ISSN 1070-4272, Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 5, pp. 623628. Pleiades Publishing, Ltd.

., 2013.
Original Russian Text E.P. Lokshin, O.A. Tareeva, I.R. Elizarova, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86, No. 5, pp. 673679.

INORGANIC SYNTHESIS
AND INDUSTRIAL INORGANIC CHEMISTRY

Recovery of Rare Earth Elements from Wet Process Extraction

Phosphoric Acid
E. P. Lokshin, O. A. Tareeva, and I. R. Elizarova

Tananaev Institute of Chemistry and Technology

of Rare Elements and Mineral Raw Materials, Apatity, Russia
e-mail: lokshin@chemy.kolasc.net.ru

Received March 27, 2013

AbstractIt is shown that an increase in the recovery of rare earth elements in fluorophosphate concentrates,
which are obtained by treating the wet process phosphoric acid by ammonium fluoride, is achieved by prior partial
neutralization of H3PO4 by ammonia. Therewith the consumption of ammonium fluoride is reduced that provides
almost complete precipitation of rare earth elements.
DOI: 10.1134/S1070427213050017

A fraction of rare earth elements (REE) of Khibine
apatite concentrate (AC), which is included in the wet
process extraction phosphoric acid (EPA), is estimated
at 30% [1, 2], but, likely, this value is overstated. Indeed,
a yield of a production EPA containing 28 wt% of P2O5
(~38.6 wt% of H3PO4) and 1.31.4 kg m3 of REE is
approximately 1.05 m3 from 1 ton of AC. Thus, by the
EPA no more than 13.515% of REE contained therein
comes in a fertilizer produced from AC.
Furthermore, at least 2.5 m3 of EPA containing 0.9
1.0 kg m3 of REE is used in feedback for decomposition
of 1 ton AC. Both the production and feedback acid, into
which, respectively, 24702660 and 42754750 tons from
sum of REE oxides (Tr2O3) go at plants in Russia, can
be used REE recovery.
An important advantage of EPA is the high content in
the REE sum of middle and yttrium groups as compared
with both the original AC and even more loparite
concentrate, the only Russian industrial source of REE
that determines the increased interest in developing
methods for recovery of REE from EPA. These methods
should be compatible with the main production of mineral
fertilizers that necessitates their operating availability at
elevated temperatures (7580C), moreover, a relatively
small production area should be occupied in their
implementation. It is important to ensure high recovery
of most valuable REE of the middle and yttrium groups.
For a long time a method of spontaneous crystallization
of REE on seeds was considered as promising [310]. It
was based on the assumption that EPA is supersaturated by
REE, mainly, by cerium [38]. Phosphates or fluorides of
rare earth elements were proposed as seeds, also gypsum
may be used [3]. However, the fact that in the presence
of gypsum, which is recommended as a possible seed
material [3], EPA remained supersaturated by REE, is
misunderstood. Therewith in the course of EPA producing
gypsum crystals were maintained a long time in a hot
sodium phosphate solution of relatively low viscosity.
This and other reasons discussed in [11] cast doubt on
the reliability of the results of [310].
Rare earth elements of EPA may be precipitated in the
form of a fluorophosphate concentrate by introduction of
compounds containing fluoride ion [12]. The method is
based on the assumption that in the presence of fluorine
REE will form fluorides poorly soluble in hot phosphoric
acid solution. Although EPA of Khibine AC always
contains relatively high concentrations of fluorine, REE
fluorides are not formed, since in EPA fluorine is bound in
strong anionic complexes with silica and, possibly, with
aluminum, titanium, and iron. However, if the content
of fluoride ion in EPA exceeds those required to form
anionic complexes, REE fluorides will be formed and

623
624 LOKSHIN et al.

