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 International Journal of Mining Science and Technology xxx (2015) xxxxxx

Contents lists available at ScienceDirect

International Journal of Mining Science and Technology

journal homepage: www.elsevier.com/locate/ijmst

A review of rare earth minerals flotation: Monazite and xenotime

Chelgani S. Chehreh a,, Rudolph M. a, Leistner T. a, Gutzmer J. a, Peuker Urs A. b
a
Helmholtz-Zentrum Dresden-Rossendorf, Helmholtz-Institute Freiberg for Resource Technology, Freiberg 71691, Germany
b
Institute of Mechanical Process Engineering and Minerals Processing, TU Bergakademie Freiberg, Freiberg 71691, Germany

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

Article history: This paper reviews rare earth minerals (monazite and xenotime) separation by flotation. A wide range of
Received 4 February 2015 monazite and xenotime flotation test results are summarized including: reasons of variation in the point
Received in revised form 26 March 2015 of zero charges on these minerals, the effects of various flotation conditions on zeta potential of monazite
Accepted 15 May 2015
and xenotime, interactions of collectors and depressants on the surface of these minerals during flotation
Available online xxxx
separation, relationship between surface chemistry of the minerals and different types of collector
adsorptions and effects of the conditioning temperature on flotation of rare earth minerals. This review
Keywords:
collects various approaches for the selective separation of monazite and xenotime by flotation and gives
Flotation
Rare earth
perspectives for further research in the future.
Monazite 2015 Published by Elsevier B.V. on behalf of China University of Mining & Technology.
Xenotime
IEP
Hydroxamate

1. Introduction has been published an updated list of now 14 critical materials

Since the development of ion exchange and other extraction
methods, rare earth elements (REEs) have been extracted commer-
cially. The first industrial beneficiation from rare earth minerals
(REMs) can be traced back to 1893 when thorium was extracted
from monazite, and was used in gas lamp mantles [1]. REEs are
used in many new electronic and advanced components (fuel cells,
mobile phones, displays, high-capacity batteries, permanent mag-
nets for wind power generation, green energy devices, etc.) [2].
Due to the high demand of REE in the last decades, their values
have been increasing significantly [1]. From 1964 to 1997, the
REE market increased by a factor of 17, and it has increased by a
factor of 20.5 from 1997 to 2007 [3].
From 1990 to 2002, Mountain Pass and Bayan Obo provided
more than 80% of the world mining of REE resources. The Mountain
Pass deposit had been suspended for around 10 years, mainly due
to environmental problems associated with the disposal of
thorium-containing waste and now China produces about 90% of
the global supply of REEs [35]. Recently China has dominated
the REE market, increased their export taxes and decreased the
trade (50,150 tons exported in 2009; decreased to 30,250 tons in
2010-around 40% decreases) [6]. This fact has greatly increased
REEs prices, causing tension and uncertainty among the worlds
high-tech markets [2]. Since June 2010, the European Commission
Corresponding author. Tel.: +49 1745356532.
E-mail address: s-chehreh.chelgani@hzdr.de (S.C. Chelgani).
(metals, group of metals or minerals) that are essential for many
important emerging technologies of its regional industries and
one of the most critical situation seems to be that of REEs,
especially the heavy REE (HREE) because of the Europe high import
dependency rate, low substitution and low recycling rate, and no
production within Europe [7]. In the same way, the US Department
of Energy (DOE) published a technical document determining a
long-term strategy for REE materials which may be considered
critical for the US economy showing a high risk of supply interrup-
tions [2,8].
The main principal commercial REE mineral sources are the
following: bastnaesite [REE(CO3)]F (7075% RE oxides), monazite
(REE)PO4 (5560% RE oxides) and xenotime (REE)PO4 (5560% RE
oxides) [13]. Because of the complexity and the fine nature of
the REE ore, flotation can be considered as one the most important
techniques to separate RE Minerals (REM) from associate minerals
and to produce the concentrates which usually contain 6070% of
mixed REM [911].
In 2013, Kristian Waterss research group at McGill University
conducted an extensive literature review on various separation
techniques that are currently employed for REM beneficiation.
