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

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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 Ó 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

(metals, group of metals or minerals) that are essential for many
Since the development of ion exchange and other extraction important emerging technologies of its regional industries and
methods, rare earth elements (REEs) have been extracted commer- one of the most critical situation seems to be that of REEs,
cially. The first industrial beneficiation from rare earth minerals especially the heavy REE (HREE) because of the Europe high import
(REMs) can be traced back to 1893 when thorium was extracted dependency rate, low substitution and low recycling rate, and no
from monazite, and was used in gas lamp mantles [1]. REEs are production within Europe [7]. In the same way, the US Department
used in many new electronic and advanced components (fuel cells, of Energy (DOE) published a technical document determining a
mobile phones, displays, high-capacity batteries, permanent mag- long-term strategy for REE materials which may be considered
nets for wind power generation, green energy devices, etc.) [2]. critical for the US economy showing a high risk of supply interrup-
Due to the high demand of REE in the last decades, their values tions [2,8].
have been increasing significantly [1]. From 1964 to 1997, the The main principal commercial REE mineral sources are the
REE market increased by a factor of 17, and it has increased by a following: bastnaesite [REE(CO3)]F (70–75% RE oxides), monazite
factor of 20.5 from 1997 to 2007 [3]. (REE)PO4 (55–60% RE oxides) and xenotime (REE)PO4 (55–60% RE
From 1990 to 2002, Mountain Pass and Bayan Obo provided oxides) [1–3]. Because of the complexity and the fine nature of
more than 80% of the world mining of REE resources. The Mountain the REE ore, flotation can be considered as one the most important
Pass deposit had been suspended for around 10 years, mainly due techniques to separate RE Minerals (REM) from associate minerals
to environmental problems associated with the disposal of and to produce the concentrates which usually contain 60–70% of
thorium-containing waste and now China produces about 90% of mixed REM [9–11].
the global supply of REEs [3–5]. Recently China has dominated In 2013, Kristian Waters’s research group at McGill University
the REE market, increased their export taxes and decreased the conducted an extensive literature review on various separation
trade (50,150 tons exported in 2009; decreased to 30,250 tons in techniques that are currently employed for REM beneficiation.
2010-around 40% decreases) [6]. This fact has greatly increased Their thorough review is focused on the current physical benefici-
REEs prices, causing tension and uncertainty among the world’s ation of bastnasite with regard to the unit operations employed,
high-tech markets [2]. Since June 2010, the European Commission and the processing plants. However, they highlighted the lack of
sufficient knowledge base for the separation of monazite and
⇑ Corresponding author. Tel.: +49 1745356532. xenotime by flotation, and the need for further research in this area
E-mail address: [email protected] (S.C. Chelgani). to provide a more complete insight into the development of

http://dx.doi.org/10.1016/j.ijmst.2015.09.002
2095-2686/Ó 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) xxx–xxx

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 [27–31].
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) [20,32–34], 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 mineral’s 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
(8.5–9) [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 1.1–3.2 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 1.1–3.2, 3.4, 6.1, 6.4, 9.0
imately the same recovery with 9–15% 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].
QEM–SEM 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. QEM–SEM 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) xxx–xxx 3

Table 3
Summary of various conditions in flotation of monazite.

References Collector pH Size Gangue minerals

Sorensen and Lundgaard [36] Sodium oleate 8 150 Silicate, sulfides, oxides
Dixit and Biswas [34] Sodium oleate 8.1–8.3 70 + 140 Ilmenite, zircon, rutile
Cheng et al. [10] Sodium oleate 8.5 5 Pure monazite
Pavez et al. [25] Sodium oleate 8 37 Silicate, oxides
Qi [38] Fatty acid-brytofa 9.8 37 + 74 Hematite, goethite, ilmenite
Liping [42] Hydroxamate 8–9 74 Barite, fluorite
Pavez et al. [25] Hydroxamate 9 37 Silicate, oxides
Pavez and Peres [32] Hydroxamate 7 37 Zircon, rutile

