J.RADIOANAL.NUCL.CHEM.

,LETTERS 135 [2/ 67-76 11989]

EXTRACTION OF RARE EARTH ELEMENTS BY PRIMARY HIGH

MOLECULAR WEIGHT AMINES FROM HYDROCHLORIC
ACID SOLUTIONS

N.S. Varezhkina, M.S. Milyukova, B.F. Myasoedov

V.I. Vernadsky Institute of Geochemistry and

Analytical Chemistry, USSR Academy of Sciences,
Moscow, USSR

Received 30 September 1988

Accepted 14 October 1988

Extraction of trivalent lanthanides: La, Ce,

Nd, Eu, Tb, Tm, Yb by primary high molecular
weight amines from 0.5-3M hydrochloric acid
solutions, containing complex-forming agent
potassium phosphotungstate /KIoP2WI7061[ has
been investigated. The effect of hYdrochloric
acid, potassium phosphotungstate and amine
concentration, the length of primary amine al-
kyl chain, organic solvents nature and elements
ionic radii on distribution coefficients have
been studied. It has been established that the
system can be used for group isolation and
separation of rare earth elements.

INTRODUCTION

The efficiency of metal extraction is known to de-

pend on various factors simultaneously. The most im-
portant factors are aqueous phase composition, extract-
ant structure and concentration and organic solvent

1 67 Elsev~Sequo~A.,La,~nne
A k ~ m ~ Kiad6, Budapest
VAREZHKINA et al.: EXTRACTION OF RARE EARTH ELEMENTS

nature. As we established earlier, primary amines can

be used for group extraction and separation lanthanides
and actinides from nitric acid solutions, containing
complex-forming agent KIoP2WI7061 /Ref. I/. The nature
of mineral acid is known to influence the extraction of
lanthanides by primary amines. Therefore, it was worth
to investigate the extraction of lanthanides from hydro-
chloric and or sulphuric acid solution in the presence
of a complex-forming agent potassium phosphotungstate.
This paper fs a continuation of our previous works 1'2

EXPERIMENTAL
140La, 144Ce, 147Nd, 152Eu, 160Tb, 170Tm 175yb iso-
topes obtained by the neutron activation method were in-
vestigated. Aliphatic primary amines with C7-C16 alkyl
radicals were used as extractants. Different solvents:
chloroform, cyclohexane, benzene, carbon tetrachloride
and dichloroethane were studied. The procedure has been
described earlier I .

RESULTS AND D I S C U S S I O N

The effect of hydrochloric and sulphuric acid con-

centration on the extraction of rare earth elements was
studied in the system: mineral acid - potassium phospho-
tungstate - 3% solution of decylamine in chloroform. Pri-
mary amines were found to extract rare earth elements
from hydrochloric acid' When extracted from sulphuric acid
a third phase, concentrating the main activity, is formed.
Data obtained for the rare earth elements extraction by
3% decylamine in chloroform from 0.5-3M hydrochloric
solutions, containing 4xlO-5M potassium phosphotungstate,
are given in Fig. i.
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 VAREZHKINA et al.: EXTRACTION OF RARE EARTH ELEMENTS

I03~ 9 Lo I
o ~\ .c~ I
9 - "'- A Nd I

o l
I k \ k% 9 T~ /

i0-I

0.5 ~.o ~.s z.o

[HCs
Fig. I. Me
3+Effect ofl hydrochloric acid concentration on
extraction with 3% decYlamine in chloro-
form

Figure 1 shows decreasing of the elements distribution

coefficients with increasing of hydrochloric acid con-
centration but by various way. Thus Ce, Eu, Tb and Tm
are quantitatively extracted into the organic phase
from 0.5-O.75M hydrochloric acid, but La and Nd are
extracted'to 50% only.
The effect of ionic radius on the distribution coef-
ficients of lanthanides is shown in Fig. 2. The dependence
is not linear~. According to extraction behaviour the
rare earth elements can be classified into two groups:
cerium and europium group, having maximum distribution
coefficient for Ce and Eu, respectively. As was des-
cribed earlier, analogous phenomenon occurs when ex-
traction with decyiamine in chloroform from nitric
acid is performed. Figure 2 shows that extraction by
decylamine from O.5-O.75M hydrochloric acid can be
used for the isolation of heavy lantbanides and their
separation from light elements of the group /La, Nd/.

