reagent in region
of reaction; r0: radius of product/ash layer; r: radius of non-
leached particle of rare earth ore) (reproduced with permission)
749
Tian et al.[63] studied the REE leaching kinetics from
weathered crust elution-deposited rare earth ore with
ammonium sulfate (NH4)2SO4 solution. It was shown
that the leaching kinetics could be described by the
shrinking core model and the rate limiting step is the
diffusion of reactants and leaching products through the
porous solid layer with the activation energy of 9.24
kJ/mol. Similar results were obtained in other kinetic in
vestigations as well. Most of them proved that the REE
leaching kinetics obeys the shrinking core model[64,65].
Zhu et al.[59] studied the chlorination kinetics of fluo-
rine-fixed REE concentrate whose process was discussed
in section 1.2.3. The application of MgO during the first
stage roasting converts REE to REO, while fixing F as
insoluble magnesium fluorine (MgF2) in the calcine. The
second stage roasting would convert the REO into the
water soluble REE-chlorides. The mechanism of the re-
actions in the FFT is that the F in the bastnasite and the
phosphate anions in the monazite is converted to an in-
soluble MgF2 (Eqs. (38) and (39)) and Mg(PO4)2 residue
(Eq. (40)), respectively. The magnesium phosphate
(Mg3(PO4)2) subsequently reacts with the MgF2 and gen-
erates an insoluble Mg2FPO4 compound (Eq. (41))[20].
(38)
(39)
(40)
(41)
Zhu et al.[59] illustrated that increasing the roasting tem-
perature from 350 to 500 ºC increases the REE leachabil-
ity due to an increase in the diffusion rate of ammonium
gas; however, increasing the temperature from 520 to
650 ºC slows down the reaction kinetics. This complex
kinetic phenomenon occurs due to the fact that at higher
temperatures the chlorinated REE decomposes to water
insoluble REO via an intermediate product REOCl. It was
stated by Zhu et al.[59] that the internal diffusion was the
rate limiting step in the chlorination process.
3 Further processing
Irrespective of the original REE source or process,
PLS frequently contains some impurities that should be
precipitated before the separation process. There are six
techniques for the separation of REE: (i) selective oxida-
tion, (ii) selective reduction, (iii) fractional crystallization,
(iv) fractional precipitation, (v) IX and (vi) SX[2]. IX was
the first separation method applied on REE solutions to
produce a high purity of single or mixed REE com-
pounds in the large quantities[66]. Whereas, by the advent
of SX technique in 1960s, IX has only been used to ob-
tain small quantities of a highly pure REE product. SX is
the current industrial practice for the separation of REE
from PLS[67–69].
750
4 Summary
REE are increasingly becoming significant in devel-
oping the latest high-tech products, particularly due to
their unique properties. REE are found in more than 250
minerals but only three minerals are commercially used
for REE extraction: bastnasite, monazite and xenotime.
Mining and comminution, ore beneficiation through flo-
tation, gravity and magnetic separation and hydrometal-
lurgical processing are the three major steps for REE re-
covery. In the hydrometallurgical step, the concentrate
should initially be digested in order to become soluble in
the water or acids. Different methods are applicable in
this step such as acid baking (frequently using H2SO4)
and alkaline cracking with NaOH solution, which are
commonly used in the industry.
In the alkaline cracking technique, an alkali is used to
digest the concentrate at a high temperature (120–150 ºC).
In this process, phosphates are dissolved in the caustic
solution while REE hydroxide precipitates remain in-
soluble. The precipitates could then be dissolved in the
different acid solutions such as HCl, H2SO4 and HNO3,
and a REE-bearing solution would be obtained. Other
alkali materials could also be utilized for cracking the
concentrate such as CaCl2 and CaCO3. For bastnasite,
HCl treatment is performed prior to the alkaline cracking
to obtain the REE chloride and fluoride species. In the
next stage, insoluble REE fluoride is converted to REE
hydroxide by alkaline cracking. The resulting REE hy-
droxide residues are then leached in HCl solution to
produce REE chloride species. Th and U are selectively
removed from the REE hydrous oxide cake in a HCl so-
lution through adjusting the solution pH value. The hy-
drous oxide cake could also be dissolved in a H2SO4 so-
lution and a REE bearing-sulfate liquor is obtained. REE
oxalate precipitates are subsequently formed using oxalic
acid solution and uranium oxalate species remain soluble
in the solution. Thorium is also selectively separated
from the oxalate precipitates by a mixed solution of
Na2CO3/NAHCO3. Obtained REE oxalate precipitates
are then calcined to produce the REE oxide precipitates.
