Separation and Purification Technology 46 (2005) 145–154

Studies on europium separation from a middle rare earth

concentrate by in situ zinc reduction technique
S.A. Sayed a , K.A. Rabie b , I.E. Salama b,∗
aChemistry Department, Faculty of Science, Helwan University, P.O. Box 11795 Ain Helwan, Cairo, Egypt
b Nuclear Materials Authority, Rare Earth Elements Separation Project, P.O. Box 530 El-Maadi, Cairo, Egypt

Received 15 October 2004; received in revised form 27 April 2005; accepted 12 May 2005

Abstract

The present work is directed to establish the laboratory conditions for europium separation from its lanthanide neighbors, which are derived
from the Egyptian monazite middle rare earth concentrate. The laboratory separation procedure is oriented to be commercialized for large
industrial scale application (utilizing the commercially available reagents in Egypt). The separation process is based on a combined reduction-
precipitation process, in which the europium is reduced by commercial zinc metal to its bivalent state followed by the precipitation of its
sparingly soluble europous sulphate. Factors affecting the efficiency of the reduction-precipitation process which include; zinc type and its
stiochiometric amount, reduction time, nature of precipitating agent and its concentration, and precipitation time were studied and evaluated
in details.
The best resulted reduction precipitation conditions were attained with a commercial zinc metal (2.5 times the stiochiometric amount),
reduction time of 60 min, sulphuric acid as the precipitating agent (3.0 M) and finally precipitation time of 2 h in a non-oxidizing atmosphere
of nitrogen.
Application of the resulted optimum laboratory conditions for the separation of europium on a middle rare earth concentrate containing
2.5 wt.% Nd, 10.13 wt.% Sm, 11.35 wt.% Eu, 2.6 wt.% Gd, and 2.7 wt.% Tb gave 95% recovery of europium (II) sulphate with a purity of
92%. In the second reduction-precipitation run, the purity was increased to 97% with a final recovery of 91%.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Europium separation; Monazite; Zinc; Reduction; Precipitation

1. Introduction Europium is one of the rarest and most costly of the

Rare earth elements have gained a great attention in the
last few decades owing to their unique properties and wide
range of applications that utilizes these elements in huge
quantities. The rare earth elements, being chemically sim-
ilar to one another, invariably occur together in the source
minerals (bastansite, monazite, and xenotime) and behave as
single chemical entity. Chemically, the mineral monazite is a
rare earth and thorium phosphates and is considered actually
as an important source for thorium and rare earth elements
especially those of low atomic numbers (cerium group, La,
Ce, Pr, Nd, Sm, Eu, and Gd) [1].
∗ Corresponding author. Tel.: +20 27585835; fax: +20 27585838.
E-mail address: dribrahimsalama@yahoo.com (I.E. Salama).
rare earth elements accounting for only about 0.05–0.1%
of the rare earth elements present in the mineral monazite
[2]. Although of the lower europium content in monazite,
it is considered to be one of the main industrial sources for
the commercial production of this element. Europium oxide
is now widely used as a phosphor activator, and europium
activated yttrium vanadate is in commercial use as the red
phosphor in colour TV tubes with an annual world consump-
tion of 20–30 tonnes [3]. Europium compounds are also used
in X-ray screens, computer monitors, high-intensity mercury
vapor lamps, neutron scintillators, charged-particles detec-
tors, and optically red memory systems.
Generally, the separation of this element begins with
the digestion of monazite sands with concentrated sodium
hydroxide or sulphuric acid to produce REEs hydrous oxides.

1383-5866/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2005.05.006
146 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154
Both methods have been developed and applied in Egypt to
produce REEs concentrates. The produced rare earth cake
was then subjected to cerium removal process [4,5]. Mid-
dle rare earth concentrates were separated from the cerium
free-rare earth cake by solvent extraction using either cross
or continuous counter current batch process utilizing di-2-
ethylhexyl phosphoric acid extractant diluted with kerosene.
