Chemical Engineering Science 54 (1999) 1903—1907

On the kinetics of rare-earth extraction into D2EHPA

Andreas Geist *, Walter Nitsch
, Jae-II Kim
Forschungszentrum Karlsruhe, Institut fu( r Nukleare Entsorgungstechnik, P.O.B. 3640, D-76021 Karlsruhe, Germany

¹echnische ºniversita( t Mu( nchen, Institut fu( r ¹echnische Chemie, ¸ichtenbergstr. 4, D-85748 Garching, Germany

Received 21 July 1998; accepted 18 December 1998

Abstract

Extraction kinetics of rare-earth elements (La>, Ce>, Pr>, Nd>, Eu>) in nitric acid, thiocyanate and formate into D2EHPA
(bis-2-ethylhexyl phosphoric acid ester, 0.05 kmol m\) is studied in a stirred cell at pH"2.1. Extraction rate is found to be limited by
diffusion. Individual mass transfer coefficients remain consistent for the metal ions investigated within a given aqueous system but are
found to be approximately 25% higher in the formate system than in others. An explanation can be given by coupled diffusion of
cationic and anionic species.  1999 Elsevier Science Ltd. All rights reserved.

Keywords: Rare-earth elements; Bis-2-ethylhexyl phosphoric acid ester; Extraction; Kinetics; Thiocyanate; Formate

1. Introduction or toluene are well established (Peppard et al., 1957:

Kolarik and Pankova, 1996; Alstad et al., 1974; Kandil
1.1. Extraction equilibria and Farah, 1979: Imai et al., 1992) and the stoichiometry
of extraction usually is determined as
The separation of rare-earth elements by chemical
extraction requires high numbers of extraction stages due Ln>#3(HX) & LnX (HX) #3H> (1)
  
to very low separation factors between adjacent rare-
with the equilibrium constant K
earth elements. The highest separation factors can be
achieved with cation-exchanging extractants, especially
[LnX (HX) ][H>]
phosphoric acid esters: reported mean separation factors K"   (2)
between adjacent rare-earth elements are in the range [Ln>][(HX) ]

of 2.5 (Peppard et al., 1957; Zheng et al., 1991) to 3.05
assuming dimerization of D2EHPA in the organic phase
(Ceccaroli and Alstad, 1981) for D2EHPA (bis-2-ethyl-
(Peppard et al., 1958). Equilibrium constants measured
hexyl phosphoric acid ester). In contrast, solvating ex-
using various diluents are reported. The differences in
tractants yield rather low mean separation factors.
equilibrium constants between aliphatic hydrocarbons
Reported values for TBP (tri-n-butyl phosphate) are in
and toluene or benzene are about three orders of mag-
the range of 1.09 (Ceccaroli and Alstad, 1981) to 1.24
nitude (i.e. a change in pH values in the range of
(Mokili and Poitrenaud, 1997). Hence, solvating extrac-  
one pH-unit) with hydrocarbons yielding the highest
tants are useful for the recovery of mixed rare-earth
K values (Kandil and Farah, 1979; Imai et al., 1992).
products, whereas cation-exchanging extractants are best
suited for the separation of rare-earth elements from one
another (Preston and Du Preez, 1992). 1.2. Extraction kinetics
Equilibrium data for the extraction of rare-earth ele-
ments into D2EHPA diluted in aliphatic hydrocarbons With knowledge of equilibrium data it is possible to
estimate the number of separation stages required for a
demanded separation efficiency. However, in order to
design an extraction process, knowledge of kinetic data is
*Corresponding author. Tel.: 00 49 7247/826249; fax: 00 49 advantageous. Here, especially, the discrimination of the
7247/823927; e-mail: geist@fzk.ine.de rate-determining step (diffusion or chemical reaction) is