Their thorough review is focused on the current physical benefici-
ation of bastnasite with regard to the unit operations employed,
and the processing plants. However, they highlighted the lack of
sufficient knowledge base for the separation of monazite and
xenotime by flotation, and the need for further research in this area
to provide a more complete insight into the development of

http://dx.doi.org/10.1016/j.ijmst.2015.09.002
2095-2686/ 2015 Published by Elsevier B.V. on behalf of China University of Mining & Technology.

Please cite this article in press as: Chelgani SC et al. A review of rare earth minerals flotation: Monazite and xenotime. Int J Min Sci Technol (2015), http://
dx.doi.org/10.1016/j.ijmst.2015.09.002
2 S.C. Chelgani et al. / International Journal of Mining Science and Technology xxx (2015) xxxxxx

separation processes for these REM [12]. Monazite and xenotime indicated that the PZC of monazite stayed around pH 5.5 and for
are mostly distributed in placer deposits. REM occurs only in very xenotime in the absence of collector is between pH 3 and 5
fine grains and standard physical separation methods are not effec- [9,10,16].
tive on them. In many deposits around 60% of the liberated mon-
azite and xenotime are smaller than 10 lm (in only few deposits
3. Monazite flotation
including placers, they can also be coarse grained) which is difficult
to recover in the beneficiation process [9]. Therefore, for technical
Monazite is a cerium and lanthanum phosphate, and represents
and economic reasons, flotation is an attractive technique for mon-
the major commercial source of cerium, an important source for
azite and xenotime separation [9,13].
thorium, lanthanum, and a variable amount of uranium [2731].
In the present article we aim to provide a comprehensive
Beach sands are the most common commercial deposits for the
review of the flotation separation of monazite and xenotime by
extraction of monazite [24,25,32]. Since 1948 flotation commer-
emphasizing surface properties and modifying reagents (collectors
cially has been used to provide monazite concentrates [9]. Due to
and depressants). We demonstrate how froth flotation has been
the very similar surface properties of monazite and associated
applied to separate these two REM from their typical gangue min-
minerals (mainly zircon and rutile) [20,3234], upgrading by
erals (silicates, carbonates, oxide minerals and zircon).
means of selective flotation requires the utilization of adequate
combinations of collectors and depressants [35].
2. Zeta potential
3.1. Collectors
The determination of minerals surface charges in different pH
values is one of the most important techniques, which have been
Sodium oleate as a collector in monazite flotation has been
used to better understand the flotation of minerals with the same
reported in many studies (Table 3) [7,10,20,25,34,36]. The carboxy-
surface characteristics [14]. The point of zero charges (PZC) and the
late adsorption on the monazite surface was studied by Viswa-
isoelectric point (IEP) are key parameters to better understand the
nathan et al. [20]. Also a comparison between the selectivity of
surface charge of various minerals [15].
oleic acid and sodium oleate as collectors in monazite flotation
Various IEPs are reported for monazite and xenotime. The IEP is
revealed that sodium oleate showed better floatabilites compared
very sensitive to surface potential-determining ions, since the
to oleic acid [36]. Infrared spectroscopy analyses showed
changing of the chemical compositions of the mineral surface
chemisorption of oleate collectors on the monazite surface
results in IEP shifting. The main reasons of wide range IEP on
[20,25]. Experimental analysis demonstrated that the sodium
REM can be summarized as: (1) variations in chemical composition
oleate adsorption and consequently flotation of monazite are
of minerals from different deposits (chemical compositions expose
pH-dependent [34]. Since above the PZC (pH 5.3) the surface of
different amounts of each element on the surface to the aqueous
monazite is negatively charged, it seems more probable that the
solution); (2) the differences in presence of impurities and crystal
sodium oleate is chemisorbed to the mineral surface. Predominant
structure (difference in the arrangement of elements in the crys-
presence of Ce(OH)2+ and La(OH)2+ species reported as the main
tal); (3) differences in the procedures for preparation (experimen-
reason for maximum floatability of monazite in this pH range
tal conditions) of the mineral samples which results in dissimilar
(8.59) [10]. The measured adhesive strength of monazite in that
amounts of charges on the particle interface [13,15]. There has
pH range showed the same results. At pH 8 oleate/monazite inter-
been a wide range of values reported in the literature for the PZC
action is strong enough to surpass the electrostatic repulsion
of monazite and xenotime (Tables 1 and 2). Recent investigations
between the negatively charged surface and the anion [25]. Above
pH 9, as the concentration of hydroxylic species decreased and the
Table 1
Summary of monazite point of zero charges (PZC).