Different experimental conditions were optimized to reach
the highest possible Eu concentration in the middle RE con-
centrate [6].
Rare earth elements are present as trivalent ions in aqueous
solution, some of which can be reduced to divalent state; Sm,
Eu, Tm, and Yb. Among these, only Eu(III) has the highest
standard redox potential, which makes its selective reduction
and recovery from a mixture containing the other trivalent
rare earth ions possible. This can be demonstrated by the
reduction potential associated with Eq. (1) [7]:
2Eu3+ 2+ 2+
(aq) + Zn(s) = 2Eu(aq) + Zn(aq)
E298K
0
= 0.33V
(1)
Europium reduction and precipitation is carried out in non-
oxidizing atmosphere, since Eu(II) is easily oxidized by oxy-
gen according to Eq. (2):
+ scale mixer settler [6]. Zinc metal was used in different forms
4Eu2+ 3+
(aq) + O2 + 4H(aq) = 4Eu(aq) + 2H2 O(l)

E298K
0
= 1.66V (2)
Several techniques based on electrochemical reduction
[8–12], photochemical reduction [13–16], radiochemical
reduction [17,18], and chemical reduction using zinc
[19–23], zinc amalgam [7,21,24–26] have been used for the
separation of europium from other rare earth elements. Sep-
aration methods based on chemical reduction are the most
utilized and applicable one. All of the separation techniques
depend mainly on the selective reduction of Eu(III) to Eu(II)
and then precipitation as EuSO4 or EuCl3 ·2H2 O by make use
of the fact that, the chemical properties of Eu(II) are similar
to those of alkaline earth ions [27].
The separation of europium using the combined chemi-
cal reduction-ion exchange methods have been used exten-
sively for the production of pure europium oxide [28–30].
The method is based on a reduction-precipitation enrich-
ment of the initial europium concentration followed by an ion
exchange separation of Eu(II) after Eu(III) reduction. Appli-
cation of the combined chemical reduction-solvent extrac-
tion techniques have been widely used for the separation of
europium [27,31].
The aim of the present work focus on the separation of
europium from the middle rare earth concentrate produced
form Egyptian monazite by the make use of the determined
optimum conditions resulted from the current study. This
work is a part of the Egyptian rare earth separation project,
which has been established in the Nuclear Materials Author-
ity (NMA) for the study and development of the different
rare earths separation methods and selecting the most suit-
able ones that could be used industrially for the production
of rare earth oxides of different grades for both the scientific
and commercial uses.
2. Experimental
2.1. Reagents and solutions
Unless otherwise stated, all reagents were of analytical
reagent grade and all solutions were prepared in calibrated
flasks with double distilled water. Pure Eu(III) synthetic solu-
tions were prepared by dissolving europium oxide (99.9 wt.%
Eu2 O3 supplied by Strem, USA) in a hot concentrated
hydrochloric acid. The natural middle rare earth concentrate
was prepared from the rare earth hydrous oxide cake derived
from acid digestion of monazite. The aforementioned rare
earth hydrous oxide cake was subjected to many chemical
processes, which involves oxidation followed by selective
precipitation of cerium [4,5]. The resulted cerium-free rare
earths raffinate was then undergoes solvent extraction pro-
cess for the preparation of middle rare earth concentrate.
Our trials reach to middle rare earth concentrates containing
7–10% Eu of the total REEs contents using laboratory bench
starting from fine powder (97% purity, −325 mesh, ARAB
LAB, UAE) to zinc sheets (98% purity, Alfa Aesar, USA) and
commercial zinc which supplied kindly by Central Metallur-
gical Research and Development Institute (98% purity, mixed
sizes <20 mesh). Before use, the zinc was washed with 2.0 M
HCl in order to remove any oxide layer that may formed on
zinc surface by air oxidation then washed twice with distilled
water to remove HCl.
