Minerals Engineering 71 (2015) 5564

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Minerals Engineering
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Beneciation studies of a complex REE ore

Xiaosheng Yang a,, Jacqueline V. Satur b, Kenzo Sanematsu b, Jukka Laukkanen a, Tuula Saastamoinen a
a
Mineral Processing Laboratory, Geological Survey of Finland, Outokumpu, Finland
b
Mineral Resources Research Group, Institute for Geo-Resources and Environment, National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan

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

Article history: The beneciations of a complex rare earth element (REE) ore containing REE minerals of carbonates, sil-
Received 2 May 2014 icates and oxides and other REE bearing minerals (e.g. zircon and pyrochlore etc.) by otation and high
Accepted 7 October 2014 gradient magnetic separation (HGMS) were investigated. The recoveries of the different group of minerals
Available online 27 November 2014
in the otation concentrates and their otation kinetics were analyzed through the mineralogical studies
by MLA. By otation nearly 90% of La and Ce and 45% of Y were recovered in the nal cumulative concen-
Keywords: trate with the mass percentage of 11.5%. The mineralogical studies indicated that over 95% of carbonates
Rare earth minerals
were recovered in the nal cumulative concentrate in which the recoveries of three major REE minerals
Flotation
Modal mineralogy
bastnaesite, parisite and synchysite reached over 96%. The recoveries of silicate REE minerals such as cer-
Mineral recovery ite(Ce) and allanite were quite high and reached 86% and 65%, respectively. The recoveries of Nb mineral
pyrochlore and Zr minerals zircon and elpidite were very low. HGMS was signicantly less selective in
recovering La and Ce but was effective in recovering Y. The ow sheet of roughercleaner otation and
the ow sheet of rougher otationcleaner HGMS were compared. The ow sheet of rougher otation
cleaner HGMS was showed to be more effective in recovery of Y.
2014 Elsevier Ltd. All rights reserved.

1. Introduction Currently, otation is still the most important beneciation

The rare earth (RE) minerals are numerous and can be classied
into six classes based on the arrangement of anionic groups such as
carbonate minerals bastnaesite and parisite, phosphate minerals
monazite and xenotime, and silicate mineral allanite. Meanwhile,
some minerals such as Nb-mineral pyrochlore could contain
substantial amounts of REEs. But about 95% of the world rare earth
resources occur in bastnaesite, monazite, and xenotime (Miyawaki
and Nakai, 1996) and by 2002 over 80% of the world rare earth
oxide (REO) production was from bastnaesite and 5% from mona-
zite (Gupta and Krishnamurth, 2005). Meanwhile, about 10% of
the world REO production from Chinas weathered crust elution
rare earth deposit or called ion adsorption rare earth ore which
occupies over 80% of the world total heavy RE reserve (Chi and
Tian, 2007). As the demands of RE materials in the world are
increasing (U.S. Geological Survey, 2002) more REE minerals
deposits will be in exploitation. For example, preliminary beneci-
ation tests have been carried out at Kvanefjeld REE deposit
containing steenstrupine as the main REE mineral in Greenland
and at Norra Krr REE deposit containing eudialyte as the main
REE mineral in Sweden.
Corresponding author at: Tutkijankatu 1, 83500 Outokumpu, Finland. Tel.: +358
50 348 6063; fax: +358 13 557 557.
E-mail address: Jason.yang@gtk. (X. Yang).
method used to recover bastnaesite, monazite, xenotime, parisite
and other RE minerals in the world by using different hydroxamic
acids and fatty acids as the collectors. The main RE minerals at
Bayan Obo REE-Nb-Fe deposit, the world largest REE deposit, are
bastnaesite and monazite. In the otation circuit naphthyl
hydroxamic acid is used as the collector of bastnaesite and mona-
zite at low alkaline condition (pH9) and temperature 3545 C
with the addition of sodium silicate as the depressant of silicates.
Bastnaesite and monazite separation is realized by further otation
using phthalic acid C6H4(CO2H)2 or benzoic acid C6H5COOH as the
collector of bastnaesite and alum as the depressant of monazite
(Yu, 2000). At the Mountain Pass deposit, another major REE
deposit in the world, the ore contains bastnaesite rich in cerium
group REEs and monazite associated with barite, calcite, strontian-
ite, chinalco and apatite etc. Flotation is used with six different
conditioning treatments at high solid percentage and high temper-
ature 7090 C with reagents added step-wise, soda ash as the pH
modier, sodium uosilicate as the depressant. Various collectors
such as fatty acids (oleic) (1982), distilled tall oil (fatty and rosin
acids), dicarboxylic acids (1985) and hydroxamates (1988) have
been used (Gupta and Krishnamurth, 2005). Additionally, otation
is also used for placer REE deposit ores to separate monazite and
xenotime from other minerals.

http://dx.doi.org/10.1016/j.mineng.2014.10.005
0892-6875/ 2014 Elsevier Ltd. All rights reserved.
56 X. Yang et al. / Minerals Engineering 71 (2015) 5564

Table 1
The contents of REEs in the ore sample by different chemical analysis methods.