precipitated. contained 38 wt% of H3PO4 and (NH4)2CO3 (chemically

Ammonium fluoride is the most accepted. It can
be produced at AC processing plants. In the case of its
application all REE were recovered practically similarly.
The precipitation of REE increased with increasing the
concentration of the fluoride ion and amounted to 92.8%
with an addition of 19.5 g L1 F, 93.6, at 39 g L1 F,
and 97.0, at 58.5 g L1 F [12]. Thus, the majority of REE
precipitated at relatively low consumption of the fluorine-
containing reagent. Its two- and three-fold increase rose
recovery of REE into the concentrate only by 0.84.2%.
The calculations using the data of [12] show that only
15.423.6% of the introduced fluorine goes into the
concentrate.
Upon the increase in the concentration of the
introduced fluorine a precipitation mass grew, mainly,
by increasing the co-precipitation of a number of
impurities (sodium, magnesium, calcium, aluminum,
etc.) that resulted in a reduction of the Tr2O3 content in
the concentrates. The concentrates also contained high
concentrations of chemically bound phosphorus. The
residual concentrations of fluorine in EPA were high
(14.949.1 g L1 of the entered fluoride ion and also
fluorine, which was present in the EPA) that complicated
fluorine recovery in processing EPA for fertilizer.
The aim of the study was to search for the REE
precipitation conditions ensuring diminishing a
consumption fluoride-ion-containing compounds
(ammonium fluoride) while increasing the REE recovery.
EXPERIMENTAL
The EPA (JSC Metakhim) was used in the study. It
pure, GOST 3770-75), NH4F (chemically pure, GOST
4518-75).
REE content and main impurities in the EPA are listed
in Table 1.
For analyzing the cationic composition of the solu-
tions a mass spectrometry was used as well as a mass
spectrometer ELAN 9000 DRC-e (Perkin-Elmer, USA)
with inductively coupled plasma and a dynamic reac-
tion system. The fluorine content was determined by
potentiometric method, and the phosphorus content, by
photocolorimetry method.
The study showed that the hypothesis of REE pre-
cipitation from EPA in the form of fluorides is inac-
curate, since it was found [13] that lanthanum, cerium,
neodymium, and samarium fluorides at 80C in 38 wt%
H3PO4 were dissolved non-congruently and only fluorides
of the yttrium group (yttrium and ytterbium fluorides),
congruently; using ammonium fluoride or ammonium
bifluoride the residual concentrations of REE in EPA
were much less than solubility of REE fluorides; the REE
concentrations in the phosphate solution containing fluo-
ride ion were reduced sharply in the case of introducing
cations Mg2+ in solution and even more NH4+.
Thus, in introducing NH4F into EPA, others than REE
fluorides were precipitated, they were significantly less
soluble fluoride or fluorophosphate complexes contain-
ing ammonium cations. The formation of complexes of
a similar composition containing magnesium cations and
other impurity cations is possible.
At the same consumption of fluoride ion the REE
precipitation efficiency increased according to the order

Table 1. Content of REE and main impurities in EPA

Content, mg L1
Y2O3 L2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Eu2O3 Gd2O3
150.9 221.6 440.5 52.5 200.7 20.2 6.3 35.5
Content, mg L1
Tb2O3 Dy2O3 2O3 Er2O3 Tm2O3 Yb2O3 Lu2O3 aTr2O3
2.62 13.42 2.21 5.43 0.6 3.13 0.37 1155.9
Content, mg L1
Na2 MgO Ca Al23 Ti2 Fe2O3 ThO2 UO2 F