2.2. Reduction and precipitation experiments
Three sets of experiments were carried out; two of them
were on a synthetic europium solution, whereas the third one
was tried on a natural middle rare earth concentrate. The
best reduction-precipitation experimental conditions, which
gave the best results, represent the basis for the suggested
europium separation process. Reduction-precipitation exper-
iments were carried out at room temperature. The utilized
reduction-precipitation apparatus consist mainly of a 250 fil-
tering flask tightly closed from direct air with a cork having
two holes. The first one works as inlet for the addition of pre-
cipitating agent and the other one for the entrance of nitrogen
gas to ensure the exclusion of air. The conical flask is stand-
ing on a magnetic stirrer. The apparatus set up is shown in
detail in Fig. 1.
For the single synthetic europium solution experiments,
pure 0.591 g europium oxide (contain 0.5 g Eu) was dissolved
in 5 ml (1:1) concentrated hot hydrochloric acid and 5 ml
glacial acetic was added which makes as a buffer solution.
The pH of the resulting solution was adjusted to a value of
2.5 with 0.1 M NaOH and then, diluted to 100 ml with dis-
 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154
Fig. 1. A schematic diagram for the employed reduction-precipitation apparatus.
tilled water. The solution was flushed with N2 for 30 min
to exclude air. In each experiment Eu(III) chloride solution
was stirred with the reductant (two times the stiochiometric
amount, according to the stiochiometric calculations, 1.18 g
zinc reductant is required to bring about the reduction of 1 g
europium oxide) for different time intervals. Sulphuric acid
or sodium sulphate solution (10 ml, 2.0 M) was then added
and stirring was continued for different time intervals under
the gas flush.
For the natural solutions, about 1 g of the natural middle
rare earth concentrate containing 2.5 wt.% Nd, 10.13 wt.%
Sm, 11.35 wt.% Eu, 2.6 wt.% Gd, and 2.7 wt.% Tb was
dissolved in the least amount of hot concentrated (1:1)
hydrochloric acid, and then, boiled and stirred well until clear
solution is obtained. The reduction-precipitation procedure
was carried out as previously described. Different sulphuric
acid concentration and zinc amounts were used to investigate
their effects on the separation efficiency.
The precipitated europium (II) sulphate was allowed
to settle, and the residual europium content in the super-
natant solution was determined spectrophotometrically by
Arzenazo(III) method using the absorption band at 650 nm
on a double beam of high-resolution power UNICAM-UV
spectrophotometer. Europium was determined in the obtained
europous sulphate spectrophotometrically using the absorp-
tion band at 394 nm [32]. On working with the natural middle
rare earth concentrate, the analysis of the individual rare
147
earth elements has been performed by combined IC–UV–Vis
instrument (DX-500) manufactured by Dionex Corp., USA.
3. Results and discussions
3.1. Reduction-precipitation separation process of Eu
from its single synthetic solution
The main objective of this section is directed to exam-
ine the effect of zinc type (reductant), reduction time, pre-
cipitating agent and precipitation time on the reduction-
precipitation efficiency, which is referred to as the percent
recovery of europium. The lake of information concerning
europium separation on a laboratory and industrial scale,
probably for proprietary reasons, led to the experiments
involving the synthetic solutions. In each experiment in
the series, the europium (III) chloride solution was stirred
with zinc in the presence of N2 for different time inter-
vals (15–90 min). About 10 ml of 2.0 M sulphuric acid (pre-
flushed with N2 for 30 min), was then added and the stirring
was continued for different time intervals (15–60 min). The
flask was maintained under N2 atmosphere to avoid the re-
oxidation of the divalent species. The reduction-precipitation
efficiency of the process was expressed as the recovery per-
cent of europium. The results of these experiments were
represented in Fig. 2.
148 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154
Fig. 2. Effect of zinc type, reduction time and precipitation time on the reduction-precipitation efficiency (percent recovery of europium).