Method La Ce Pr Nd Sm Eu Sc Gd Tb Dy Ho Er Tm Yb Y TREE HR/LR

(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
XRF 660.0 1060.0 280.0
ICP- 558.5 278.0
OES
ICP-MS 636.5 1095.0 126.5 489.0 87.0 4.6 <20 83.9 10.9 58.3 11.6 34.0 4.6 28.9 330.0 3000.6 18.7:
81.3

The bold value means the content of total REEs.

For carbonatite type of REE deposit ores the adsorption mecha-
nisms of hydroxamic acids and fatty acids as otation collectors on
REE minerals have been investigated. The research by Pradip and
Fuerstenau (1991) indicated that the chemical adsorption occurs
between fatty acid collectors and REE minerals for carbonatite type
of REE ores at high temperature with the addition of soda ash and
lignin sulfonate as modiers. Pavez et al. (1996) concluded that
sodium oleate chemisorbs onto the surface of bastnaesite and the
adsorption onto the surface of monazite depends on pH. In the
pH range above the isoelectric point the chemisorptions are possi-
ble. Otherwise, a physical adsorption occurs. However, for octyl
hydroxamate chemical adsorptions occur on both minerals. Assis
et al. (1996) reported that the selectivity of minerals by otation
with hydroxamates depends on a balance between the solubility
of the minerals and the stability of the complex formed between
the cation in the lattice and hydroxamate with the cation of the lat-
tice. A favourable condition for the selective utilisation of hydroxa-
mates as collectors is visualised if the mineral to be oated is the
most soluble in the system and the chelate formed between the
cation in the lattice and hydroxamate is the most stable.
For placer deposit ores the otation mechanisms by using
sodium oleate and hydroxamate as the collectors also have been
studied. Surface properties and otation behaviour of xenotime
using sodium oleate as a collector were investigated by Cheng
et al. (1994). It was found that the adsorption process on xenotime
surface is strongly pH dependent. As sodium oleate used as collec-
tor for otation of monazite and xenotime, the point of zero charge
(pzc) of monazite and xenotime occurs at pH 5.3 and pH 3.0, and
the maximum oatability of both minerals occurs at pH > 7 where
both are chemisorbed and xenotime is slightly more oatable than
monazite (Cheng et al., 1993). When sodium oleate and hydroxa-
mates were used as collectors for monazite, sodium metasilicate
and sodium sulphide as depressants for zircon (ZrSiO4) and rutile
(TiO2), the best selectivity condition (effective depression of zircon
and rutile and little effect on monazite) was achieved with either
oleate or commercial hydroxamate as collector at pH10. The effect
of the conditioning temperature was also studied, revealing that, in
some instances, a higher temperature enhances the selectivity, but
in other cases the oatability of zircon and rutile is more strongly
improved than that of monazite (Pavez and Peres, 1993).
As an important beneciation technique magnetic separation
has been applied in REE ore processing to eliminate ferromagnetic
minerals such as magnetite and other Fe-oxides prior to further
separation steps as well as to separate individual paramagnetic
REE minerals (Jordens et al., 2013). Wet low and medium intensity
magnetic separators are used in the beneciation of Chinas bast-
naesite REE ores to remove Fe-bearing minerals prior to otation
(Yu, 2000; Zhang and Edwards, 2012). Wet high intensity magnetic
separators are applied to REE placer deposits to separate paramag-
netic monazite and xenotime from non-magnetic heavy minerals
such as zircon and rutile (Gupta and Krishnamurth,2005; Jordens
et al., 2013; Zhang and Edwards, 2012). However, for the REE ores
with ne grain sizes (<100 lm) high gradient magnetic separation
(HGMS) has been approved to be a more effective method.
In this paper, the beneciations of a complex REE ore containing
REE minerals of carbonates, silicates and oxides and other REE
bearing minerals (e.g. zircon and pyrochlore etc.) by otation and
high gradient magnetic separation (HGMS) were investigated.
The recoveries of the different group of minerals in the otation
concentrates and their otation kinetics were analyzed through
the mineralogical studies by MLA. The owsheet of rougherclea-
ner otation and the owsheet of rougher otationcleaner HGMS
were compared.
2. Experimental
2.1. Sample and preparation
A drill core composite sample around 110 kg from the National
Institute of Advanced Industrial Science and Technology (AIST),
Japan, was received at GTK Mineral Processing Laboratory in Fin-
land. This is a REE-Zr-Nb ore consists of peralkaline granite intru-
sions inuenced by hydrothermal alteration. The outcropping
granites are relatively weathered and unweathered rocks found
below 30 m approximately from the surface.

Table 2
Modal mineralogy of the sample.

Silicate wt% Carbonate wt% Oxide and other wt%

K-feldspar 26.61 Parisitea 0.19 Fluorite 0.51
Albite 27.37 Bastnaesitea 0.12 Rutile 0.14
Quartz 33.34 Synchysite-Ya 0.02 Hematite 0.72
Arfevdsonite 7.57 Calcite 0.19 Ilmenite 0.05
Echemannite 0.74 Pyrochlorea 0.17
Gittinsitea 0.07 Chlorite 0.34
Britholitea 0.12 Unknown 0.48
Elpiditea 0.91
Zircona 0.34
Sum 97.07 0.52 2.41 100.00

The bold values mean the sum of percentages of minerals.