1" 69
VAREZHKINA et al.: EXTRACTION OF RARE EARTH ELEMENTS

D
10'

10 z

10

t0-~

I0"2
LaCe Nd Eu Tb TmYb

Fig. 2. Dependence of distribution coefficients of tri-

valent lanthanides upon their ionic radius when
extracted with 3% de~ylamine in chloroform from
HCI containing 4xlO-JM KIoP2WI7061

Extraction of trivalent rare earth elements strongly

depends on phosphotungstate concentration in the initial
aqueous phase. Europium as the most extractable element
and neodymium, as the least extractable element were
used to investigate the dependence of extraction on the
potassium phosphotungstate concentration in the initial
aqueous phase when extracted from O.5-O.75M hydrochloric
acid. Figure 3 shows that the distribution coefficients
increase with an increase in potassium phosphotungstate
concentration. KIoP2W17061 concentration required to
reach maximum extraction depends on the acidity of the
aqueous solution. The higher is the hydrochloric acid
concentration, the higher KIoP2WI7061 concentration is
required to obtain maximum extraction. For example: when
extracted from O.5-O.75M hydrochloric acid 4xlO-5M

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 VAREZHKINA et al.: EXTRACTION OF RARE EARTH ELEMENTS

IO0

8O
1.5M

6O

40 o Eu
9 Nd

2C

I I I I 1 I.,,
10- ~ 2 5 10 -4 2 5 10- 3
[ K loPzWftO61 ], M

Fig. 3. Effect of KI^P~W_70_ 1 concentration in initial

aqueous s o l ~ i 6 n ~ o~ neodymium and europium ex-
traction with 3% decylamine in chloroform

KIoP2WI7061 is enough for the quantitative extraction

-3
of Eu and 25% Nd extraction, while i0 KIoP2WI7061 al-
lows to quantitatively extract europium and neodymium
from 1.5M and IM hydrochloric acid, respectively. Lo-
J

garithmic dependence of Eu and Nd distribution coeffi-

cientson potassium phosphotungstate concentration is
linear. Slope of the straight line equals to i. /Fig. 4./
Consequently, under this conditions lanthanides is like-
ly to form anion LnP2WI701; entering into extracted
complex. The effect of the structure of the extractant on
the extraction of rare earth ions has been studied. Data
obtained for 152Eu when extracted by 1.38xlO-3M amine
solutions in chloroform from 1.5M hydrochloric acid,
containing 4xlO-5M KIoP2WI7061 are given in Fig. 5. The
highest distribution coefficients for Eu were obtained
when extracted with C8-C 9 alkyl amines. Increasing the
length of the alkyl chain from i0 to 16 results in a
71
VAREZHKINA et al.: EXTRACTION OF RARE EARTH ELEMENTS

I o

////O
9

/ /1.sM
9w f 05M 2"

-1

-5 -4 -a
tg [ K 10 P2 Wl? 051 ]
Fig. 4. Dependence of e u r o p i u m and n e o d y m i u m distribution
coefficients upon p o t a s s i u m p h o s p h o t u n g s t a t e con-
centration

i0-I

J I ,
Ce C9 Cio C12

Fig. 5. Effect of the length of primary amine alkyl chain

on e u r o p i u m extraction with 1 . 3 8 x l O - i M amine in
chloroform

decrease of europium extraction. While, when extracted

from nitric acid solutions, maximum distribution coef-
ficients were o b t a i n e d when C7-CIo alkyl chain p r i m a r y
amines were used I.

Effect of extractant concentration on the extraction

of lanthanides was studied taking Eu as an example. Data

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 VAREZHKINA et al.: EXTRACTION OF RARE EARTH ELEMENTS

~o-!