3.1.1. Effect of zinc type
The choice of zinc to act as the reductant in this work
was mainly due to the many advantages exhibited by this
metal (higher reduction efficiency and acceptable losses of
the metal). Preston and du Preez [24] have been indicated
the advantages of zinc powder over other reducing agents
in the literature. The authors compared reactive metals Zn
and Mg, metal amalgams Zn, Na and Eu, metal hydride and
nitrogenous reductants for europium reduction in pure, syn-
thetic, and commercial solutions. Both zinc metal and metal
amalgams (Zn and Eu) worked well with the mixed rare earth
solutions. Europium amalgam was further discarded owing to
the inconvenience of having to divert at least one-third of the
europium content of the feed liquors through the electrolytic
amalgam formation step. The final selection in this study was
to bring about the reduction process by zinc. The zinc particle
size, surface area and its shape has a marked influence on the
completeness of the reduction process, which in turn affects
the separation process overall. Zinc metal may be used in
any form, but high surface area forms are preferred includ-
ing sponge, porous frits, shredded, wool-like, granular, and
combinations. For granular zinc, a size of form about 10–20
mesh size is preferred.
From the results obtained in Fig. 2, it can be seen that,
in all experiments zinc powder is more efficient reductant,
while the commercial zinc metal (having different particles
size) comes in the second order and prior to zinc sheets. These
differences arise due to the difference in the exposed surface
of the reductant.
Zinc powder has been widely used with success for achiev-
ing the reduction process of europium [21,24,33,34]. Despite
the good results obtained with zinc powder over the other two
types, it suffers from the difficulty in separating the unreacted
zinc as a result of its small grain size. The resulted europium
sulphates get contaminated very badly with the unreacted zinc
as well as the raffinate left behind. This problem becomes
more easier by employing the commercial zinc which has a
larger particle seize. Also the dissolved zinc in case of powder
zinc is more than that of commercial and sheets zinc.
The amount of dissolved zinc for zinc powder, sheets, and
commercial one at a reduction time of 60 min and a precipita-
tion time of 60 min was 2.1, 1.2, and 1.5 g L−1 , respectively.
These values show that commercial zinc has the smallest
amount of dissolved zinc compared with those of powder zinc
and zinc sheets. In addition, the commercial zinc has an eco-
nomic advantage over the other two zinc types as it costs less
much. This makes the commercial Zn metal to be the most
suitable one for the reduction process. Preston and du Preez
[24] reported the contamination of the resulted europium sul-
phate and the rare earth leach liquor with zinc. They suggested
the use of solvent extraction technique to get ride of the dis-
solved zinc. They removed zinc from the raffinate by solvent
extraction into a 10 vol% solution of Cyanex 925 in xylene.
The zinc can be readily stripped from the organic phase by
contact with water at temperature above ambient.
3.1.2. Effect of reduction time
The results obtained in Fig. 2 indicate that, in general
the percent recovery of europium increases with increasing
reduction time. In all experiments, the percent recovery of
europium increases sharply with the increase in reduction
time. This behavior is predominant in all precipitation time
intervals and with all zinc types. As evidently illustrated in
Fig. 2 it could be concluded that the maximum reduction was
reached after 1 h in all experiments.
Preston and du Preez [24], stated that the europium (III)
chloride solution should stirred with the reductant for 45 min
to carry out the reduction process. In the process introduced
by McCoy [21], the reduction process was judged to be fin-
ished when litmus was no longer bleached. Otto [33], reported
 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154
that, after 2 h of reduction with continuous stirring, the entire
europium had been converted to the bivalent state.
3.1.3. Effect of precipitation time
Generally, the percent recovery of europium increase with
increasing precipitation time as declared in Fig. 2. At lower
reduction time intervals, the increase in precipitation time
lead to a sharp increase in the percent recovery. However, at
higher reduction time intervals the effect of the precipitation
time began to be less effective and in sometimes it could
be insignificant. For example, the percent recovery shows
no change upon the increase of the precipitation time from
30–60 min at reduction time of 90 min in case of commercial
zinc. On the contrary, this percent increase from 36.5–42%
at a reduction time of 15 min.
The increase in precipitation time as well as the vio-
lent stirring may results in the co-precipitation of the other
rare earth sulphate with europium (II) sulphate. This co-
precipitation decreases the purity of the resulted europium
(II) sulphate [33]. In other words, stirring for extended peri-
ods for the precipitation of EuSO4 would have an adverse
effect upon the purtiy of the separated compound.