monazite recovery dropped significantly [10]. These evaluations
indicate the possibility of a physical adsorption mechanism of
References Year PZC of monazite sodium oleate on the monazite surface below the PZC (5.2) (the
Choi and Whang [17] 1963 3.4 collector is not ionized at low pH) [25].
Parks [18] 1967 1.13.2 On monazite from the Kerala and Chennai deposits (India) dif-
Salatic [19] 1967 6.4
ferent anionic collectors were examined (sodium laurate, sodium
Viswanathan et al. [20] 1970 5.5
Abeidu [9] 1972 5.5 oleate, Neofat 140 (mixture of oleic and linoleic acid), Acintol
Ney [21] 1973 9.0 FA1, Acintol FA2, Acintol FAX (Fatty Acids)) for monazite flotation.
Cuif [22] 1988 6.1 The acintols showed better selectivity than sodium oleate (approx-
Houot et al. [16] 1991 1.13.2, 3.4, 6.1, 6.4, 9.0
imately the same recovery with 915% higher grade) [28]. On mon-
Cheng et al. [10] 1993 5.3
Harada et al. [23] 1993 3.1, 5.1, 5.5, 6.8
azite from the Rosetta black sand deposits (Egypt) various cationic
Pavez and Peres [24] 1993 5.2 collectors (Amine 22, Armac and Armac T (amine collectors)) were
Pavez et al. [25] 1996 5.2 used to float monazite. Direct flotation was not successful; there-
Cheng [13] 2000 7.0 fore, monazite particles were depressed with lactic acid and the
Ren et al. [26] 2000 4.7
residual minerals floated with 3-lauril amine hydrochloride con-
Zhang et al. [15] 2013 5.0
centrate. In this study monazite recovery and grade were 75.5%
and 70%, respectively [25].
QEMSEM is used to study the floatability of monazite in the
Table 2 presence of sodium oleate, and the liberation of monazite particles.
Summary of xenotime point of zero charges (PZC).
The optimum size fraction for the flotation was selected between
References Year PZC of xenotime 74 + 37 lm. QEMSEM results demonstrated that monazite was
Cheng et al. [10] 1993 3 mainly associated with the iron minerals especially ilmenite,
Harada et al. [23] 1993 7 further grinding of the flotation products was necessary to liberate
Pereira and Peres [22] 1997 2.3, 3, 4, 5 monazite from its association with the iron minerals.
Cheng [13] 2000 7
The low selectivity of fatty acids as REM collectors led to
Zhang et al. [15] 2013 3
investigations to find reagents with more selectivity. In several

Please cite this article in press as: Chelgani SC et al. A review of rare earth minerals flotation: Monazite and xenotime. Int J Min Sci Technol (2015), http://
dx.doi.org/10.1016/j.ijmst.2015.09.002
 S.C. Chelgani et al. / International Journal of Mining Science and Technology xxx (2015) xxxxxx
Table 3
Summary of various conditions in flotation of monazite.
References
Sorensen and Lundgaard [36]
Dixit and Biswas [34]
Cheng et al. [10]
Pavez et al. [25]
Qi [38]
Liping [42]
Pavez et al. [25]
Pavez and Peres [32]
investigations hydroxamic acids were chosen to increase selectiv-
ity in REM flotation [3741]. Several investigations demonstrated
the ability of hydroxamic acids to adsorb through a stable metallic
complex with cations (REE) on REM surfaces. Chemisorption of
hydroxamates onto monazite was reported in various studies.