10": I , 9 L. . . . . . . . . . J

[C)A], N
Fig. 6. Effect of extractant concentration on Eu extraction
from 1.5M hydrochloric acid solutions, contain-
ing 4xlO-5M KIoP2WI7061

obtained for europium extraction from 1.5M hydrochloric

acid, containing 4xlO-5M KIoP2WI7061 are given in Fig. 6.
The dependence of distribution coefficients on concentra-
tion has a complex character with maximum and ininimum. Ap-
parently, it may be explained by various degree of amines
i

solvatation by solvents or various degree of plcimary amir~e

association du@ing increasing amine concentrat:Lon or by
the joint influence of these factors. Similar ,]ependence
was observed when lanthanides and actinldes were extracted
by primary amines from nitric acid solution 2.
The nature of the organic solvent strongly affects the
extraction of lanthanides. For europium the data are com-
piled in Table i, which shows that the best solvent is
chloroform. In some solvents a third phase, concentrat-
ing main activity is formed.

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VAREZHKINAet al.: EXTRACTIONOF RARE EARTH ELEMENTS

TABLE 1

Distribution coefficients /D/ of Eu extracted with 3%

decylamine in various solvents from IM HCl, containing
4 x l O - 5 M KIoP2WI7061

Solvents D

Chloroform 9.23
Carbon tetrachloride 0.79
Dichloroethane 4.21x10 -3
Cyclohexane 0.70
Benzene 1.54x10- 2

Data obtained allows to conclude that the rare earth

elements can be extracted by primary amines from hydro-
chloric acid solutions, containing potassium phospho-
tungstate. When hydrochloric acid and potassium phospho-
tungst~te concentrations in the initial aqueous solutions
are changed, the rare earth elements can be jointly ex-
tracted or separated from each other. So, all elements
are quantitatively extracted by O.IM octyl-, nonyl-,
and decylamine solutions in chloroform from 0.5-1.5M
-3
hydrochloric acid, containing iO KIoP2WI7061 ~
Separation factors of trivalent rare earth elements
in solution of various hydrochloric acid concentration
are given in TaSle 2. The separation factors of several
rare earth element pairs when extracted from hydrochloric
acid are higher than the same factors when extracted
from nitric acid solutionl~ Therefore the extraction of
lanthanides by primary amines from hydrochloric acid
solutions has some advantages over extraction from nit-
ric acid solutions.

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 VAREZHKINA et al.: EXTRACTION OF RARE EARTH ELEMENTS

TABLE 2

Separation factors /S/ of trivalent lanthanides extracted

with 3% decylamine in chloroform from hydrochloric acid,
containing 4xlO-5M KIoP2W17061

S O.5M O.75M I.OM 1.25M 1.5M 1.75M

Ce/La 977.11 32.34 6.61 7.81 9.78

Ce/Nd 2.3xlO 3 49.00 8.21 5.08 3.46
Ce/Yb 10.42 12.86
Ce/Tm 3.75
Eu/La 1.3xlO 3 315.24 25.78 10.32 15.43 22.31
Eu/Nd 3.2xlO 3 477.64 32 7.5 5.46 3.05
Eu/Tm 5.91 10.36
Eu/Yb 7.86 13.7520.29 30.85
Tb/La 9.14xlO 3 965.80 38.5 11.31 12.39
Tb/Nd 2.15xlO 3 1.4xlO 3 47.79 8.23 4.38
Tb/Tm 2.45
Tb/Yb 11.75 13.75 4.75
Tm/La 740.42 58.34 12.81 4.63
Tm/Nd 1.74xlO 3 88.39 15.90 3.36
Tm/Yb 3.91 6.17
Yb/La 7.07 6.8 3.28
Yb/Nd 16.65 10.30 4.07

The reextraction of the elements into the aqueous

phase can be carried out with 5M hydrochloric acid or
by 3M nitric acid solution.

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VAREZHKINA et al.: EXTRACTION OF RARE EARTH ELEMENTS

REFERENCES

1. M.S. Milyukova, N.S. Vareshkina, B.F. Myasoedov,

J. Radioanal. Nucl. Chem.~ Lett., 105 /1986/ 249.

2. M.S. Milyukova, N.S. Vareshkina, B.F. Myasoedov,

J. Radioanal. Nucl. Chem., Lett., 121 /1988/ 403.

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