Authors have not studied the effect of the precipita-
tion time on the separation efficiency widely in literature.
The separation process introduced by McCoy [21], requires
5 h to precipitate europium (II) sulphate. Preston and du
Preez [24], employed a less much precipitation time, exactly
15 min for synthetic europium solution. They studied the
precipitation rate of europium (II) sulphate from a syn-
thetic middle rare earth mixture by using zinc amalgam and
Fig. 3. Effect of precipitating agent (H2 SO4 and Na2 SO4 ) on the reduction-precipitation efficiency (percent recovery of europium) at two different reduction
time intervals of 60 and 90 min employing a precipitation time of 60 min.
149
europium amalgam. Efficient removal of europium from solu-
tions was achieved after about 1 h. But on working with
authentic rare earth solution the precipitation of europium
(II) sulphate proceeds considerably more slowly than in the
case of the synthetic solutions. It takes over 2 h to bring
about 92% removal of the present europium. Otto [33],
also reported that, precipitation steps needs 2 h in order
to assure complete removal of europium from the working
solution.
3.1.4. Effect of precipitating agent
To investigate the effect of the precipitating agent on the
separation efficiency, the percent recovery of sulphuric acid
and sodium sulphate at 60 and 30 min precipitation time were
plotted in Fig. 3. This figure shows the recovery percents of
the two precipitating agents at reduction time of 60 and 90 min
and utilizing commercial zinc as a reductant. It can be figuring
out that, sulphuric acid exhibit a higher percent recovery than
sodium sulphate over all the reduction and precipitation time
intervals.
In addition, it is apparent that, by employing sulphuric acid
as the precipitating agent, maximum separation efficiency
reaches in a less much time than sodium sulphate. Although
the difference in percent recoveries between the two precip-
itant is not quite huge, the sulphuric acid is favored because
of its low price and owing to the low solubility of sodium sul-
phate (approximately 0.5 mol L−1 at 20 ◦ C). Also on working
with a rare earth mixture containing europium, sodium sul-
phate tends to form alkali rare earth double sulphates that
co-precipitate with europium (II) sulphate [33]. This results
150 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154
Fig. 4. Effect of sulphate ion concentration on the recovery and purity of obtained europous sulphate.
in decreasing the purity of the precipitated europium (II) sul-
phate.
Various precipitating agent have been utilized by work-
ers to achieve the precipitation of europous sulphate. McCoy
[20], in his early work for the separation of europium by
zinc chemical reduction used magnesium sulphate as the pre-
cipitant. Preston and du Preez [24], have been studied the
precipitation of europium (II) sulphate using ammonium sul-
phate. Otto [33], suggested the use of strontium or barium
sulphate as the precipitating agent.
3.2. Reduction-precipitation separation process of Eu
from natural middle rare earth concentrate
In this section, we studied the effects of molar ratio
SO4 2− /Eu, and the ratio of zinc added amount /stiochiomet-
ric zinc amount on the separation efficiency. We have been
preferred to study these effects on the naturally occurring
mixture instead of a synthetic solution, because these fac-
tors are significantly influenced by the other rare earths that
accompany the europium in the natural mixture.
3.2.1. Effect of molar ratio of SO4 2− /Eu (effect of
sulphuric acid concentration)
The sulphuric acid concentration has a marked effect upon
both the recovery and purity of the separated europium (II)
sulphate. In order to inspect this effect, different concentra-
tion of sulphuric acid has been used for the precipitation of
Eu+2 as EuSO4 . The sulphuric acid concentration was varied
from 0.5 to 5 M. The volume added was set at 10 ml, which
corresponds to change in the concentration from 0.005 to
0.5 mol sulphuric acid in a total 10 ml volume. The percent
recovery and purity for each employed concentration were
declared in Fig. 4.
The results obtained show that, both the recovery and
grade of the obtained europium sulphate are significantly
affected by sulphate concentration in the precipitation vessel.