investigations hydroxamic acids were chosen to increase selectiv- surface properties of the associated minerals) (Table 4)
ity in REM flotation [37–41]. Several investigations demonstrated [8,19,20,24,37]. Sodium silicate, disodium sulfide, and sodium
the ability of hydroxamic acids to adsorb through a stable metallic oxalate are common depressants that are used for depression of
complex with cations (REE) on REM surfaces. Chemisorption of monazite associated minerals [8,16,24].
hydroxamates onto monazite was reported in various studies. As a depressant, disodium sulfide (Na2S) is used in the flotation
These studies suggested that the hydroxylated RE ions (i.e., RE of various minerals (sulfides and oxides). Na2S acts as a selective
(OH)2+ and RE(OH)2+) may adsorb on the REM surfaces and con- depressant in the flotation of REM with fatty acids. The hydrolysis
tribute to chemisorption [42]. The infrared spectrum of monazite of disodium sulfide and the presence of hydrosulfite and hydroxyl
after hydroxamate adsorption also indicated hydroxamate ions were reported as the main factors of depression. Flotation
chemisorption, with formation of a metallic hydroxamate bond results demonstrated that increasing the disodium sulfide concen-
[25]. tration effectively depressed pyrochlore and zircon and did not
Pavez and Peres [24] compared the capability of two different affect monazite flotation. Experimental results showed that the
hydroxamates in monazite particle ( 0.210 + 0.105 mm) flotation, depression was due to the effect of hydrosulfite ions, and not
and demonstrated that commercial hydroxamate (FLOTINOR hydroxyl ions. Sodium sulfide activates the surface of monazite
V3759) is a significantly stronger collector than the pure potassium grains due to the adsorption of S2 and SH ions and subsequent
octyl hydroxamate (CH3(CH2)6CONHO-K). The best floatability partial displacement of phosphate sites [8]. Infrared spectroscopy
range of monazite with V3759 was observed between pH 3 and and radiometric results indicated that the attached sulfur at mon-
pH 7 [32]. The separation processing of monazite from the beach azite surfaces was in oxidized form (due to strong oxidizing of RE
sand in Sao Goncalodo Sapucai (Brazil) was performed with cations) [37]. Furthermore these analyses suggest that SH is the
hydroxamate and sodium oleate as collectors and in the presence active agent of sodium sulfide to desorb the collector from the sur-
of sodium silicate (a depressant). Results demonstrated that the face of these gangue minerals [37].
selectivity of monazite flotation increased using a hydroxamate The effect of sodium silicate on the flotation of non-sulfidic
instead of a fatty acid (assays: 57.59% vs 49.07%). minerals is well-understood. The adsorption of hydrolysis products
All the reported investigations show that monazite can be read- of sodium silicate on the surface of minerals decreases their floata-
ily floated with fatty acid-based collectors (i.e. sodium oleate) as bility and depresses them [43]. Surface activation of monazite by
well as hydroxamic acid or hydroxamate based collectors in the sodium silicate was reported by Beloglazov and Osolodkov [44].
pH range above the PZC. With respect to the surface charge of In 1966, Sorensen and Lundgaard used sodium silicate as a pH
monazite (above the PZC), it is estimated that chemisorption is modifying reagent. They reported that sodium silicate caused a
the preferred adsorption mechanism of these collectors on the suppression of the collector adsorption on monazite surface [36].
monazite surface. From the investigations it can be concluded that Chan observed that with the use of Na2S and sodium silicate as
regarding selectivity, the use of hydroxamates showed the depressants and sodium oleate as a collector, the froth conditions
appropriate performance whereas sodium oleate indicated better and recovery of REM significantly improved. Based on these obser-
recovery in the same condition (Fig. 1). vations, further work was directed toward the development of a
selective Fe depressant. The addition of WW82/Quebracho as a sat-
3.2. Depressants isfactory iron depressant and pH modifier made it possible to
recover more than 60% of total REO at a concentrate grade of above
Generally, in flotation of REM, collector and depressant concen- 50% total REO [9].
trations must be well-defined. There is an agreement that the In 1993, Pavez and Peres reported that sodium meta-silicate is
selective flotation of monazite requires depressants (due to similar 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
100
90
in the presence of oleate and hydroxamate, disodium sulfide
80 slightly depresses monazite [24,35].
70 Also it was reported that in the presence and absence of sodium
Recovery (%)