Ball mill autoclave digestion is another method for
monazite cracking to enhance the efficiency of the proc-
ess through removing the hydroxide layer formed on the
monazite particles’ surfaces and consequently
re-generating fresh monazite surfaces. It was illustrated
that the mechanical ball milling in the presence of CaO
and CaCl2 under Ar atmosphere decomposes monazite
which leads to the formation of REE oxychloride and
calcium chlorapatite.
Alkaline compounds such as NaOH, MgO and CaO
are often used to decompose difficult-to-treat mixed REE
concentrates. H2SO4 roasting is also applicable to treat
these minerals; however, the produced SO2 and HF
off-gases must be treated.
JOURNAL OF RARE EARTHS, Vol. 35, No. 8, Aug. 2017
In acid baking process, a highly concentrated H2SO4
solution is mainly used to disintegrate the structure of
concentrate and generate the water soluble sulfates. This
method is widely used for monazite and xenotime con-
centrates treatment. However, Search Minerals Inc. has
developed a process to apply the acid baking on the
crushed coarse ore. Bastnasite needs to be decomposed
into REO and REE fluoride oxides at the elevated tem-
peratures (400– 560 ºC) prior to sulfuric, nitric or hydro-
chloric acid baking. In Baotou in China, bastnasite con-
centrate is disintegrated by a H2SO4 solution at 400–500
ºC to become soluble in HCl and oxalic acid is subse-
quently used to precipitate REE oxalate out of solution.
Another way to treat bastnasite concentrate is the re-
moval of the CaCO3 minerals through leaching the con-
centrate in a 10% HCl solution. The enriched concentrate
is then calcined in order to convert the fluorocarbonates
to the REO and oxidize Ce(III) to Ce(IV) as CeO2. The
resulting precipitates containing REO are subsequently
dissolved in a 30% HCl solution while both CeO2 and
ThO2 remain insoluble. REE double sulfate salt
(NaRE(SO4)2·H2O) precipitates are then formed by addi-
tion of Na2SO4 to the solution. Direct decomposition of
REE-bearing phosphate ores is another process which is
introduced to treat the ores containing a high concentra-
tion of iron oxide. Although this process has some
drawbacks such as significant dissolution of iron oxide
and hydroxides in the solution and the problem associ-
ated with the REE recovery from phosphate solutions, it
could be carried out in a way that approximately all of
the iron and phosphorous remain in the solid phase,
leaving behind the REE nitrates in the solution by ad-
justing the temperature in the range of 180–220 ºC.
Various REE ores exhibit different leaching kinetics.
Kinetic studies for the different REE ores illustrated that
the leaching process proceedes in four steps: (i) Diffu-
sion of the solvent through the liquid layer; (ii) Diffusion
of the solvent or the liquid products through the product
layer; (iii) Chemical reaction; and (iv) Diffusion of liquid
products to the leaching environment. The results ob-
tained from the kinetic studies on the REE leaching re-
vealed that the reaction rate of the leaching process could
be described by shrinking core model and is controlled
by diffusion through the product layer. Kim et al.[60]
stated that the leaching process occurs in two stages. In
the beginning, the process is controlled by the chemical
reaction and then diffusion through the product layer be-
comes the rate controlling step.
Depending on the type of the concentrate (monazite,
bastnasite or mixed) and its impurities, different REE
products are produced through either the alkali cracking
or acid baking processes. The impure products require a
further processing including purification and separation.
The last steps employed in the hydrometallurgical proc-
essing are the selective oxidation, selective reduction,
Farzaneh Sadri et al., A review on the cracking, baking and leaching processes of rare earth element concentrates 751

fractional crystallization, fractional precipitation, IE and [18] Alkane Resources, Edison Investment Research, 19 Octo-
SX methods to produce a final REE product with a high ber 2015. Available online at http://www.alkane.com.au/
purity. images/pdf/broker/20151019.pdf.
[19] Chen Z H. Global rare earth resources and scenarios of fu-
ture rare earth industry. J. Rare Earths, 2011, 29(1): 1.
References: [20] Shi W Z, Zhu G C, Hua J, Chi R A. Recovery of RE from
Baotou rare earth concentrate with chlorination roasting.
[1] Tyler G. Rare earth elements in soil and plant systems – A
Trans. Nonferrous Met. Soc. Chin., 2003, 13: 438.
review. Plant Soil, 2004, 267: 191.
[21] Habashi F. (Ed.). Handbook of Extractive Metallurgy.