2.73 1.40 1.72 2.56 1.20 2.82 0.009 0.0017 5.75

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 5 2013

 RECOVERY OF RARE EARTH ELEMENTS 625

NH4F > NH4FHF >> HF. This fact is due to an increase
in the solubility in phosphoric acid solution of the formed
REE compounds with increasing an acidity of the solu-
tion [12]. It was suggested that a decrease in the acidity
of the solution by partial neutralization of H3PO4 will
help solve the problem.
An effect of the degree of neutralization of H3PO4
by ammonia and of the concentrations of introduced
fluoride ion in the form NH4F on a precipitation effi-
ciency of REE from EPA was examined. The degree of
neutralization (%) was defined as the molar ratio of
amounts of the introduced ammonia and first proton of
H3PO4. In the sample of EPA heated to 80C (NH4)2CO3
was introduced in amounts providing = 10.548.7%. In
the case of introduction of a large amount of (NH4)2CO3
crystallization of NH4H2PO4 started. Then NH4F was
entered. The resulting suspension was kept for 1 h, the
resulting precipitate was filtered, REE concentrations and
main impurities in the mother liquor were analyzed. The
precipitation efficiency of REE and controlled impurities
was evaluated by the difference in their concentrations in
the initial and the mother liquor.
The conditions of the experiments are shown in Ta-
ble 2, therewith the total concentration of the ammonium
cation entered with both reagents was accounted for. The
recovery into a sediment of REE is given in Table 3.
In some experiments the composition of fluorophos-
phate concentrates of REE, which was not pre-washed
with water and dried, was analyzed. The content of REE
and the main impurities in fluorophosphate concentrates
is given in Table 4; recovery of main impurities into these
concentrates, in Table 5.
The analysis of experimental data was performed
in view of the fact that the concentrations of REE and
cationic impurities in EPA used in this study and in [12]
differed slightly that allowed comparing results obtained
in them.
Table 3 shows that fluoride ion reacts efficiently
with REE, thorium, and aluminum with the formation
of poorly soluble compounds, which in all investigated
conditions are precipitated with more efficiency than other
main impurities (Table 3, runs nos. 3, 8). At low fluorine
consumption (5.14 g L1) the difference in the precipita-
tion of REE and the main impurities enables production
of concentrates with the high content of REE (Table 4,
run no. 3), but the recovery of REE into the concentrate,
especially, of the middle and heavy groups in this case
significantly decreases.
Comparison of the Table 3 data with those of [12]
shows that the prior partial neutralization of phosphoric
acid contributes to a significant reduction of the fluo-
rine-containing reagent consumption and, therefore, to
reducing the residual concentration of fluorine in EPA
while increasing the REE deposition. The most complete
precipitation of REE was achieved with = 21% and
the concentration of fluorine introduced c 15.4 g L1
(runs nos. 5, 6). In the 10.27 g L1 fluorine introduction
(runs nos. 2, 4, 10) the sufficiently high precipitation

Table 2. Conditions of the experiments

NH4+/34, Introduced F, g L1 Residual F F in precipitate, %

Run nol , %
mol% (NH4F) total in EPA, g L1 of introduced F

1 10.5 13.52 7.71 13.45 11.9 20.1

2 10.5 24.2 10.27 16.02 13.75 22.1
3 21.0 26.4 5.14 10.89 8.6 40.7
4 21.0 32.0 10.27 16.02 12.4 35.2
5 21.0 37.5 15.40 21.15 16 33.4
6 21.0 43.0 20.54 26.29 17.2 44.3
7 31.6 16.4 7.71 13.46 11.1 69.4
8 48.7 54.1 5.14 10.89 8 56.2
9 48.7 57.0 7.71 13.46 8.2 68.2

10 48.7 59.8 10.27 16.02 11.4 45.0

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626 LOKSHIN et al.