As shown in Fig. 4, the percent recovery is directly propor-
tional to the sulphate concentration. At sulphate concentra-
tions lower than 3 mol L−1 , the percent recovery increases
sharply with the increase of sulphate concentration, whereas
it slightly increases with sulphate concentration higher than
3 M H2 SO4 . The europium recovery is nearly independent of
acid concentration higher than 3 mol L−1 . The sulphuric acid
concentration was increased up to 5 mol L−1 as an attempt
to shift reaction (3) to the right, which in turn increases the
europium recovery.
Eu2+ 2−
(aq) + SO4(aq) = EuSO4 (3)
Based on the reaction stoichiometry, 0.0066 mol of H2 SO4 is
needed to precipitate the 0.1 g europium present in the feed
solution. Thus, the 10 ml of 3 mol L−1 H2 SO4 , is 4.5 times
the stiochiometric amount needed to bring about the precip-
itation of 0.1 g europium as sulphate. Preston and du Preez
[24], utilized 100 ml of a 2 M (NH4 )2 SO4 solution to pre-
cipitate 11.85 g Eu present in an authentic middle rare earth
concentrate. This concentration is 2.5 times the stiochiomet-
ric amount of ammonium sulphate. In addition, McCoy [21],
in his early work utilized two times the stiochiometric amount
of magnesium sulphate to precipitate about 250 g europium
oxide. Otto [33], employed a stiochiometric amount of one
to precipitate a much larger europium content of 450 g. It
seems sound that, as the europium concentration (content) in
the feed solution increases, the less stiochiometric amount of
the precipitating gent will be needed to carry out the precip-
itation reaction.
On the contrary, to the percent recovery, the purity of
the resulted europium sulphate decreases with the increase
 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154
of sulphate concentration. At sulphate concentration below
3 mol L−1 , a slight decrease in the europium sulphate purity
is observed with increasing the sulphate concentration, as
seen in Fig. 4. The purity of the europium sulphate began
to decrease sharply at sulphate concentration higher than
3 mol L−1 . The purity decreases by about 2% on the increase
of sulphate concentration from 0.005 to 0.03 mol L−1 , while
this percent increase to 13% by increasing the sulphate con-
centration from 0.03 to 0.05 mol L−1 .
Generally, the decrease in the europium sulphate purity
with the increase in sulphate concentration originates from
the co-precipitation of the other rare earths that accompany
europium in the middle rare earth concentrate. Higher sul-
phate concentration causes the precipitation of these elements
together with europium sulphate, which decreases its purity.
This was confirmed by investigating the composition of the
resulted product at sulphate concentration of 5 mol L−1 (80%
Eu, 14.1% Sm, 3.5% and 0.7% Nd) and at 3 mol L−1 (92.9%
Eu, 5.4% Sm, 1.1% Gd and 0.5% Nd). This suggests that,
the contaminant metals are incorporated into the europium
(II) sulphate crystal lattice. This process becoming more
favorable as the radius of the trivalent cations becomes more
closely approximates to that of Eu+2 (Eu+2 1.09 A◦ , Sm+3
0.96, Gd+3 0.94, Nd+3 1.00, and Pr+3 1.01 A◦ ). Preston and
du Preez [24], mentioned the decrease of europium recovery
from a middle rare earth strip liquor compared with the recov-
eries obtained with pure europium solutions owing to the
co-precipitation which occurs during the precipitation reac-
tion.
It was noticed that 1-h precipitation time was not enough
to bring about a complete precipitation of europium sulphate
in case of the natural middle rare earth mixture. In other
words, the precipitation of europium (II) sulphate proceeds
more slowly than in the case of the single synthetic solu-
tion. This may be as a result of the slow reduction of certain
impurities that are present in the natural mixture, such as par-
Fig. 5. Effect of ratio of zinc added amount /stiochiometric zinc amount on the recovery and purity of obtained europous sulphate.