These studies suggested that the hydroxylated RE ions (i.e., RE
(OH)2+ and RE(OH)2+) may adsorb on the REM surfaces and con-
tribute to chemisorption [42]. The infrared spectrum of monazite
after hydroxamate adsorption also indicated hydroxamate
chemisorption, with formation of a metallic hydroxamate bond
[25].
Pavez and Peres [24] compared the capability of two different
hydroxamates in monazite particle ( 0.210 + 0.105 mm) flotation,
and demonstrated that commercial hydroxamate (FLOTINOR
V3759) is a significantly stronger collector than the pure potassium
octyl hydroxamate (CH3(CH2)6CONHO-K). The best floatability
range of monazite with V3759 was observed between pH 3 and
pH 7 [32]. The separation processing of monazite from the beach
sand in Sao Goncalodo Sapucai (Brazil) was performed with
hydroxamate and sodium oleate as collectors and in the presence
of sodium silicate (a depressant). Results demonstrated that the
selectivity of monazite flotation increased using a hydroxamate
instead of a fatty acid (assays: 57.59% vs 49.07%).
All the reported investigations show that monazite can be read-
ily floated with fatty acid-based collectors (i.e. sodium oleate) as
well as hydroxamic acid or hydroxamate based collectors in the
pH range above the PZC. With respect to the surface charge of
monazite (above the PZC), it is estimated that chemisorption is
the preferred adsorption mechanism of these collectors on the
monazite surface. From the investigations it can be concluded that
regarding selectivity, the use of hydroxamates showed the
appropriate performance whereas sodium oleate indicated better
recovery in the same condition (Fig. 1).
3.2. Depressants
Generally, in flotation of REM, collector and depressant concen-
trations must be well-defined. There is an agreement that the
selective flotation of monazite requires depressants (due to similar
100
90
80
70
Recovery (%)
60
50
40 Sodium oleate
30 Hydroxamate
20
10
1 2 3 4 5 6 7 8
pH
Fig. 1. A comparison between floatability of monazite in the present of different
collectors as a function of pH (152 mg/L sodium oleate; 26 mg/L commercial
hydroxamate [25]).
Please cite this article in press as: Chelgani SC et al. A review of rare earth minerals flotation: Monazite and xenotime. Int J Min Sci Technol (2015), http://
dx.doi.org/10.1016/j.ijmst.2015.09.002
3
Collector pH Size Gangue minerals
Sodium oleate 8 150 Silicate, sulfides, oxides
Sodium oleate 8.18.3 70 + 140 Ilmenite, zircon, rutile
Sodium oleate 8.5 5 Pure monazite
Sodium oleate 8 37 Silicate, oxides
Fatty acid-brytofa 9.8 37 + 74 Hematite, goethite, ilmenite
Hydroxamate 89 74 Barite, fluorite
Hydroxamate 9 37 Silicate, oxides
Hydroxamate 7 37 Zircon, rutile
surface properties of the associated minerals) (Table 4)
[8,19,20,24,37]. Sodium silicate, disodium sulfide, and sodium
oxalate are common depressants that are used for depression of
monazite associated minerals [8,16,24].
As a depressant, disodium sulfide (Na2S) is used in the flotation
of various minerals (sulfides and oxides). Na2S acts as a selective
depressant in the flotation of REM with fatty acids. The hydrolysis
of disodium sulfide and the presence of hydrosulfite and hydroxyl
ions were reported as the main factors of depression. Flotation
results demonstrated that increasing the disodium sulfide concen-
tration effectively depressed pyrochlore and zircon and did not
affect monazite flotation. Experimental results showed that the
depression was due to the effect of hydrosulfite ions, and not
hydroxyl ions. Sodium sulfide activates the surface of monazite
grains due to the adsorption of S2 and SH ions and subsequent
partial displacement of phosphate sites [8]. Infrared spectroscopy
and radiometric results indicated that the attached sulfur at mon-
azite surfaces was in oxidized form (due to strong oxidizing of RE
cations) [37]. Furthermore these analyses suggest that SH is the
active agent of sodium sulfide to desorb the collector from the sur-
face of these gangue minerals [37].