Table 3. Recovery of individual REE in precipitation

Introduced F, Recovery, %
Run no. , %
g L1 Y L Ce Pr Nd Sm Eu Gd
1 10.5 7.71 23.6 48.0 44.0 41.0 38.7 21.2 23.3 29.0
2 10.5 10.27 94.0 99.2 98.7 98.2 97.9 92.9 91.5 92.1
3 21.0 5.14 62.6 67.5 59.9 56.6 54.8 49.0 47.7 69.1
4 21.0 10.27 99.2 99.3 98.8 98.9 98.8 96.9 97.0 98.3
5 21.0 15.40 99.8 99.9 99.9 99.9 99.9 99.4 99.7 99.8
6 21.0 20.54 99.8 99.9 99.8 99.9 99.9 98.9 99.8 99.9
7 31.6 7.71 90.1 94.5 91.6 89.3 88.7 83.1 80.8 83.2
8 48.7 5.14 61.8 80.1 74.9 74.1 72.9 31.2 29.8 52.9
9 48.7 7.71 96.1 97.6 96.8 96.3 95.8 89.5 89.2 93.1
10 48.7 10.27 98.8 99.0 98.7 98.6 98.5 96.7 91.6 97.9
Tb Dy Er Tm Yb Lu Tr
1 10.5 7.71 22.7 21.0 21.0 18.9 15.7 3.9 11.7 38.6
2 10.5 10.27 87.2 83.9 81.1 78.8 73.2 69.0 60.0 96.8
3 21.0 5.14 46.3 43.6 42.5 40.3 34.5 27.8 23.2 60.2
4 21.0 10.27 96.8 96.6 96.4 95.9 94.7 91.7 88.6 98.8
5 21.0 15.40 99.7 99.7 99.7 99.7 99.7 99.4 99.2 99.8
6 21.0 20.54 99.3 99.9 99.9 99.9 99.8 99.7 99.7 99.8
7 31.6 7.71 79.8 76.6 75.5 72.3 64.3 58.7 50.0 89.8
8 48.7 5.14 21.0 14.1 5.9 7.4 6.7 15.7 8.1 70.3
9 48.7 7.71 87.8 85.8 83.7 77.5 63.3 36.7 21.6 95.9
10 48.7 10.27 96.5 96.2 95.7 93.9 99.0 79.9 73.8 98.5
Na Mg Ca Al Ti Fe Th U
1 10.5 7.71 34.0 11.7 16.0 17.6 7.1 4.6 40.7 7.1
2 10.5 10.27 10.8 50.3 75.5 77.9 15.4 11.2 94.3 14.2
3 21.0 5.14 3.9 0.7 0.3 26.6 0.2 0.0 67.3 0.6
4 21.0 10.27 7.0 9.2 61.3 73.7 0.2 2.6 98.7 1.8
5 21.0 15.40 7.7 14.3 73.2 79.5 0.8 4.1 99.7 2.9
6 21.0 20.54 22.9 73.4 76.8 84.2 8.3 9.16 99.6 4.6
7 31.6 7.71 13.6 38.6 66.1 67.6 16.7 13.1 92.3 14.6
8 48.7 5.14 4.4 21.3 0.2 24.7 1.7 0.6 43.3 0.0
9 48.7 7.71 17.3 31.9 62.0 79.0 4.2 1.8 93.1 2.9
10 48.7 10.27 23.6 54.2 78.0 88.5 10.4 26.8 97.7 4.7

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 5 2013

 RECOVERY OF RARE EARTH ELEMENTS 627

of the REE sum was also reached, but that of middle
and, especially, heavy groups depended markedly on
the degree of neutralization. Best results were obtained
with = 21% (run no. 4), therewith the recovery in the
concentrate of ytterbium and lutetium, whose fluorides
dissolve congruently in hot phosphoric acid solution,
was 91.7 and 88.6% respectively. Despite the fact that
an increase in the fluorine consumption in 1.5 time (run
no. 5) rises recovery of REE of middle and heavy groups,
economically it hardly advisable.
If thorium recovered in the fluorophosphate concen-
trates in an amount almost equal to that of REE, uranium
mostly remains in EPA (Table 4). Thorium oxide content
in the sediments relative to Tr2O3 is 1.081.30; UO2
content, 0.00120.0108 wt%. Thus, the radioactivity of
precipitates is mainly determined by a high content of
thorium. According to the values of the concentration of
thorium and uranium the precipitates (runs nos. 7, 10)
obtained with the acceptable recovery of REE (89.8
98.5%) refer to materials with a high content of natural
radionuclides of class II [14]. This determines the need
to separate the radionuclides in the further processing the
fluorophosphate concentrate.
The main impurity cations are precipitated usually
somewhat more difficult than REE and the efficiency of
precipitation of alkaline earth metals and aluminum is
high (Table 3). Transfer of calcium, aluminum, magne-
sium to the REE concentrate is most complete and that of
sodium occurs to a lesser extent. Precipitation of titanium
and iron, which form, apparently, enough soluble fluo-
ride complexes in the phosphoric acid solution, occurs
incompletely. At the same amount of the fluorine intro-
duced equal to 10.27 g L1, the minimum precipitation
of cationic impurities was at the degree of neutralization
of 10.5% (run no. 2).
It should be noted that the precipitation efficiency
of the main impurities calculated by changing their
concentration in the solutions or by their content in
sediments within an analysis accuracy is insignificantly
distinguished in the case of calcium, aluminum, and
thorium. For sodium, titanium, and iron the precipitation
efficiency calculated by the change in their concentration
in the solution is higher than that found by their content
in the sediments. This indicates that these impurities are
partially crystallized after separation of REE concentrates
and cooling to room temperature of EPA entering the
analysis.
The increased content of REE in the sediment obtained
in run no. 3 is due to a low efficiency of precipitation of
majority cationic impurities present in EPA (Table 5).
Increasing the degree of neutralization contributes to
increasing the precipitation efficiency of these impurities.
The exception is magnesium that is apparently due to its
displacement by the ammonium cation from containing