151
tially hydrolyzed iron (III) species. In this work, there was a
maximum in the europium recovery at a sulphuric acid con-
centration of 3 mol L−1 , corresponding to 0.03 mol H2 SO4
in the system, with a purity of 92.9%. This corresponds to a
SO4 2− /Eu molar ratio of 46.
3.2.2. Effect of ratio of zinc added
amount/stiochiometric zinc amount
According to the stiochiometric calculations, 1.18 g zinc
reductant is required to bring about the reduction of 1 g
europium oxide. The effect of ratio of zinc added amount
/stiochiometric zinc amount on the separation efficiency was
investigated by employing different stiochiometric amount of
zinc to reduce 1 g middle rare earth concentrate. The resulted
recovery and purity percents were represented in Fig. 5. The
results illustrated in this figure declare that, the increase of
zinc amount is usually accompanied by an increase in the per-
cent recovery, which tends to become independent at ratios
higher than 2.5. On the contrary, the purity of the resulted
europium (II) sulphate seems to be nearly independent of the
stiochiometric amount of zinc.
McCoy employed a stiochiometric zinc amount of 2.5 for
the reduction of a rare earth chloride solution containing 250 g
europium oxide. Preston and du Preez [24], have been carried
out the reduction step with two equivalents of reductant.
It could be noticed that, the reduction efficiency reach its
maximum at a relatively higher stiochiometric zinc amount
of 2.5, as a result of the consumption of the reductant by the
other reducible species that my be present in the working
solution. The required stiochiometric zinc amount is greatly
influenced by the reducible ions, such as ferric, lead, nitrate,
sulphate and tin, which may be encountered in the working
solutions. Therefore, it is highly recommended to remove
any reducible ions prior to the addition of the reductant to
the europium chloride solution. This can be done by treating
the chloride solution with hydrogen sulphide to precipitate
152 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154

Fig. 6. A proposed flowsheet for the suggested europium separation process.

 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154
lead, iron and tin as their insoluble sulphides. Also addition
of barium chloride solution guarantees the effective removal
of sulphate as insoluble barium sulphate.
It should be reported that, the reduction and precipitation
processes were traditionally done together in the same time.
In other words, the reducing agent was added to the work-
ing solution followed directly by the addition of precipitant.
This represents a disadvantage in the old procedure because
it causes an interference between the europium and sulphate,
which are already reducible by zinc metal. An improvement
to the old reduction-precipitation procedure was introduced
in this work wherein, the precipitating agent was introduced
after the accomplishment of the reduction process in order to
decrease the competition between europium and sulphate.
3.3. Suggestion and application of a full separation
process for europium
From the results of the aforementioned reduction–
precipitation experiments, the optimum conditions for ach-
ieving the reduction-precipitation process that would be used
to separate europium from a natural middle rare earth con-
centrate can be summarized in a process input box as follow:
• Reductant: commercial zinc metal of mixed size particles.
• Stiochiometric amount of reductant: 2.5 zinc equivalents.
• Reduction time: 60 min.
• Precipitating agent: sulphuric acid.
• Concentration of the precipitating agent: 3 M or to a final
molar ratio SO4 2− /Eu of 46.
• Precipitation time: 2 h.
• Non-oxidizing gas: nitrogen.
Based on the above research results, a process was sug-
gested, developed and applied for the separation of europium
from the middle rare earth concentrate produced from Egyp-
tian black sand monazite. Fig. 6 gives a schematic flowsheet
for the proposed europium separation process. The separation
process was carried out by using the in situ zinc reduction
apparatus, which has been described previously in Section
2.2. As the europium sulphate has a retrograde solubility, so
it is very favorable to heat the precipitation solution to about
80 ◦ C to encourage the stability of the precipitate.