a
REE minerals and REE bearing minerals.
 X. Yang et al. / Minerals Engineering 71 (2015) 5564
Fig. 1. SEM images of REE minerals, bastnaesite, synchysite, parisite, britholite, pyrochlore and zircon.
The sample was crushed by a jaw and a roll crusher to 1.5 mm
and split into 1.5 kg amount of subsamples for otation and mag-
netic separation experiments. One of the subsamples was further
split into 100 g amount of samples for chemical and mineralogical
analyses.
2.2. Mineralogical analysis
A Mineral Liberation Analyzer (MLA) was used for mineralogical
analysis which consists of the standard modern SEM (FEI Quanta
600) with the energy dispersive X-ray analyzer (EDAX Genesis
with two detectors) and the software package developed originally
by JKTech (Australia). The modal mineralogy of the samples was
analyzed by the XMOD-STD method.
2.3. Flotation and reagents
Flotation experiments were carried out using an Outotec labo-
ratory otation machine. The samples of 1.5 kg with the size of
1.5 mm were ground at a laboratory rod mill as the head samples
for otation. The otation cells with the volumes of 4 and 1.5 liters
were used in the rougher and cleaner otation, respectively. Tap
water was used for wet grinding and otation. The room tempera-
ture (2023 C) was applied for otation conditioning.
Hydroxamate type of reagent Aero6494, fatty acid type of
reagent Aero704 and sulfosuccinamate type of reagent Aero 845
from Cytec and sodium oleate (Na-oleate) powder (P82 wt% fatty
acids as oleic acid) manufactured by SigmaAldrich were tested as
the collectors. Sodium silicate (Na2SiO3) and starch were used as
the depressants of silicate minerals during otation. Aero 6494,
Aero 704 and Aero 845 were used without dilution and sodium
oleate was diluted into 5 wt% solution for use. The value of pH
was adjusted by using soda ash and sulfuric acid.
57
2.4. High gradient magnetic separation (HGMS)
A laboratory high gradient magnetic separator (Sala HGMS 10-
15-20 SCR) was used for the magnetic separation experiments. The
matrix type used was 3.5 XRO with the aperture size of 850 lm.
The HGMS experiment consisting of one rougher and one scaven-
ger was carried out at the magnetic intensities of 0.05 T and 0.3
T, respectively. Additionally, HGMS was used as the cleaner for
the concentration of otation rougher concentrate. Three times of
cleaning by HGMS were applied at the intensities of 2.0, 0.5, and
0.05 T.
3. Results and discussion
3.1. Chemical analysis
Chemical analyses of the sample by XRF, ICP-OES and ICP-MS
were conducted at Labtium Oy Finland. The contents of rare earth
elements (REEs) by different chemical analysis methods are shown
in Table 1. The content of total REEs (TREE) by ICP-MS is 3000 ppm
or 0.3% in which the content of the heavy REEs (Gd to Y) is 562 ppm
or 0.056%. The ratio of the heavy REEs to the light REEs is 18.7
81.3%.
3.2. Modal mineralogy
The data of modal mineralogy of the sample are shown in
Table 2. A total of 20 minerals were identied by MLA in which sil-
icates take up 97.1%, carbonates 0.52%, and oxides and other min-
erals 2.41% in mass. The identied REE minerals and REE-bearing
minerals are parisite, bastnaesite, synchysite-(Y), pyrochlore, git-
tinsite, britholite, elpidite and zircon. REEs are distributed not only
in carbonates and oxides (parisite, bastnaesite, synchysite-(Y),
58 X. Yang et al. / Minerals Engineering 71 (2015) 5564

Table 3
REE otation performance comparison at the grinding size of P80 = 50 lm and 80 lm.

Collector Grinding size, P80 lm La Ce Y REE (La, Ce, Y)

% Rec% % Rec% % Rec% % Rec%
Aero 704, 845a 50 0.37 55.76 0.61 56.65 0.09 30.56 1.07 52.42
80 0.41 57.63 0.66 57.98 0.10 30.13 1.16 53.76
Aero 6494a 50 0.12 52.49 0.19 53.50 0.03 36.66 0.34 50.81
80 0.11 54.60 0.17 55.14 0.03 38.20 0.32 52.53
a
Dosage 200 g/t.

pyrochlore) but also in silicate minerals (gittinsite, britholite, elpi-
dite and zircon). Light REEs are mainly contained in carbonate min-
erals (parisite, bastnaesite) and silicate mineral (britholite) while Y
and heavy REEs are mainly contained in Zr silicate minerals (zir-
con, elpidite, gittinsite), Nb mineral (pyrochlore) and carbonate
mineral (synchysite-(Y)).
The SEM images of REE minerals in Fig. 1 show the appearance
of bastnaesite, synchysite, parisite, britholite, pyrochlore and zir-
con in ne grains.
of collectors varied in the range of 70200 g/t the different ota-
tion recoveries of the total REE (La, Ce, Y) were obtained. The
curves of the grade versus recovery of REE (La, Ce, Y) in the concen-
trate for different collectors are shown in Fig. 2. It was demon-
strated that higher recovery and grade of REE (La, Ce, Y) were
obtained by using Na-oleate as the collector. That is, comparing
with Aero 704, 845 and Aero 6494, Na-oleate was more selective
for REE otation for this ore.