60 silicate, the recovery of the monazite and its gangue minerals

50 changed from order (1) to order (2) [38]:
40 Sodium oleate
30 Hydroxamate (1) Apatite > monazite = hematite > ilmenite > Ca.
20
10
Fe phosphate > goethite.
1 2 3 4 5 6 7 8 9 10 11 12 (2) Apatite > monazite > Ca.
pH Fe phosphate > goethite = ilmenite > hematite.
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 It was concluded that sodium silicate depressed the flotation of
hydroxamate [25]). all the iron minerals to a greater extent than the phosphate

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
4 S.C. Chelgani et al. / International Journal of Mining Science and Technology xxx (2015) xxx–xxx

Table 4
Summary of various depressants for different gangue minerals in flotation of monazite.

References Depressant Gangue minerals pH Collector

Zakharov et al. [37] Sodium sulfide Pyrochlore, zircon 6.7 Sodium oleate
Abeidu [8] Sodium sulfide Zircon 8.5 Sodium oleate
Pavez and Peres [24,35] Sodium silicate Zircon, rutil 10 Oleate and hydroxamate
Liping [42] Na2O
SiO2 Carbonates, silicates, oxides 8.5–9.5 Hydroxamate

minerals [38]. Sodium silicate can also depress silicate minerals in of temperature on monazite recovery was investigated, in order
monazite flotation [40]. Liping reported that water–glass (a to determine optimum conditions of flotation with H205 (hydroxa-
compound containing sodium oxide and silica: Na2O
SiO2) is an mate collector). Results demonstrated that at pH 8–9 with increas-
ideal reagent to depress intergrowth minerals in monazite ores. ing temperature from 10 °C to 50 °C, the monazite recovery
The mechanism of the intergrowth minerals depression by decreased from 70% to 60% approximately [42].
water–glass can be explained as: at pH value 8.5–9.5, H2SiO3, Also effects of conditioning temperature on monazite flotation
HSiO3 and gummy SiO2 (hydrolyzed from water–glass) were (zircon, rutile and monazite system) were studied in the presence
selectively adsorbed on the gangue minerals, and made them of various reagents (collectors and depressants). Results indicated
hydrophilic [42]. Further studies indicated that sodium silicate is that in the presence of sodium oleate, and sodium metasilicate at
very effective on depression of titanium, zircon and other gangue pH 10, increasing the temperature (20–70 °C) slightly increased
minerals and it is not effective on the monazite flotation. the monazite recovery (1–3%), which was non-effective on zircon
The selective depression of monazite from bastnaesite was and rutile recovery. With the same condition and in the presence
practiced by using potassium alum. Potassium alum can efficiently of commercial hydroxamate, increase in temperature decreased
depress monazite at pH 5 without significant impact on the recov- monazite recovery (the rutile and zircon recoveries increased
ery of bastnaesite with benzoic acid (C₇H₆O₂-the collector). The slightly). But the increasing conditioning temperature in the pres-
depressing effect of potassium alum appeared to be due to the ence of pure hydroxamate increased monazite recovery, and rutile
preferential adsorption of hydrolyzed aluminum species (not from and zircon recoveries remained constant. Also it was reported that
potassium or sulfate) on monazite in comparison to bastnaesite. monazite recovery in the presence of sodium sulfide and collectors
Considering all the reported depressing effects, it can be con- (sodium oleate and hydroxamate) improved with increasing tem-
cluded that the common oxide and silicate depressants, sodium sil- perature [24]. Observation indicated that by increasing tempera-
icate and sodium sulfide, do not significantly affect monazite ture in the presence of potassium octyl hydroxamate, generally
floatability in the presence of suitable collectors. In contrast these the recovery of the theses three minerals increased. Increasing
depressants were selectively adsorbed at common gangue miner- temperature from 21 °C to 68 °C improved monazite recovery by
als (zircon and rutile), making them hydrophilic and improving 40%. At 48 °C, 130 mg/L and 300 mg/L of the collector showed the
monazite flotation selectivity. The optimum concentrate of sodium same recovery (75%) [25].
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 4. Xenotime flotation
of sodium sulfide (Fig. 2).
Xenotime is a widespread accessory mineral in many
3.3. Temperature rock-types, ranging from magmatic to sedimentary and metamor-
phic environments. It is more common in certain alkali magmatic
The effect of the conditioning temperature on the flotation of rocks, carbonates and in certain hydrothermal mineral deposits.
REM was investigated mostly for selective separation of bastnaesite Xenotime lies at one end of a compositional solid-solution with
[39,45]. In the selective separation of monazite with oleic acid in monazite, and basically represents a major source HREE (e.g. Eu
Greenland (where generally water is 1–5 °C), it was observed that and Gd) [47,48]. Small quantities of the slightly larger light rare
below 14 °C the bubble adsorption took place slowly and the recov- earth elements (LREE) (La to Eu) may also be accommodated as
ery decreased [36]. Experimental results showed that an increase in well [49–51]. Froth flotation has been used to increase recovery
the conditioning temperature slightly decreased the bubble attach- and grade of xenotime. Recovery of xenotime depends on pH,
ment time (remaining constant after 64 °C). An increase in oleate flotation time, collector concentration, and temperature. Some
concentration and temperature (from 24 °C to 64 °C) decreased investigations indicated that xenotime is slightly more floatable
the bubble time attachment by 30% (11.2–7.9 ms) [46]. The effect than monazite [10,15].