It was reported by McCoy [21], that the hot magnesium
sulphate solution gave rise to the ␤-form of europous sul-
phate, rather than the ␣-form. This is desirable as the former
is less soluble and much denser than the latter. After heat-
ing, the precipitate was then removed from the solution by
filtration in a Gooch-type crucible. The precipitate consisted
largely of excess zinc, and europium sulphate, together with
considerable rare earths. Analysis of the europium (II) sul-
phate product showed it to contain (as a percentage from the
total rare earths content): 92% europium, 3.5% samarium,
2% neodymium, 1% cerium, 0.6% praseodymium, and 5%
gadolinium with a percent europium recovery of 95%.
In order to increase the purity of the obtained europium (II)
sulphate, it was subjected to another reduction-precipitation
153
process. No change in the reduction process was introduced
in the purification process, on contrary to the precipita-
tion process in which the utilized sulphuric concentration
was decreased to 2 M to reduce the amount of the other
rare earths that co-precipitated along with europium sul-
phate. In addition, the precipitation time was reduced to
60 min instead of 2 h for the previously mentioned rea-
son. The result of this working-up is a europium yield of
about 96% of the amount employed with a purity of about
97%.
3.4. Shortcomings in the proposed separation process
and solution of them
The use of the oxalate precipitation, in spite of its difficulty
and inapplicability for large-scale production was necessary
for the complete removal of the remained zinc in both the
resulted product and the raffinate. The proposed separation
process suffers from a significant shortcoming, which lies in
the contamination of the raffinate containing Sm and Gd with
a large proportion of dissolved zinc, which in turn requires
further chemical treatment process for the removal of this
foreign ion. The reason for this contamination is; the disso-
lution of zinc during both the reduction and precipitation step
because of its reaction with the hydrochloric and sulphuric
acid, respectively.
The aforementioned problem not annoys us because the
reasons are known and could be solved either by:
i. The use of acetic acid instead of hydrochloric acid for
the dissolution step, wherein the dissolved Zn may be
later removed from solution as ZnS by using H2 S gas
or Na2 S taking the advantage of being insoluble in
acetic acid whereas it is readily soluble in HCl and
H2 SO4 .
ii. Avoiding the acid–Zn metal contact by placing Zn metal
in a specific designed column. This is the other worked
technique for carrying out the separation process in which
the reduction process occurs by the passage in a zinc col-
umn, wherein its outlet is dipped in a precipitation kettle.
This configuration guarantees the occurring of the precip-
itation reaction without any contact between the reductant
and precipitating agent.
3.5. The advantage of the proposed reduction-
precipitation commercial process
i. The economic of the process overcome the loss in the
europium content.
ii. The local availability of the reagents inside the Egyptian
markets and one can say that the by-product of metallur-
gical process and phosphoric acid industry are the main
reducing-precipitating reagents which are Zn metal and
sulphuric acid, respectively.
iii. The other REEs especially precious middle members (Sm
and Gd) not affected seriously.
154 S.A. Sayed et al. / Separation and Purification Technology 46 (2005) 145–154
4. Conclusion
Factors affecting the europium separation by utilizing the
reduction–precipitation process were studied on synthetic
and natural europium solutions in detail. The obtained results
shows the great dependence of the process efficiency on zinc
reductant type and its stiochiometric amount, reduction and
precipitation time, and finally the nature of sulphate source
and its concentration. The best resulted reduction precipi-
tation conditions were found to be: reductant: commercial
zinc metal of mixed size particles; stiochiometric amount
of reductant: 2.5 zinc equivalents; reduction time: 60 min;
precipitating agent: sulphuric acid; concentration of the pre-
cipitating agent: 3 M or to a final molar ratio SO4 2− /Eu of
46; precipitation time: 2 h, non-oxidizing gas: nitrogen.
Based on the obtained optimum reduction-precipitation
conditions a process was suggested and applied on authen-
tic europium acid solution containing 2.5% Nd, 10.13% Sm,
11.35% Eu, 2.6% Gd, and 2.7% wt Tb which was prepared
by solvent extraction procedures on a laboratory mixer set-
tler. Europium was separated successfully with a purity of 92
and 95% efficiency using commercial zinc metal reductant
and sulphuric acid as precipitant. In the second reduction-
precipitation run the purity was increased to 97% with a final
recovery of 91%.
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