3.3.3. Depressant dosage

3.3. Determination of otation conditions
Because of the high content of silicates in the ore the depression
of silicate minerals is important for REE otation. Two levels of
3.3.1. Grinding size
300 g/t and 50 g/t of Na2SiO3 dosage were tested using Na-oleate
The previous mineralogical analyses by AIST in Japan on the
as the collector. The otation results were shown in Fig. 3. It is
grain size of REE minerals in the ore have shown that the reason-
obvious that higher grade and recovery of REE (La, Ce, Y) in ota-
able grinding size for the beneciation would be around 80% pass-
tion concentrates were obtained at dosage 300 g/t than 50 g/t.
ing 50100 lm. To select a suitable grinding size the otation tests
By the otation experiments discussed above on the grinding
were carried out at the grinding size of P80 = 50 lm and
size, collector type and Na2SiO3 dosage the otation conditions
P80 = 80 lm by using Aero 704, 845 (in the ratio 1:1) and Aero
were determined: grinding size P80 = 80 lm, collector Na-oleate
6494 as the collectors at the dosage of 200 g/t and Na2SiO3 as the
at dosage 200300 g/t and depressant Na2SiO3 at dosage 300 g/t.
depressant at the dosage of 300 g/t. The desliming of 20 lm by
Starch could be added to improve the depression of Fe-oxides.
the hydrodynamic settling method was applied before otation.
The results showed in Table 3 indicated that the otation perfor-
mances of the REE minerals at the two grinding sizes were not
3.4. Rougher otation and results
obviously different.
The rougher otation experiment was carried out at the grind-
3.3.2. Collector type ing size of P80 = 80 lm. The particle size distribution of the feed
To select a proper collector the otation tests using Aero 704, measured by a laser sizer is shown in Table 4. Na-oleate was used
845 (in the ratio of 1:1), Na-oleate and Aero 6494 as the collectors as the collector at the dosage of 270 g/t and Na2SiO3 and starch as
were carried out in the presence of sodium silicate (Na2SiO3) as the the silicate depressants at the dosages of 300 g/t and 150 g/t. The
depressant. The grinding size was P80 = 50 lm and the tempera- otation pH was natural in 8.89.3 and the pulp temperature for
ture during pulp conditioning was at 2023 C. When the dosages conditioning and otation was at 2023 C.

Fig. 2. Effect of collector type on the otation of REE (La, Ce, Y).
 X. Yang et al. / Minerals Engineering 71 (2015) 5564 59

Fig. 3. Effect of Na2SiO3 on the otation of REE (La, Ce, Y).

Table 4
The weights of cumulative concentrates and the grades and
Particle size distribution of the feed. recoveries of elements in the cumulative concentrates calculated
from the experimental data in Table 5 are shown in Table 6.
Particle size, lm 3.19 12.40 38.88 72.79 81.18 103.90
Cumulative percentage, 10.00 20.00 50.00 75.00 80.00 90.00
The mass percentage of the nal cumulative concentrate Conc
vol.% (1,2,3,4,5,6) was 11.5%. Nearly 90% of La and Ce were recovered
but the recovery of Y was only 42%. The relationships of grade ver-
sus recovery of La, Ce and Y in the cumulative concentrates are
shown in Fig. 6.
The ow sheet of the experiment is shown in Fig. 4. The total
otation time was 28 min. Six froth concentrates (concentrate 1
6) were respectively pulled in the otation periods of 02 min,
3.5. Mineralogical studies of otation products
24 min, 46 min, 69 min, 914 min, and 1428 min and the tail
was the material left in the cell. The otation products of Conc 16
In order to investigate the otation recoveries and kinetics of
and Tail were ltered, tried, weighed and sent for assay by XRF. The
different minerals, the mineralogical analyses by MLA were con-
recoveries of elements in the products were calculated based on
ducted on the concentrates 1, 3 and 5 and the tail. The modal min-
the weights and assays. The element contents of the feed were
eralogy of these three concentrates and the tail were obtained.
recalculated based on the data of products. All the experimental
Based on the trend lines of mineral contents in otation products
data are shown in Table 5.
versus otation time the modal mineralogy of concentrates 2, 4
For analyzing the experimental errors the element contents of
and 6 were achieved by calculation. The modal mineralogy of all
the feed by XRF (Analysis feed) are listed in Table 5. The standard
the concentrates and the tail are shown in Table 7.
deviation (SD) between the calculated feed (X1) and the analysis
Comparing the data in Table 7 with the modal mineralogy of ore
feed (X2) was determined by
in Table 2 all the major identied minerals and REE minerals are
r consistent. But some silicate minerals such as smectite, garnet,
1 X and allanite, and carbonate mineral siderite, were not identied
SD X i  X m 2;
21 in the analysis of ore. Among them allanite is a REE mineral.
It is revealed in Table 7 that as the increase of otation time the
where Xm is the mean value of X1 and X2. grades of carbonate and oxide minerals decrease and the grades of
The standard deviations between the calculated feed and the silicate minerals increase in the otation concentrates from con-
analysis feed on La, Ce and Y are shown in Fig. 5. centrate 1 to concentrate 6.

Fig. 4. Flow sheet of rougher otation.

60 X. Yang et al. / Minerals Engineering 71 (2015) 5564

Table 5
Assays of the otation products and the calculated feed.

