YTTRIUM AND RARE EARTHS STRIPPING BY SOLVENT EXTRACTION WITH

Di(2-ETHYLHEXYL)PHOSPHORIC ACID USING A STATISTICAL APPROACH

Afonso Henriques Martins
Universidade Federal de Minas Gerais
Departamento de Engenharia Metalrgica e de Materiais
Rua Esprito Santo 35 sala 206, Belo Horizonte(MG), CEP 30160-030, BRAZIL.

Abstract
Bench scale shake out experiments were performed to study heavy rare earths and yttrium
extraction and stripping with di(2-ethylhexyl)phosphoric acid in a chloride system. The effect of
some important parameters, such as hydrochloric acid concentration in the stripping solution,
time of contact between phases and temperature were studied using a factorial design.
Rare earth and yttrium oxides used in the experiments were obtained from a metallurgical
processing of a Brazilian xenotime concentrate(Pitinga-Brazil).
Ytterbium presented the highest chemical affinity for the organic phase and remained into the
organic phase even for high HCl concentration stripping solutions. The increase of HCl
concentration in the aqueous phase raises the dysprosium, yttrium and erbium stripping
percentages as well as diminishes terbium recovery.

Introduction
Yttrium and rare earth elements are widely used in metallurgy, catalysis and ceramics.
Superconductivity, an outstanding topic is one of the high technology applications for rare
earths.
Rare earths separation is considered a complex chemical process. Solvent extraction and ion
exchange with polymeric resins are widely used in mineral industry plants. Many researchers 1-11
have reported separation procedures based on solvent extraction with di(2ethylhexyl)phosphoric acid(D2EHPA) reaching good results for heavy rare earth elements.
This paper presents experimental results for the heavy rare earth separation with D2EHPA and
tributylphosphate(TBP) as modifier solubilized in kerosene. Rare earth oxides used in the
experiments were obtained from a metallurgical processing of a Brazilian xenotime
concentrate(Pitinga-Amazonas).
The variables studied were hydrochloric acid concentration in the stripping solution, temperature
and time of contact between organic and aqueous phases. A statistical approach using factorial
design for experimental planning was adopted in order to analyse the individual and interactions
effect of some variables on the separation performance of the solvent extraction system.

Experimental Procedure
The D2EHPA used in this experimental work was a general purpose reagent grade 90% pure.
The organic phase was prepared by solubilizing D2EHPA and tributylphosphate(TBP) as
modifier in kerosene. All other chemicals used were analytical grade.
The aqueous solution for the organic phase loading was prepared by solubilizing 3.0 gramms of
rare earth and yttrium oxides in HCl concentrate at the boiling temperature. Deionized water was
added to prepare 1 litre of yttrium and rare earth chlorides solution. The chemical composition
of the loading solution is shown in Table 1.

Table 1- Chemical Composition of the Loading Solution

compounds

chemical
composition(g/L)

Tb4O7
Y2O3
Dy2O3
Er2O3
Yb2O3

0.06
1.43
0.47
0.52
0.73

A cylindrical 100 mL glass beaker was used as solvent extraction reactor for the organic phase
loading and metal separation experiments. The reactor was immersed into a constant
temperature bath and mixed via a magnetic stirring device.
The organic phase composition was 16% D2EHPA and 2.3% TBP in kerosene. 40 mL of
aqueous solution with pH adjusted to 1.60 was poured into the reactor with 20 mL of organic
phase and submitted to intense magnetic stirring at 30oC for 20 minutes. Under these conditions
all Tb, Dy, Y, Er and Yb ions were extracted into the organic phase.
Separation experiments were carried out with 20 mL of organic phase loaded with rare earths
and yttrium obtained from the previous stage and 20 mL of stripping solution.
The Tb, Dy, Y, Er and Yb concentration in aqueous solutions was determined by ionic
chromatography with the anionic method12 by High Performance Liquid Chromatography
(HPLC) system.
The statistical procedure selected to study the influence of the hydrochloric acid concentration in
the stripping solution, temperature and time of contact between phases on the rare earth
separation was the factorial design method for planning of experiments13-15.

Results
The statistical design for the variables and their experimental levels is shown in Table 2. The
experimental results for terbium, dysprosium, yttrium, erbium and ytterbium are presented in
Table 3. Each experiment was performed twice.