The effect of sodium silicate on the flotation of non-sulfidic
minerals is well-understood. The adsorption of hydrolysis products
of sodium silicate on the surface of minerals decreases their floata-
bility and depresses them [43]. Surface activation of monazite by
sodium silicate was reported by Beloglazov and Osolodkov [44].
In 1966, Sorensen and Lundgaard used sodium silicate as a pH
modifying reagent. They reported that sodium silicate caused a
suppression of the collector adsorption on monazite surface [36].
Chan observed that with the use of Na2S and sodium silicate as
depressants and sodium oleate as a collector, the froth conditions
and recovery of REM significantly improved. Based on these obser-
vations, further work was directed toward the development of a
selective Fe depressant. The addition of WW82/Quebracho as a sat-
isfactory iron depressant and pH modifier made it possible to
recover more than 60% of total REO at a concentrate grade of above
50% total REO [9].
In 1993, Pavez and Peres reported that sodium meta-silicate is
more effective than disodium sulfide as a depressant for zircon
and rutile. They found that even a high concentration of disodium
sulfide is not effectively depressing these minerals indicating that
in the presence of oleate and hydroxamate, disodium sulfide
slightly depresses monazite [24,35].
Also it was reported that in the presence and absence of sodium
silicate, the recovery of the monazite and its gangue minerals
changed from order (1) to order (2) [38]:
(1) Apatite > monazite = hematite > ilmenite > Ca.
Fe phosphate > goethite.
9 10 11 12 (2) Apatite > monazite > Ca.
Fe phosphate > goethite = ilmenite > hematite.
It was concluded that sodium silicate depressed the flotation of
all the iron minerals to a greater extent than the phosphate
4 S.C. Chelgani et al. / International Journal of Mining Science and Technology xxx (2015) xxxxxx
Table 4
Summary of various depressants for different gangue minerals in flotation of monazite.
References Depressant
Zakharov et al. [37] Sodium sulfide
Abeidu [8] Sodium sulfide
Pavez and Peres [24,35] Sodium silicate
Liping [42] Na2O
SiO2
minerals [38]. Sodium silicate can also depress silicate minerals in
monazite flotation [40]. Liping reported that waterglass (a
compound containing sodium oxide and silica: Na2O
SiO2) is an
ideal reagent to depress intergrowth minerals in monazite ores.
The mechanism of the intergrowth minerals depression by
waterglass can be explained as: at pH value 8.59.5, H2SiO3,
HSiO3 and gummy SiO2 (hydrolyzed from waterglass) were
selectively adsorbed on the gangue minerals, and made them
hydrophilic [42]. Further studies indicated that sodium silicate is
very effective on depression of titanium, zircon and other gangue
minerals and it is not effective on the monazite flotation.
The selective depression of monazite from bastnaesite was
practiced by using potassium alum. Potassium alum can efficiently
depress monazite at pH 5 without significant impact on the recov-
ery of bastnaesite with benzoic acid (CHO-the collector). The
depressing effect of potassium alum appeared to be due to the
preferential adsorption of hydrolyzed aluminum species (not from
potassium or sulfate) on monazite in comparison to bastnaesite.
Considering all the reported depressing effects, it can be con-
cluded that the common oxide and silicate depressants, sodium sil-
icate and sodium sulfide, do not significantly affect monazite
floatability in the presence of suitable collectors. In contrast these
depressants were selectively adsorbed at common gangue miner-
als (zircon and rutile), making them hydrophilic and improving
monazite flotation selectivity. The optimum concentrate of sodium
silicate in the present of different collectors (sodium oleate and
hydroxamate) and in the same condition, indicated better depres-
sion on gangue minerals in comparison with the optimum dosage
of sodium sulfide (Fig. 2).