Product Weight La Ce Y Fe SiO2 ZrO2 C

g % ppm Rec% ppm Rec% ppm Rec% % Rec% % Rec% % Rec% % Rec%
Conc 1 21.10 1.41 19,400 44.80 31,000 43.50 2190 11.16 3.00 1.20 22.30 0.43 0.29 1.17 2.97 19.10
Conc 2 20.30 1.35 8600 19.11 14,200 19.17 1630 7.99 4.52 1.73 37.00 0.69 0.45 1.73 2.04 12.62
Conc 3 16.30 1.09 5100 9.10 8500 9.21 1350 5.32 5.57 1.71 46.00 0.68 0.57 1.77 1.79 8.89
Conc 4 19.10 1.27 2810 5.87 4680 5.94 1010 4.66 6.08 2.19 56.60 0.99 0.60 2.18 1.21 7.05
Conc 5 31.10 2.07 1460 4.97 2480 5.13 750 5.63 6.67 3.92 64.20 1.82 0.63 3.73 0.82 7.77
Conc 6 64.50 4.30 642 4.53 1093 4.69 482 7.51 6.39 7.78 69.24 4.08 0.55 6.74 0.50 9.81
Tail 1327.80 88.51 80 11.62 140 12.36 180 57.73 3.25 81.47 75.30 91.31 0.33 82.67 0.09 34.76
Calcd feed (X1) 1500.20 100.00 609 100.00 1002 100.00 276 100.00 3.53 100.00 72.99 100.00 0.35 100.00 0.22 100.00
Analysis feed (X2) 660 1060 280 3.16 73.90 0.35 0.21
Standard deviation (SD) 36.00 40.73 2.85 0.26 0.64 0.00 0.01

had not only high recoveries of over 96% in the nal cumulative
concentrate but also high otation kinetics. At the time of 6 min
their recoveries reached 8190%. After the otation of carbonate
REE minerals two silicate REE minerals of cerite(Ce) and allanite
were oated at slower kinetics. The recoveries of cerite(Ce) and
allanite reached 79% and 48% at the otation time of 15 min. How-
ever, the recoveries of one Nb mineral pyrochlore and two Zr min-
erals zircon and elpidite were very low and their otation kinetics
were the slowest. Because these minerals are the main bearing
minerals of Y and other heavy REEs the low recoveries of them
caused the low recoveries of Y and other heavy REEs in
concentrates.

3.6. High gradient magnetic separation (HGMS)

Fig. 5. Standard deviations between the calculated feed and the analysis feed on La,
Ce and Y.
As shown in Table 8 the recoveries of minerals in the cumula-
tive concentrates at different otation times were calculated based
on the modal mineralogy in Table 7 and the mass percentages of
otation products. Over 95% of carbonates were recovered in nal
cumulative concentrate in which the recoveries of three major REE
minerals bastnaesite, parisite, synchysite and synchysite-(Y)
reached over 96%. Meanwhile, very high recoveries of calcite and
siderite (94% and 92% respectively) were obtained in the nal
cumulative concentrate. The recovery of uorite reached as high
as 98% but the recoveries of other oxide minerals such as pyroch-
lore and Fe-oxide were below 30%.
Although the recoveries of major silicates minerals quartz, pla-
gioclase, K-feldspar and arfvedsonite were quite low in the range of
717% those of silicate REE minerals such as cerite(Ce) and allanite
were quite high and reached 86% and 65%. This means the collector
Na-oleate was quite selective for the recovery of silicate REE min-
erals from other major silicates.
The recoveries of different REE minerals in cumulative concen-
trates at different times are shown in Fig. 7. The carbonate group of
REE minerals (bastnaesite, parisite, synchysite and synchysite-(Y))
As shown in Fig. 6 the recovery of Y in the rougher otation con-
centrate was only 45%. The poor recovery of Y can be explained by
the poor recoveries of Y bearing minerals pyrochlore, zircon and
elpidite as discussed above.
A high gradient magnetic separation (HGMS) experiment was
carried out. The matrix type of 3.5 XRO with the aperture size of
850 lm was used. Two stages of rougher and scavenger separa-
tions were applied at the intensities of 0.05 T and 0.3 T, respec-
tively. The rougher and scavenger magnetic concentrates were
combined as the nal concentrate. The recoveries of La, Ce and Y
versus concentrate mass for otation and HGMS are shown in
Fig. 8. Comparing to otation HGMS was signicantly less selective
for recoveries of La and Ce. Only 74.7% recovery of La and Ce was
obtained at a high mass percentage (35.8%). But the recovery of Y
reached 67.1%. That is, HGMS could be more selective for the
recoveries of pyrochlore, zircon and elpidite than otation using
Na-oleate as the collector.
3.7. Cleaning process and comparison of ow sheets
Although the results of HGMS could be improved by optimizing
the conditions it is not capable to replace otation at rougher stage
due to low La and Ce recoveries and grades. After rougher otation

Table 6
Weights of cumulative concentrates, and grades and recoveries of elements in the cumulative concentrates.