[2] Gupta C K, Krishnamurthy N. Extractive Metallurgy of
Weinheim: Wiley-VCH, 1997.
Rare Earths. Florida: CRC Press, 2005.
[22] Cuthbert F L. Thorium Production Technology. Massa-
[3] Jordens A, Cheng Y P, Waters K E. A review of the ben-
chusetts: Wesley Publishing Company Inc., 1958. 72.
eficiation of rare earth element bearing minerals. Miner.
[23] Welt M A, Smutz M. Processing methods of monazite
Eng., 2013, 41: 97.
sands. JOM, 1960, 19: 321.
[4] Neill D A, Speed E. The strategic implications of China’s
[24] Abdel-Rehim A M. An innovative method for processing
dominance of the global rare earth elements (REE) market,
Egyptian monazite. Hydrometallurgy, 2002, 67: 9.
DRDC CORA TM 2012-204. Available online at
[25] Merrit R R. High temperature methods for processing
http://cradpdf.drdc-rddc.gc.ca/PDFS/unc121/p536767_A1
monazite: I. Reaction with calcium chloride and calcium
b.pdf.
carbonate. J. Less-Common Met., 1990, 166: 197.
[5] Kanazawa Y, Kamitani M. Rare earth minerals and re-
[26] Zelikman A W. Metallurgy of Rare Metals. Washington:
sources in the world. J. Alloys Compd., 2006, 408-412:
US NASA and NSF Publication, 1966. 258.
1339.
[27] Doyle F M, Duyvesteyn S. Aqueous processing of miner-
[6] Huang Y K, Zhang T A, Dou Z H, Liu J, Tang F F. Study
als, metals and materials. J. Miner. Met. Mater. Soc., 1992,
on leaching rare earths from bastnaesite treated by calcifi-
45(4): 46.
cation transition. J. Rare Earths, 2014, 32: 1043.
[28] Hilal O M, Kiwan A M. Extraction of uranium from
[7] Gupta C K, Mukherjee T K. Hydrometallurgy in Extrac-
monazite after separation of thorium and rare earths. In-
tion Processes, Florida: CRC Press, 1990. 2.
dian J. Technol., 1968, 6(1): 17.
[8] Harlov D E, Andersson U B, Forster H J, Nystromc J O,
[29] Verbaan N, Bradley K, Brown J, Mackie S. A review of
Dulski P, Broman C. Apatite-monazite relations in the
hydrometallurgical flowsheets considered in current REE
Kiirunavaara magnetite-apatite ore, northern Sweden. J.
projects. In: Simandl G J, Neetz M, (Eds.), Symposium on
Chem. Geol., 2002, 191: 47.
Strategic and Critical Materials Proceedings, November
[9] Clavier N, Podor R., Dacheux N. Crystal chemistry of the
13-14, 2015, Victoria, British Columbia. British Columbia
monazite structure. J. Eur. Ceram. Soc., 2011, 31: 941.
Ministry of Energy and Mines, British Columbia Geologi-
[10] Huang X W, Long Z Q, Li H W, Ying W, Zhang G, Xue X
cal Survey Paper, 2015, 3: 147.
X. Development of rare earth hydrometallurgy technology
[30] Kim E, Osseo-Asare K. Aqueous stability of thorium and
in China. J. Rare Earths, 2005, 23(1): 1.
rare earth metals in monazite hydrometallurgy: Eh–pH
[11] Wang W, Pranolo Y, Cheng C Y. Metallurgical processes
diagrams for the systems Th–, Ce–, La–, Nd–(PO4)–
for scandium recovery from various resources: a review.
(SO4)–H2O at 25 ºC. Hydrometallurgy, 2012, 113-114: 67.
Hydrometallurgy, 2011, 108: 100.
[31] Amer T E, Abdella W M, Abdel Wahab G M, El-Sheikh E
[12] Xie F, Zhang T A, Dreisinger D, Doyle D. A critical re-
M. A suggested alternative procedure for processing of
view on solvent extraction of rare earths from aqueous so-
monazite mineral concentrate. Int. J. Miner. Process, 2013,
lutions. Miner. Eng., 2014, 56: 10.
125: 106.
[13] Borai E H, Mady A S. Separation and quantification of
[32] Alex P, Suri A K, Gupta C K. Processing of xenotime
238U, 232Th and rare earths in monazite samples by ion
concentrate. Hydrometallurgy, 1998, 50: 331.
chromatography coupled with on-line flow scintillation
[33] Mahmoud K F. Controlled alkali treatment of Rosetta
detector. Appl. Radiat. Isot., 2002, 57: 463.
monazite for the preparation of uranium-free trisodium
[14] Savel’eva I L. The rare-earth metals industry of Russia:
phosphate. Sci. J. Fac. Sci. Minufia Univ., 2008, 22: 113.
present status, resource conditions of development. Geogr.