3.3. Temperature
The effect of the conditioning temperature on the flotation of
REM was investigated mostly for selective separation of bastnaesite
[39,45]. In the selective separation of monazite with oleic acid in
Greenland (where generally water is 15 C), it was observed that
below 14 C the bubble adsorption took place slowly and the recov-
ery decreased [36]. Experimental results showed that an increase in
the conditioning temperature slightly decreased the bubble attach-
ment time (remaining constant after 64 C). An increase in oleate
concentration and temperature (from 24 C to 64 C) decreased
the bubble time attachment by 30% (11.27.9 ms) [46]. The effect
100
80
Recovery (%)
60
Monazite
Zircon
40
Rutile
20
0 100 200 300 400 500
Sodium metasilicate (mg/L)
(a)
Fig. 2. Floatability of monazite, zircon and rutile as a function of depressants concentration (a) sodium metasilicate, (b) sodium sulfide, 152 mg/L sodium oleate; pH = 10 [25].
Please cite this article in press as: Chelgani SC et al. A review of rare earth minerals flotation: Monazite and xenotime. Int J Min Sci Technol (2015), http://
dx.doi.org/10.1016/j.ijmst.2015.09.002
Gangue minerals pH Collector
Pyrochlore, zircon 6.7 Sodium oleate
Zircon 8.5 Sodium oleate
Zircon, rutil 10 Oleate and hydroxamate
Carbonates, silicates, oxides 8.59.5 Hydroxamate
of temperature on monazite recovery was investigated, in order
to determine optimum conditions of flotation with H205 (hydroxa-
mate collector). Results demonstrated that at pH 89 with increas-
ing temperature from 10 C to 50 C, the monazite recovery
decreased from 70% to 60% approximately [42].
Also effects of conditioning temperature on monazite flotation
(zircon, rutile and monazite system) were studied in the presence
of various reagents (collectors and depressants). Results indicated
that in the presence of sodium oleate, and sodium metasilicate at
pH 10, increasing the temperature (2070 C) slightly increased
the monazite recovery (13%), which was non-effective on zircon
and rutile recovery. With the same condition and in the presence
of commercial hydroxamate, increase in temperature decreased
monazite recovery (the rutile and zircon recoveries increased
slightly). But the increasing conditioning temperature in the pres-
ence of pure hydroxamate increased monazite recovery, and rutile
and zircon recoveries remained constant. Also it was reported that
monazite recovery in the presence of sodium sulfide and collectors
(sodium oleate and hydroxamate) improved with increasing tem-
perature [24]. Observation indicated that by increasing tempera-
ture in the presence of potassium octyl hydroxamate, generally
the recovery of the theses three minerals increased. Increasing
temperature from 21 C to 68 C improved monazite recovery by
40%. At 48 C, 130 mg/L and 300 mg/L of the collector showed the
same recovery (75%) [25].
4. Xenotime flotation
Xenotime is a widespread accessory mineral in many
rock-types, ranging from magmatic to sedimentary and metamor-
phic environments. It is more common in certain alkali magmatic
rocks, carbonates and in certain hydrothermal mineral deposits.
Xenotime lies at one end of a compositional solid-solution with
monazite, and basically represents a major source HREE (e.g. Eu
and Gd) [47,48]. Small quantities of the slightly larger light rare
earth elements (LREE) (La to Eu) may also be accommodated as
well [4951]. Froth flotation has been used to increase recovery
and grade of xenotime. Recovery of xenotime depends on pH,
flotation time, collector concentration, and temperature. Some
investigations indicated that xenotime is slightly more floatable
than monazite [10,15].
100
80
Recovery (%)
60
40
20
600 700 0 50 100 150 200 250 300
Sodium sulphide (mg/L)
(b)
 S.C. Chelgani et al. / International Journal of Mining Science and Technology xxx (2015) xxxxxx
4.1. Collector
Xenotime can typically be recovered in two flotation steps: first,
separating xenotime and monazite from associated gangue miner-
als (such as ilmenite, zircon, and silicates) by a reverse flotation,
and second, using direct flotation to separate xenotime from mon-
azite [23,5255]. Various collectors were used in these two steps.
Recent investigations observed that using anionic collectors pro-
vided a poor selectivity whereas amphoteric collector (F74286)
in acidic condition (pH 4.1) provided high selectivity toward sili-
cates and ilmenite in the first part [54].