Cumulative conc Weight La Ce Y Fe SiO2 ZrO2 C

g % % Rec% % Rec% % Rec% % Rec% % Rec% % Rec% % Rec%
Conc 1 21.10 1.41 1.94 44.80 3.10 43.50 0.22 11.16 3.00 1.20 22.30 0.43 0.29 1.17 2.97 19.10
Conc (1,2) 41.40 2.76 1.41 63.90 2.28 62.67 0.19 19.15 3.75 2.93 29.51 1.12 0.37 2.90 2.52 31.72
Conc (1,2,3) 57.70 3.85 1.16 73.00 1.87 71.88 0.18 24.47 4.26 4.64 34.17 1.80 0.43 4.67 2.31 40.61
Conc (1,2,3,4) 76.80 5.12 0.94 78.87 1.52 77.82 0.16 29.13 4.71 6.83 39.75 2.79 0.47 6.86 2.04 47.66
Conc (1,2,3,4,5) 107.90 7.19 0.71 83.84 1.16 82.95 0.13 34.76 5.28 10.75 46.79 4.61 0.52 10.59 1.69 55.43
Conc (1,2,3,4,5,6) 172.40 11.49 0.47 88.38 0.76 87.64 0.10 42.27 5.69 18.53 55.19 8.69 0.53 17.33 1.24 65.24
 X. Yang et al. / Minerals Engineering 71 (2015) 5564 61

Fig. 6. Relationships of grade versus recovery of La, Ce and Y in cumulative concentrates.

Table 7
Modal mineralogy of otation products by MLAa.

Mineral Product Conc 1 Conc 2 Conc 3 Conc 4 Conc 5 Conc 6 Tail Feed
Flotation time, min 02 24 46 69 914 1428 >28
Silicate Quartz 7.48 15.81 18.80 23.45 26.33 32.03 35.54 33.34
Plagioclase (Albite) 6.01 12.21 15.00 17.06 20.59 22.51 23.06 27.37
K-felspar 4.15 7.26 10.75 12.41 15.80 23.56 26.91 26.61
Arfvedsonite 4.07 7.81 11.07 14.16 17.46 16.88 8.68 7.57
Gittinsite 0.07
Smectite 1.92 4.22 5.68 6.54 6.18 4.72 3.64
Garnet 0.68 0.91 1.00 0.93 0.61 0.27 0.02
Cerite(Ce) (Britholite) 1.68 1.34 1.02 0.70 0.29 0.13 0.01 0.12
Allanite 0.21 0.19 0.17 0.19 0.18 0.11 0.01
Zircon 0.58 0.89 1.10 1.20 1.17 0.75 0.45 0.34
Elpidite 0.15 0.24 0.33 0.35 0.42 0.51 0.52 0.91
Other 0.02 0.03 0.04 0.01 0.74
Total 26.95 50.88 64.95 76.98 89.07 101.74 98.84 97.07
Carbonate Calcite 16.09 11.22 7.56 4.47 2.12 0.93 0.04 0.19
Siderite 1.43 2.16 2.43 2.25 1.14 0.49 0.02
Bastnaesite(Ce) 9.52 4.81 1.65 0.40 0.23 0.10 0.01 0.12
Parisite 4.93 3.39 1.67 1.25 0.28 0.12 0.00 0.19
Synchysite(Y) 0.39 0.26 0.12 0.09 0.02 0.01 0.00 0.02
Synchysite(Ce) 3.24 1.52 0.45 0.34 0.15 0.06 0.00
Other 0.04 0.13 0.10 0.01
Total 35.63 23.37 14.01 4.04 1.71 0.08 0.52
Oxide and other Fluorite 34.52 24.61 16.86 9.83 3.48 1.49 0.03 0.51
Pyrochlores 0.26 0.30 0.36 0.30 0.26 0.19 0.08 0.17
Fe-oxide 0.94 1.25 1.65 1.52 1.47 1.20 0.43 0.72
Other 1.70 2.18 1.68 0.54 1.01
Total 37.42 26.16 21.05 6.89 2.88 1.08 2.41
REE
La 1.94 0.86 0.51 0.28 0.15 0.06 0.01 0.06
Ce 3.10 1.42 0.85 0.47 0.25 0.11 0.01 0.10
a
Flotation conditions: Na-oleate 270 g/t, Na2SiO3 300 g/t, starch 150 g/t, pH 8.89.3. Unit of mineralogy: wt%.

the combined concentrate of Conc 1,2,3,4,5,6 was respectively
cleaned by otation and HGMS. The ow sheet is shown in Fig. 9.
In the cleaner otation Na-oleate was used as the collector and
three time cleaners were applied. In the cleaner HGMS stage three
time cleaners were applied at the intensities of 2.0, 0.5 and 0.05 T
and the matrix type was 3.5 XRO with the aperture size of 850 lm.
The testwork results for the two ow sheets are shown in Fig. 10.
The recoveries of La and Ce were 6873% and not obviously
different for the two ow sheets. The grade of La plus Ce reached
4.2%. But the ow sheet of otationHGMS was showed to be
more effective for recovery of Y. That is, comparing to the ow
sheet of otationotation a higher recovery of Y was obtained
by the ow sheet of otationHGMS at the same recovery of La
and Ce.
The assays of the two cleaned concentrates from the ow sheets
of otationotation and otationHGMS are shown in Table 9.
The grades of REE (La, Ce, Y) for the two ow sheets were 4.9%
and 4.5%, respectively, at the recoveries of 53.9% and 67.4%. The
62 X. Yang et al. / Minerals Engineering 71 (2015) 5564

Table 8
Recoveries of minerals in cumulative concentrates.