[34] Wu W Y, Bian X. Reaction process of monazite and bast-
Nat. Resour., 2011, 32: 122.
naesite mixed rare earth minerals calcined by CaO-
[15] Abreu R D, Morais C A. Purification of rare earth elements
NaCl-CaCl2. Trans. Nonferrous Met. Soc. Chin., 2007, 17:
from monazite sulphuric acid leach liquor and the produc-
864.
tion of high-purity ceric oxide. Miner. Eng., 2010, 23: 536.
[35] Kim W, Bae I, Chae S, Shin H. Mechanochemical de-
[16] Parhi P K, Park K H, Nam C W, Park J T. Liquid-liquid
composition of monazite to assist the extraction of rare
extraction and separation of total rare earth (RE) metals
earth elements. J. Alloys Compd., 2009, 486: 610.
from polymetallic manganese nodule leaching solution. J.
[36] Zhang J, Lincoln F J. The decomposition of monazite by
Rare Earths, 2015, 33: 207.
mechanical milling with calcium oxide and calcium chlo-
[17] Jorjani E, Bagherieh A H, Chelgani S C. Rare earth ele-
ride. J. Alloys Compd., 1994, 205: 69.
ments leaching from Chadormalu apatite concentrate:
[37] Peelman S, Sun Z H I, Sietsma J, Yang Y. Leaching of rare
Laboratory studies and regression predictions. Korean J.
earth elements: Past and present, ERES2014: First Euro-
Chem. Eng., 2011, 28: 557.
752
pean Rare Earth Resources Conference. Milos, Greece,
2014.
[38] Kul M, Topkaya Y, Karakaya I. Rare earth double sulfates
from pre-concentrated bastnasite. Hydrometallurgy, 2008,
93: 129.
[39] Wang X Y, Liu J M, Li M, Fan H L, Yang Q S. Decompo-
sition reaction kinetics of Baotou RE concentrate with
concentrated sulfuric acid at low temperature. Rare Met.,
2010, 29: 121.
[40] Calkins G D. Recovery of Th and U values from aqua's
solution. United States: US 823, 976, 1958.
[41] Kumari A, Panda R, Kumar Jha M, Lee J Y, Kumar J R,
Kumar V. Thermal treatment for the separation of phos-
phate and recovery of rare earth metals (REMs) from Ko-
rean monazite. J. Ind. Eng. Chem., 2014, 21: 696.
[42] Xu Y, Liu H, Meng Z, Cui J, Zhao W, Li L. Decomposi-
tion of bastnasite and monazite mixed rare earth minerals
calcined by alkali liquid. J. Rare Earths, 2012, 30: 155.
[43] Sadri F, Rashchi F, Amini A. Hydrometallurgical digestion
and leaching of Iranian monazite concentrate containing
rare earth elements Th, Ce, La and Nd. Int. J. Miner.
Process, 2017, 159: 7.
[44] Lim H, Ibana D, Eksteen J. Leaching of rare earths from
finr-grained zirconosilicate ore. J. Rare Earths, 2016,
34(9): 908.
[45] Abdelfattah N A, Abdou A A, Bakry A R. A novel proce-
dure for the recovery of Rosetta Monazite metal values
through its acid treatment. J. Appl. Sci. Res., 2014, 1: 22.
[46] Vijayalakshmi R, Mishra S L, Singh H, Gupta C K. Proc-
essing of xenotime concentrate by sulphuric acid digestion
and selective thorium precipitation for separation of rare
earths. Hydrometallurgy, 2001, 61: 75.
[47] Kohl A L, Nielsen R B. Gas Purification. Houston: Gulf
publishing Company, 5th ed., 1997.
[48] Güntner J, Kolehmainen E, Tiihonen M, Karonen J,
Haavanlammi L, Hammerschmidt J. Recovery of rare
earth elements from complex raw materials by Outotec
Technology, XXVIII International Mineral Processing
Congress (IMPC). Quebec, Canada, 2016.
[49] Dreisinger D, Verbaan N, Johnson M. The Search Miner-
als Direct Extraction Process for Rare Earth Element Re-
covery. San Fransisco: Rare Metal Technology, 2016.