Sodium oleate as a collector was as well used in xenotime
flotation. As the surface of xenotime is negatively charged above
the PZC (pH 3) sodium oleate can chemisorb above this point onto
the mineral. Results demonstrated that the collector adsorption on
a xenotime surface strongly depends on pH range; therefore, the
recovery of xenotime starts to fall at pH > 7, and drops sharply
from pH 5 [47].The optimum pH is 78. This phenomenon can be
explained by the oleate stability diagram results which indicated
that the concentration of oleate species (RCOO , (RCOO)22 and
(RCOO)2H ) decreased at pH values below 7 [22,56,57], and as a
result the collector adsorption on the surface of xenotime particles
would be stopped. By using the vibrating bubble apparatus it was
demonstrated that the recovery of xenotime is higher and the
probability of detachment is lower than for monazite, further
emphasizing the higher floatability of xenotime [47]. This result
was in agreement with the study conducted by Gross and Miller
who measured the bubble attachment time and reported 13.9 ms
and 18.9 ms for xenotime and monazite, respectively [46]. These
results also were confirmed by the chemical modeling of the
speciation of xenotime. It was found that the distribution of
the first hydroxyl rare earth species, RE(OH)2+, showed a good
correlation with the collector adsorption, bubble-particle adhesion
strength, and flotation results. Therefore, it was suggested that
the distribution of the first hydroxyl species is the key factor
in the flotation of xenotime with sodium oleate as a collector
[47].
Also hydroxamate was chosen to increase the selectivity in
xenotime separation (size range-212 + 106 lm). In the presence
of commercial hydroxamate (Flotinor V3759 Hoechst) at pH 10,
the recovery was above 90%. Hydroxamate does not change zeta
potential above the PZC (pH 3), and renders the zeta potential of
xenotime negative near and below the pH of PZC. Keeping the zeta
potential negative in the pH range 2.03.0 (close to PZC) is the
main role of hydroxamate which leads to a chemisorption mecha-
nism of this collector on xenotime surfaces [58].
Various collectors were examined in the second stage to sepa-
rate xenotime from monazite. In this stage at pH 10.6, F74286
(no more information is available about this reagent) can be used
to separate xenotime from monazite [54]. Also laboratory results
indicated that collectors with C1314 and two ethoxylation groups
(a mixture of ethylene oxide with alcohols and phenols) could
selectively separate xenotime from monazite [55]. In addition,
the effect of two collectors; dodecylamonium chloride (DAC) and
sodium dodecylsulfate (SDS) (with the same length of hydrocarbon
chain (hydrophobic entity)-C18) was examined for this separation
by flotation (150160 lm). Results demonstrated that for both
minerals the floatability has wider pH range for cationic collector
(DAC) in comparison with anionic collector (SDS). According to
the measured PZCs (5.5 for monazite and 7 for xenotime), the sep-
aration could mainly be controlled by the electrostatic interaction
between mineral surface and collector ions. Results indicated that
the separation of xenotime from monazite could be achieved at pH
7.5. Xenotime was concentrated in the roughing tail. Also, the
positive effect of ferric ion (Fe3+) on monazite flotation at low pH
rage (3) in the presence of FeCl3 was observed [23].
Please cite this article in press as: Chelgani SC et al. A review of rare earth minerals flotation: Monazite and xenotime. Int J Min Sci Technol (2015), http://
dx.doi.org/10.1016/j.ijmst.2015.09.002
5
Similar to monazite flotation, the reported investigations
demonstrate that xenotime is readily floatable with sodium oleate
as a collector in a certain pH range above the PZC (pH 57). Due to
the negatively charged xenotime surface in that range, a chemical
adsorption mechanism is suggested. Furthermore, selective
separation between xenotime and monazite could be possible by
considering the difference in PZC and controlling the electrostatical
interaction between mineral surface and collector.