Conc 1 Conc 1,2 Conc 1,2,3 Conc 1,2,3,4 Conc 1,2,3,4,5 Conc 1,2,3,4,5,6 Calcd feed
wt% Rec% wt% Rec% wt% Rec% wt% Rec% wt% Rec% wt% Rec% wt% Rec%
Quartz 7.48 0.31 11.56 0.93 13.61 1.53 16.05 2.40 19.02 4.00 23.89 8.03 34.20 100.00
Plagioclase 6.01 0.38 9.05 1.11 10.73 1.84 12.31 2.81 14.69 4.71 17.62 9.03 22.43 100.00
K-felspar 4.15 0.23 5.67 0.61 7.11 1.07 8.42 1.69 10.55 2.97 15.42 6.92 25.59 100.00
Arfvedsonite 4.07 0.62 5.91 1.77 7.36 3.07 9.05 5.02 11.48 8.94 13.50 16.81 9.23 100.00
Smectite 1.92 0.71 3.05 2.23 3.79 3.86 4.48 6.06 4.97 9.45 4.87 14.81 3.78 100.00
Garnet 0.68 11.14 0.79 25.59 0.85 38.37 0.87 52.31 0.80 67.16 0.60 80.76 0.09 100.00
Cerite(Ce) 1.68 27.69 1.51 48.83 1.37 61.72 1.21 72.11 0.94 79.10 0.64 85.65 0.09 100.00
Allanite 0.21 10.29 0.20 19.59 0.19 26.10 0.19 34.48 0.19 47.55 0.16 64.75 0.03 100.00
Zircon 0.58 1.62 0.73 4.03 0.83 6.41 0.92 9.47 0.99 14.32 0.90 20.80 0.50 100.00
Elpidite 0.15 0.42 0.19 1.06 0.23 1.78 0.26 2.67 0.31 4.38 0.38 8.76 0.50 100.00
Silicate 26.93 0.39 38.67 1.11 46.09 1.84 53.77 2.85 63.93 4.77 77.98 9.29 96.43 100.00
Calcite 16.09 35.37 13.70 59.09 11.97 71.93 10.10 80.83 7.80 87.71 5.23 93.93 0.64 100.00
Siderite 1.43 12.39 1.79 30.42 1.97 46.68 2.04 64.30 1.78 78.80 1.30 91.78 0.16 100.00
bastnaesite(Ce) 9.52 55.87 7.21 83.04 5.64 90.52 4.34 92.64 3.15 94.64 2.01 96.51 0.24 100.00
Parisite 4.93 42.32 4.18 70.35 3.47 81.40 2.91 91.10 2.15 94.61 1.39 97.76 0.16 100.00
Synchysite(Y) 0.39 44.09 0.33 72.85 0.27 83.33 0.23 92.93 0.17 96.69 0.11 100.00 0.01 100.00
Synchysite(Ce) 3.24 56.13 2.40 81.54 1.85 87.63 1.47 92.91 1.09 96.68 0.71 100.00 0.08 100.00
Carbonate 35.59 38.53 29.60 62.87 25.16 74.48 21.09 83.11 16.15 89.39 10.75 95.06 1.30 100.00
Fluorite 34.52 37.65 29.66 63.48 26.05 77.69 22.01 87.40 16.67 92.99 10.99 97.98 1.29 100.00
Pyrochlores 0.26 3.68 0.28 7.70 0.30 11.55 0.30 15.38 0.29 20.79 0.25 28.86 0.10 100.00
Fe-oxide 0.94 2.51 1.09 5.73 1.25 9.14 1.32 12.82 1.36 18.61 1.30 28.41 0.53 100.00
Oxide and other 35.72 26.22 31.04 44.70 27.60 55.40 23.63 63.14 18.32 68.78 12.55 75.25 1.92 100.00

The bold values mean the sum of percentages of silicate group minerals, the sum of percentages of carbonate group minerals and the sum of percentages of oxide and other
group minerals.

Fig. 7. Recoveries of REE minerals in cumulative concentrates versus otation time.

Fig. 8. Recoveries of REE (La, Ce) and Y versus concentrate mass for otation and HGMS.
 X. Yang et al. / Minerals Engineering 71 (2015) 5564 63

Fig. 9. Flow sheet of cleaning.

Fig. 10. La plus Ce and Y grade versus recovery for roughercleaner otation ow sheet and rougher otationcleaner HGMS ow sheet.

Table 9
Assays of the concentrates from ow sheets of otationotation and otationHGMS.