Table 2- Statistical Planning of the Experiments for Rare Earths Separation

variables

upper
level(+)

lower
level(-)

A-HCl concentration (M)

3.0

1.5

B-Temperature (oC)

70.0

25.0

C-Time of contact (minutes)

60.0

20

Table 3- Experimental Replicated Results for Rare Earths Separation by Solvent Extraction
test

Tb (%)

Dy (%)

Y (%)

Er (%)

Yb (%)

32.9

34.8

44.7

47.5

31.4

31.6

20.9

22.7

1.5

1.8

13.7

13.1

56.1

54.3

50.6

53.7

32.7

38.5

6.3

6.5

48.4

47.1

58.3

54.3

61.5

57.3

42.7

39.7

0.7

0.5

13.8

14.3

59.3

57.8

52.5

50.5

35.9

37.2

1.8

2.1

35.2

35.9

49.1

49.1

35.9

35.9

23.5

23.1

1.8

1.8

13.9

14.4

50.1

56.4

44.9

48.6

28.8

25.6

0.5

0.5

46.4

47.1

54.6

55.6

49.7

57

45

49.5

9.4

7.5

14.1

13.7

66.4

64.3

58.9

62.9

46.8

44.9

26

22.8

Ytterbium exhibited low recovery remaining strongly adsorbed in the organic phase. Due to
these results any additional statistical analysis can be performed in order to study the ytterbium
stripping performance.
Table 4 shows the statistical effects of variables and interactions on stripping of the organic
phase determined from the factorial design.

Table 4- Effect of Variables and Their Interactions on the Yttrium and Rare Earths Stripping

variables and
interactions
A
B
AB
C
AC
BC

statistical effect in the experimental response

Tb
Dy
Y
Er
-24.4
3.7
-8.8
2.9
2.6
-3.5

6.7
8.3
-0.4
1.2
1.0
1.5

6.6
15.8
-6.8
-0.5
0.3
2.2

2.2
16.4
-5.2
1.4
-2.3
6.2

The variable A (HCl concentration in the stripping solution) had the highest and negative effect
on terbium stripping followed by a positive effect on dysprosium and yttrium. The variable A
showed the lowest effect for erbium recovery.
The variable B (temperature of the stripping system) presented an increasing effect from terbium
to erbium while the variable C (time of contact between phases) had a negative effect only on
yttrium recovery.
The interaction AB presented a strong negative effect for all elements with the exception for
dysprosium whose effect was almost negligible.
The interaction AC showed a behaviour similar to the variable A effect and it might be
explained by the much stronger influence of the HCl concentration than time of contact between
phases.
Unfortunately, the numerical analysis is limited because it is difficult to visualize any dynamic
information involving the interactions effects when variables change their values from the lower
to the upper levels. Due to this limitation a graphical analysis was performed and Figure 1
presents the statistical graphical analysis for terbium, dysprosium, ytttrium and erbium stripping
in function of the variables interactions.
It is important to note in Figure 1 the metal recovery percent profile associated to the behaviour
of the lines representing a variable when the experimental value moves from the lower level to
the upper level. So that, parallel lines represent no statistical significance for the interaction,
convergent and divergent lines might represent negative or positive effect depending on the lines
shift. Whenever lines cross each other there is a changing of the signal in the interaction effect
on the experimental response.
The interaction AB shows a distinct effect for terbium stripping concerning to the others. The
negative effect of the interaction trends to be positive when the HCl concentration in the
stripping solution increases. After the crossing point, the effect would become positive if the
experimental value of the variable changes from the lower to the upper level.
The interaction AC had similar behaviour for yttrium and erbium stripping, i.e. continuous
tendency to negative effect. The interaction AC exhibited continuous positive effect for terbium
in the range of HCl concentration and temperature values. On the other hand, the statistical

analysis suggests that the positive effect of the interaction AC for dysprosium would become
negative for values higher than 3.0 M HCl.
The interaction BC presented different efects on the solvent extraction system. For instance, the
negative effect for terbium increases when temperature of the solvent extraction system values
are close or higher to 70oC, as well as the positive effect for dysprosium when the temperature is
higher than 25oC. For yttrium, only temperatures much higher than 70oC would allow the
interaction AC to have a positive effect increase. It is important to remark that D2EHPA is not
chemicaly stable under temperatures higher than 80oC. The interaction BC has a positive effect
for erbium stripping, however there is a negative effect tendency for high temperatures.
Focusing on industrial applications, the interaction BC evaluation is not considered for practical
routine because most of the solvent extraction plants run at room temperature. So that, the
interaction AC which presented different effects for terbium, dysprosium and the pair yttriumerbium could be used to perform a full separation. In fact, the HCl concentration in the stripping
solution and time of contact between phases are the most widely variables used to achieve
yttrium and rare earths separation in solvent extraction plants.
Acknowlegments
The authors wish to express their gratitude to Dr. David B. Dreisinger (The University of British
Columbia-Canada) for his stimulating advisory and for helpful discussions. Financial support
from Fundao de Amparo Pesquisa do Estado de So Paulo-Brazil is also gratefully
acknowledged.
References
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Figue 1- Interactions of variables effect in the rare earth separation by solvent extraction.