4.2. Depressant
There is evidence that optimum amount of depressants can
improve the grade and recovery of xenotime through flotation
[55,58]. The effect of sodium silicate (Na2SiO3) and sodium fluo-
rosilicate (Na2SiF6) (to depress ilmenite, chromite, rotile, zircon,
and cassiterite) in the presence of fatty acid and phosphoric acid
esters throughout xenotime flotation was studied. The best selec-
tivity for both collectors was achieved at pH10 using Na2SiO3
depressant, but Na2SiF6 did not show significant improvement in
xenotime grade and recovery [55,56]. Various depressants (lignin
sulfonate, quebracho, conventional corn starch (RMB), amylopectin
(SIGMA), sodium metasilicate PA-weight ratio SiO2:Na2O = 1:1 for
zircon depression) were examined in flotation separation of xeno-
time from zircon [58]. Microflotation tests of samples in the pres-
ence of commercial hydroxamate as collector and the depressants
indicated that quebracho and amylopectin were effective on xeno-
time and decreased its recovery; whereas sodium silicate, starch,
and lignin sulfonate were effective only on zircon. Sodium silicate
as the strongest depressant decreased the zircon recovery whereas
the recovery of xenotime remained above 90% [58].
4.3. Temperature
Recent studies showed that in the constant concentration of
oleate (1  10 5) an increase in the conditioning temperature from
24 C to 64 C slightly decreased the bubble attachment time from
13.9 ms to 10.7 ms on xenotime (remain constant above 64 C).
And an increase in concentration of oleate decreased the bubble
attachment time to 3.9 ms [46]. In the same study, Cheng et al.
demonstrated that the xenotime recovery in the presence of
sodium oleate was decreased with increasing the conditioning
temperature (which it is not logical). They found that in high tem-
perature, the oleic acid species become more predominant at
higher pH (oleic acid is a weak acid with limited solubility:
16 mg/L at 25 C). The adsorption isotherm studies revealed that
the orientation of oleate molecules vertically adsorb to the xeno-
time surfaces at 25 C (having a cross-sectional area of 21 ), with
temperature rise the adsorption orientation mostly changes to flat
(having a cross-sectional area of 42 ). It was concluded that the
solubility of oleic acid decreased with increasing temperature,
and as a result, the recovery of xenotime at a higher temperature
decreased [47].
5. Conclusions
Rare earth mineral separation by flotation is a complex proce-
dure. The objective of this review was to present and identify the
effects of different flotation conditions on monazite and xenotime
flotation. From the available literature, it can be concluded that the
main reason for PZC differences in monazite and xenotime is
attributed to the different anion properties. It has been found that
any slight variation of the chemical composition of the mineral
surface is effective on the surface of these minerals. Several studies
indicated that monazite and xenotime have PZC values within the
acidic pH range (for pure minerals: pH 5.5 for monazite and pH 4
6 S.C. Chelgani et al. / International Journal of Mining Science and Technology xxx (2015) xxxxxx
for xenotime). The concentrations of collectors and depressants
must be well-defined to prevent a significant increase in the flota-
tion of gangue minerals. Both minerals are readily floatable using
anionic collectors such as sodium oleate. The highest floatability
of monazite grains in the presence of sodium oleate was observed
at pH 8, and for xenotime at pH 78. Hydroxamic acids increased
selectivity. The highest selectivity of monazite grains in the pres-
ence of hydroxamate was observed at pH 9, and for xenotime at
pH 10. Although hydroxamate indicated higher selectivity com-
pared to sodium oleate in monazite and xenotime flotation,
sodium oleate showed higher recoveries. The adsorption mecha-
nism of fatty acids and hydroxamates onto surface of monazite
and xenotime particles was established to be chemical in nature
and the selectivity adsorption of these collectors can increase with
increasing temperature. Sodium silicate is an efficient depressant
for most gangue minerals, in the presence of various collectors,
and affecting only slightly the floatability of monazite and xeno-
time. The effect of the conditioning temperature revealed that, in
some instances a higher temperature enhances the selectivity,
but in other cases the floatability of gangue minerals (such as zir-
con and rutile) is strongly improved as well. Size reduction
(increasing liberation), and PZC of monazite and xenotime are
the main keys for the separation of xenotime from monazite.
Results indicated that the separation of xenotime from monazite
could be achieved at pH 7.5, monazite was floated and xenotime
was concentrated in the roughing tail.
Acknowledgments
The authors would like to thank Sara Makaremi for editing and
proofreading the manuscript.
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