100 100

80 80
Recovery (%)
Recovery (%)

60 60
Monazite
Zircon 40
40
Rutile
20 20

0 100 200 300 400 500 600 700 0 50 100 150 200 250 300
Sodium metasilicate (mg/L) Sodium sulphide (mg/L)
(a) (b)

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://
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 S.C. Chelgani et al. / International Journal of Mining Science and Technology xxx (2015) xxx–xxx 5

4.1. Collector Similar to monazite flotation, the reported investigations

demonstrate that xenotime is readily floatable with sodium oleate
Xenotime can typically be recovered in two flotation steps: first, as a collector in a certain pH range above the PZC (pH 5–7). Due to
separating xenotime and monazite from associated gangue miner- the negatively charged xenotime surface in that range, a chemical
als (such as ilmenite, zircon, and silicates) by a reverse flotation, adsorption mechanism is suggested. Furthermore, selective
and second, using direct flotation to separate xenotime from mon- separation between xenotime and monazite could be possible by
azite [23,52–55]. Various collectors were used in these two steps. considering the difference in PZC and controlling the electrostatical
Recent investigations observed that using anionic collectors pro- interaction between mineral surface and collector.
vided a poor selectivity whereas amphoteric collector (F74286)
in acidic condition (pH 4.1) provided high selectivity toward sili- 4.2. Depressant
cates and ilmenite in the first part [54].
Sodium oleate as a collector was as well used in xenotime There is evidence that optimum amount of depressants can
flotation. As the surface of xenotime is negatively charged above improve the grade and recovery of xenotime through flotation
the PZC (pH 3) sodium oleate can chemisorb above this point onto [55,58]. The effect of sodium silicate (Na2SiO3) and sodium fluo-
the mineral. Results demonstrated that the collector adsorption on rosilicate (Na2SiF6) (to depress ilmenite, chromite, rotile, zircon,
a xenotime surface strongly depends on pH range; therefore, the and cassiterite) in the presence of fatty acid and phosphoric acid
recovery of xenotime starts to fall at pH > 7, and drops sharply esters throughout xenotime flotation was studied. The best selec-
from pH 5 [47].The optimum pH is 7–8. This phenomenon can be tivity for both collectors was achieved at pH10 using Na2SiO3
explained by the oleate stability diagram results which indicated depressant, but Na2SiF6 did not show significant improvement in
that the concentration of oleate species (RCOO , (RCOO)22 and xenotime grade and recovery [55,56]. Various depressants (lignin
(RCOO)2H ) decreased at pH values below 7 [22,56,57], and as a sulfonate, quebracho, conventional corn starch (RMB), amylopectin
result the collector adsorption on the surface of xenotime particles (SIGMA), sodium metasilicate PA-weight ratio SiO2:Na2O = 1:1 for
would be stopped. By using the vibrating bubble apparatus it was zircon depression) were examined in flotation separation of xeno-
demonstrated that the recovery of xenotime is higher and the time from zircon [58]. Microflotation tests of samples in the pres-
probability of detachment is lower than for monazite, further ence of commercial hydroxamate as collector and the depressants
emphasizing the higher floatability of xenotime [47]. This result indicated that quebracho and amylopectin were effective on xeno-
was in agreement with the study conducted by Gross and Miller time and decreased its recovery; whereas sodium silicate, starch,
who measured the bubble attachment time and reported 13.9 ms and lignin sulfonate were effective only on zircon. Sodium silicate
and 18.9 ms for xenotime and monazite, respectively [46]. These as the strongest depressant decreased the zircon recovery whereas
results also were confirmed by the chemical modeling of the the recovery of xenotime remained above 90% [58].
speciation of xenotime. It was found that the distribution of
the first hydroxyl rare earth species, RE(OH)2+, showed a good
4.3. Temperature