Element La Ce Y REE (La, Ce, Y) Fe SiO2 Al2O3 ZrO2 C

% Rec% % Rec% % Rec% % Rec% % Rec% % Rec% % Rec% % Rec% % Rec%
FlotationFlotation conc 1.76 59.30 2.85 60.50 0.24 17.98 4.85 53.85 2.72 1.62 11.50 0.33 1.11 0.23 0.38 2.27 3.47 35.19
FlotationHGMS conc 1.59 72.84 2.60 75.07 0.27 27.92 4.45 67.40 12.48 10.10 37.06 1.44 4.76 1.36 0.86 7.02 3.19 44.08
Feed 0.06 100.00 0.10 100.00 0.03 100.00 0.19 100.00 3.51 100.00 73.09 100.00 9.94 100.00 0.35 100.00 0.21 100.00

grade of REE (La, Ce, Y) in the ore from Table 1 was 0.19%. So that,
the enrichment ratios for the two processes were 25.7 and 23.7,
respectively. These are quite high values of beneciation enrich-
ment for this type of complex ore.
Table 9 also indicates that the both concentrates had high con-
tents of C and the otationHGMS concentrate had a high content
of Fe. That is, calcite and Fe-oxides were also concentrated in the
cleaned concentrates. To further increase the grade of REE in the
concentrates calcite and Fe-oxides should be eliminated. Further
otation by using more selective collectors or properly controlling
pH value could be effective to remove calcite and further magnetic
separation by adjusting the magnetic intensity or gradient could
work to decrease the content of Fe-oxides.
Acid leaching (sulfuric or hydrochloric acids) at high concentra-
tion after roasting (200400 C) could be used for the downstream
metallurgical processing of the concentrates. REE carbonate miner-
als (bastneasite, parisite etc.) should be dissolved in the acids at
high recoveries. Due to high content of calcite a pre-leaching with
diluted HCl at room temperature may be needed to dissolve calcite
and purify the material prior to REE leaching. The leachability of
REEs in silicate minerals may be low and the caustic pre-treat-
ments with calcium hydroxide or sodium hydroxide should be
needed to transform them into soluble salts prior to leaching.
4. Conclusions
Using Na-oleate as the collector at the dosage of 270 g/t and
Na2SiO3 and starch as the silicate depressants at the dosages of
300 g/t and 150 g/t, nearly 90% of La and Ce were recovered but
the recovery of Y was 45% in the nal cumulative concentrate with
the mass percentage of 11.5%. The mineralogical studies indicated
that over 95% of carbonates were recovered in the nal cumulative
concentrate in which the recoveries of three major REE minerals
bastnaesite, parisite and synchysite reached over 96%. They
showed also high otation kinetics. At the otation time of 6 min
their recoveries reached 8190%. Meanwhile, the recoveries of
silicate REE minerals such as cerite(Ce) and allanite were quite
high and reached 85.6% and 64.7%, respectively. Their otation
kinetics was slower than that of carbonate REE minerals and the
recoveries of cerite(Ce) and allanite reached 79.1% and 47.6% at
the otation time of 15 min. However, the recoveries of Nb mineral
pyrochlore and Zr minerals zircon and elpidite were very low.
The cumulative concentrate of otation was cleaned by ota-
tion and high gradient magnetic separation HGMS. The grades of
REE (La, Ce, Y) for the two ow sheets were 4.9% and 4.5%, respec-
tively, at the recoveries of 53.9% and 67.4%. The enrichment ratios
for the two processes were 25.7 and 23.7 for the beneciation of
64 X. Yang et al. / Minerals Engineering 71 (2015) 5564
REE (La, Ce, Y). Comparing the results by the two ow sheets a
higher recovery of Y was obtained by the ow sheet of otation
HGMS at the same recovery of La and Ce.
References
Assis, S.M. et al., 1996. Utilisation of hydroxamates in minerals froth otation.
Miner. Eng. 9 (1), 103114.
Cheng, Ta-Wui, Holtham, P.N., Tran, Tam, 1993. Froth otation of monazite and
xenotime. Miner. Eng. 6 (4), 341351.
Cheng, Ta-Wui et al., 1994. The surface properties and otation behavior of
xenotime. Miner. Eng. 7 (9), 10851098.
Chi, Ruan, Tian, Jun, 2007. Introduction of weathered crust elutiondeposited rare
earth ore. J. Chinese Rare Earth Soc. 25 (6), 641649 (Chinese).
Gupta, C.K., Krishnamurth, N., 2005. Extractive Metallurgy of Rare Earths. CRC Press.
Jordens, A., Cheng, Y.P., Waters, K.E., 2013. A review of the beneciation of rare
earth element bearing minerals. Miner. Eng. 41, 97114.
Miyawaki, R., Nakai, I., 1996. Crystal chemical aspects of rare earth minerals. In:
Jones, Adrian P., Wall, Frances, Terry Williams, C. (Eds.), Rare Earth Mineral:
Chemistry, origin and ore deposits. Chapman & Hall, pp. 2137.
Pavez, O., Peres, A.E.C., 1993. Effect of sodium metasilicate and sodium sulphide on
the otability of monazite-zircon-rutile with oleate and hydroxamates. Miner.
Eng. 6 (1), 6978.
Pavez, O. et al., 1996. Technical note adsorption of oleate and octyl-hydroxamate
onto rare-earths minerals. Miner. Eng. 9 (3), 357366.
Pradip, Fuerstenau, D.W., 1991. The role of inorganic and organic reagents in the
otation separation of rare-earth ores. Int. J. Miner. Eng. 32, 122.
U.S. Geological Survey, 2002. Rare earth elements-critical resources for high
technology, USGS Fact Sheet 087-02.
Yongfu Yu, 2000. Mineral processing techniques of rare earths and development in
China, West China Exploration Engineering, series No.63, pp. 14. (Chinese).
Zhang, J., Edwards, C., 2012. A review of rare earth mineral processing technology.
In: 44th Annual Meeting of the Canadian Mineral Processors. CIM, Ottawa, pp.
79102.