Table 4. Contents of REE and main impurities in fluorophophate concentrates at different precipitation conditions

Introduced F, Precipitate Content, wt %

Run no. , %
g L1 weight, g Na2 MgO Ca Al23 Si2 Ti2
3 21.0 5.14 0.492 1.93 6.45 7.99 16.8 6.34 0.19
7 31.6 7.71 1.227 0.91 1.63 5.88 6.13 2.18 0.40
10 48.7 10.27 1.26 1.41 1.48 6.16 9.04 4.02 0.51
Fe2O3 ThO2 UO2 F 25 Tr2O3
3 21.0 5.14 0.492 0.50 0.148 0.00014 27.1 17.2 11.37
7 31.6 7.71 1.227 0.91 0.044 0.00044 7.7 44 4.07
10 48.7 10.27 1.26 1.34 0.055 0.00038 15.0 29.2 4.40

Table 5. Recovery of main impurities into fluorophophate concentrates at different precipitation conditions

Introduced F, Precipitate Recovery, wt %

Run no. , %
g L1 weight, g Na Mg Ca Al Ti Fe
3 21 5.14 0.492 7.0 45.3 45.7 64.6 1.6 1.7
7 31.6 7.71 1.227 8.2 28.6 84.0 58.8 8.3 7.9
10 48.7 10.27 1.26 13.1 26.6 90.2 89 10.7 12.0

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 5 2013

628 LOKSHIN et al.
REE complexes of a complex composition, since the
solubility of complexes containing ammonium cation is
significantly less than the solubility of similar complexes
with magnesium. Note that the ratio of sodium and sili-
con in the sediments (Table 4) suggests that a significant
portion of silicon precipitates in the form distinct from
Na2SiF6.
The precipitation of fluorine increases with the degree
of neutralization (Table 2, runs nos. 1, 7 and 9, or 2, 4 and
10), and in the case of the same degree of neutralization
it is complicated: at = 21% and the concentration of
fluoride ion 5.1420.54 g L1 a minimum is observed at
introduction of 1015 g L1 of fluoride ion; at = 48.7%
and the concentration of fluoride ion 5.1410.24 g L1 a
maximum in fluorine precipitation occurs at introduction
of 7.71 g L1 of fluorine.
Precipitation of REE under the conditions of run no.
9 is of some interest, when the consumption of the fluo-
ride ion was small, and a significant part of the fluorine
precipitated at a small decrease in REE recovery.
CONCLUSIONS
(1) The optimal degree of neutralization of = 21%
of the wet process extraction phosphoric acid prior to the
ammonium fluoride introduction rises REE recovery in
precipitate from 93.697.0 to 98.899.8% with reducing
the ammonium fluoride consumption in term of fluoride
ion from 3958.5 to 10.315.4 g L1.
(2) The increase of from 21 to 48.7% diminishes
the precipitation efficiency of heavy REE (ytterbium,
lutetium) and rises that of impurities, especially, of
calcium and aluminum.
(3) Increasing the REE content in the concentrate can
be achieved by reduction of the contributed fluoride ion
but in this case REE recovery in concentrate decreases.
(4) Thorium precipitates practically equally with REE
while uranium at the investigation parameters mainly
remains in solution. REE concentrates obtained under
optimal conditions are products with a high content of
natural radionuclides of class II.
ACKNOWLEDGMENTS
This work was supported by the Program of the
Presidium of Russian Academy of Sciences no. 27 The
fundamental basis of innovative technology forecasting,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 86 No. 5 2013
assessment, production, and deep complex processing of
strategic mineral raw materials need to modernize the
Russian economy.
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