correlation with the collector adsorption, bubble-particle adhesion
strength, and flotation results. Therefore, it was suggested that
Recent studies showed that in the constant concentration of
the distribution of the first hydroxyl species is the key factor
oleate (1  10 5) an increase in the conditioning temperature from
in the flotation of xenotime with sodium oleate as a collector
24 °C to 64 °C slightly decreased the bubble attachment time from
[47].
13.9 ms to 10.7 ms on xenotime (remain constant above 64 °C).
Also hydroxamate was chosen to increase the selectivity in
And an increase in concentration of oleate decreased the bubble
xenotime separation (size range-212 + 106 lm). In the presence
attachment time to 3.9 ms [46]. In the same study, Cheng et al.
of commercial hydroxamate (Flotinor V3759 Hoechst) at pH 10,
demonstrated that the xenotime recovery in the presence of
the recovery was above 90%. Hydroxamate does not change zeta
sodium oleate was decreased with increasing the conditioning
potential above the PZC (pH 3), and renders the zeta potential of
temperature (which it is not logical). They found that in high tem-
xenotime negative near and below the pH of PZC. Keeping the zeta
perature, the oleic acid species become more predominant at
potential negative in the pH range 2.0–3.0 (close to PZC) is the
higher pH (oleic acid is a weak acid with limited solubility:
main role of hydroxamate which leads to a chemisorption mecha-
16 mg/L at 25 °C). The adsorption isotherm studies revealed that
nism of this collector on xenotime surfaces [58].
the orientation of oleate molecules vertically adsorb to the xeno-
Various collectors were examined in the second stage to sepa-
time surfaces at 25 °C (having a cross-sectional area of 21 Å), with
rate xenotime from monazite. In this stage at pH 10.6, F74286
temperature rise the adsorption orientation mostly changes to flat
(no more information is available about this reagent) can be used
(having a cross-sectional area of 42 Å). It was concluded that the
to separate xenotime from monazite [54]. Also laboratory results
solubility of oleic acid decreased with increasing temperature,
indicated that collectors with C13–14 and two ethoxylation groups
and as a result, the recovery of xenotime at a higher temperature
(a mixture of ethylene oxide with alcohols and phenols) could
decreased [47].
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 5. Conclusions
chain (hydrophobic entity)-C18) was examined for this separation
by flotation (150–160 lm). Results demonstrated that for both Rare earth mineral separation by flotation is a complex proce-
minerals the floatability has wider pH range for cationic collector dure. The objective of this review was to present and identify the
(DAC) in comparison with anionic collector (SDS). According to effects of different flotation conditions on monazite and xenotime
the measured PZCs (5.5 for monazite and 7 for xenotime), the sep- flotation. From the available literature, it can be concluded that the
aration could mainly be controlled by the electrostatic interaction main reason for PZC differences in monazite and xenotime is
between mineral surface and collector ions. Results indicated that attributed to the different anion properties. It has been found that
the separation of xenotime from monazite could be achieved at pH any slight variation of the chemical composition of the mineral
7.5. Xenotime was concentrated in the roughing tail. Also, the surface is effective on the surface of these minerals. Several studies
positive effect of ferric ion (Fe3+) on monazite flotation at low pH indicated that monazite and xenotime have PZC values within the
rage (3) in the presence of FeCl3 was observed [23]. acidic pH range (for pure minerals: pH 5.5 for monazite and pH 4

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://
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6 S.C. Chelgani et al. / International Journal of Mining Science and Technology xxx (2015) xxx–xxx

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