[50] Kuzmin V I, Pashkov G L, Lomaev V G, Voskresenskaya
E N, Kuzmina V N. Combined approaches for compre-
hensive processing of rare earth metal ores. Hydrometal-
lurgy, 2012, 129-130: 1.
[51] Aly Monir M, Mohammed Nabawia A. Recovery of lan-
thanides from Abu Tartur phosphate rock, Egypt. Hydro-
metallurgy, 1999, 52: 199.
[52] Bunus F T, Dumitrescu R. Simultaneous extraction of rare
earth elements and uranium from phosphoric acid. Hy-
drometallurgy, 1992, 28: 331.
[53] van Weert G, Shang Y. Iron control in nitrate hydrometal-
lurgy by (auto) decomposition of iron(II) nitrate. Hydro-
metallurgy, 1993, 33: 255.
[54] Kuzmin V I, Lomayev V G, Pashkov G L. Processing of
JOURNAL OF RARE EARTHS, Vol. 35, No. 8, Aug. 2017
theores weathered carbonatite crusts is the future of the
rare metal industry of Russia. Non-Ferrous Met. (Russ.),
2006, 12: 62.
[55] Mustafa S, Nawab G. Temperature effect on phosphate
sorption by iron hydroxide. Environ. Technol., 2004, 25: 1.
[56] Wu B, Shang H, Wen J K. Sulfuric acid leaching of low-
grade refractory tantalum-niobium and associated rare
earths minerals in Panxi area of China. Rare Met., 2015,
34(3): 202.
[57] Hung N T, Chung N T, Dinh L X. Study on recovering di-
rectly the commercial cerium oxide and total of residue
rare earths from Dongpao bastnasite concentrate. The an-
nual report for 2001-2002, VAEC. Available online at
http://www.iaea.org/inis/collection/NCLCollectionStore/_
Public /35/095/35095869.pdf
[58] Zou D, Chen J, Li D Q. Separation chemistry and clean
technique of cerium(IV): A review. J. Rare Earths, 2014,
32(8): 681.
[59] Zhu G, Chi R, Shi W, Xu Z. Chlorination kinetics of fluo-
rine-fixed rare earth concentrate. Miner. Eng., 2003, 16:
671.
[60] Kim C J, Yoon H S, Chung K W, Lee J Y, Kim S D, Shin
S M, Lee S J, Joe A R, Lee S I, Yoo S J, Kim S H. Leach-
ing kinetics of lanthanum in sulfuric acid from rare earth
element (REE) slag. Hydrometallurgy, 2014, 146: 133.
[61] Feng X L, Long Z Q, Cui D L, Wang L, Huang X, Zhang
X C. Kinetics of rare earth leaching from roasted ore of
bastnasite with sulfuric acid. Trans. Nonferrous Met. Soc.
Chin., 2013, 23: 849.
[62] Xue B, Chen J L, Zhao Z H, Yin S H, Luo Y, Zhang F Y,
Wu W Y. Kinetics of mixed rare earths minerals decom-
posed by CaO with NaCl-CaCl2 melting salt. J. Rare
Earths, 2010, 28: 86.
[63] Tian J, Chi R A, Yin J Q. Leaching process of rare earths
from weathered crust elution-deposited rare earth ore.
Trans. Nonferrous Met. Soc. China, 2010, 20: 892.
[64] Xiao Y F, Liu X S, Feng Z Y, Huang X W, Huang L, Chen
Y Y, Wu W Y. Role of minerals properties on leaching
process of weathered crust elution-deposited rare earth ore.
J. Rare Earths, 2015, 33(5): 545.
[65] Xiao Y F, Feng Z Y, Hu G H, Huang L, Huang X W, Chen
Y Y, Li M L. Leaching and mass transfer characteristics of
elements from ion-adsorption type rare earth ore. Rare
Met., 2015, 34(5): 357.
[66] Shokobayev N M, Bouffier C, Dauletbakov T S. Rare
earth metals sorption recovery from uranium in situ leach-
ing process solutions. Rare Met., 2015, 34(3): 195.
[67] Jamrack W D. Rare Earth Extraction by Chemical Engi-
neering Techniques. London: Pergamon press, 1963.
[68] Kumar M. Recent trends in chromatographic procedures
for separation and determination of rare earth elements: a
review. Analyst, 1994, 119: 2013.
[69] Reddy B R, Kumar B N, Radhika S. Solid–liquid extrac-
tion of terbium from phosphoric acid medium using bi-
functional phosphinic acid resin, tulsion, CH- 96. Solvent
Extr. Ion Exch., 2009, 27: 695.