0009-2509/99/$ — see front matter  1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 0 1 4 - 7
1904 A. Geist et al./Chemical Engineering Science 54 (1999) 1903—1907
important. However, not much is published on the
kinetics of rare-earth extraction into D2EHPA. Ex-
perimental results are usually explained by a rate con-
trolling chemical reaction with diffusional influence (Lim
et al., 1996; Danesi and Vandergrift, 1981; Danesi et al.,
1982).
The goal of this work is to further elucidate extraction
kinetics of rare-earth elements (here: La>, Ce>, Pr>,
Nd>, Eu>) into D2EHPA dissolved in kerosene. Pre-
vious results on the extraction kinetics of Eu>/HNO
 pH"2.1.
into D2EHPA over a wide range of both metal and
extractant concentrations indicate that mass transfer is
limited by diffusion (Knei{l et al., 1998). Based on these
results, a possible influence of aqueous-phase composi-
tion (either nitric acid, formate or thiocyanate) on extrac-
tion kinetics is investigated. Formate and thiocyanate are
used since both are commonly used in several systems
tested for Am>/Eu> separation (Kolarik and Mu( llich,
1997; Madic et al., 1997; Chiarizia et al., 1995; Borkowski
et al., 1994). Ceccaroli and Alstad (1981) report an in-
crease in separation factors between rare-earth elements
if thiocyanate is used.
The apparatus used for kinetic experiments is a Nitsch
stirred cell (Nitsch et al., 1973) in its improved design
described by Waubke (1988). This cell has been calib-
rated on heat transfer and the physical mass transfer
showing that the rates of processes limited by transport
phenomena is linearly dependent on stirrer speed over
a wide range (Nitsch et al., 1973). Limitation by chemical
reaction can be identified by the so-called plateau rates,
i.e. above a distinct stirring speed mass transfer does not
further increase with stirring speed (Nitsch and Kruis,
1978) (see Fig. 1). Hence, this kind of stirred cell allows
for an easy discrimination between limitation by diffu-
sion and limitation by chemical reaction.
2. Experimental
Kinetic experiments in the stirred cell were carried
out at 293 K. Phase volumes are » "» "3.75;
 
Fig. 1. Flux dependency on stirrer speed in a Nitsch stirred cell: limita-
tion by chemical reaction vs. limitation by diffusion.

10\ m (375 cm), the interfacial area is A"4.42;
10\ m (44.2 cm).
Aqueous-phase composition was La>, Ce>, Pr>,
Nd>, Eu>(10 mg l\ each) in
(a) nitric acid, pH"2.1,
(b) ammonium thiocyanate 1.0 kmol m\, adjusted with
nitric acid to pH"2.1,
(c) formic acid 0.975 kmol m\#sodium formate
0.025 kmol m\#sodium nitrate 0.008 kmol m\;
Rare earths were used as nitrates.
Organic phase was D2EHPA (Bayer AG, Germany)
0.05 kmol m\ (concentration of dimeric species) in kero-
sene (Fluka, Germany). Both chemicals were used as
received.
The stirred cell was filled with aqueous and organic
phases, stirrers were started with appropriate stirring
numbers (aqueous"organic), 1 ml of a concentrated
solution containing all five rare-earth elements (as ni-
trates) was injected. Samples (1 ml) from the aqueous
phase were taken every 15 min and the same volume of
water was added in order to exactly maintain the level of
liquid/liquid interface. Samples were analyzed by ICP-
OES (Spectro, Germany). The measured concentration
was plotted vs. time and initial metal fluxes were cal-
culated from initial slopes
D[Ln>]»
j >" . (3)
* DtA
3. Results and discussion
3.1. Extraction regime
Figs. 2—4 show initial metal fluxes j normalized to
R
initial metal concentrations [Ln>] over stirring
R
speed n . As can be seen from the linear increase of initial

metal flux with stirrer speed, extraction rates are limited
by diffusion regardless of aqueous-phase composition
(shown are the results for the extraction of Pr> as other
elements investigated yield the same results). This means
that the chemical reaction is fast and an equilibrium is
established at the liquid/liquid interface.
Experimental conditions chosen maintain mass trans-
fer resistance in the aqueous phase, i.e. mass transfer is
limited by diffusion of rare-earth metal ions. This can be
achieved by initial conditions that maintain high distri-
bution coefficients D,
[LnX (HX) ]
D"   (4)
[Ln>]
of metallic species during the kinetic experiment by
keeping the pH well above pH and using an excess of

 A. Geist et al./Chemical Engineering Science 54 (1999) 1903—1907
Fig. 2. Initial flux dependency on stirring speed for extraction of rare-
earth elements (La>, Ce>, Pr>, Nd>, Eu>) into D2EHPA (figure
shows Pr>). [(HX) ]"0.05 kmol m\; [Ln>] "10 mg l\ (each);
 R
n "n ; aqueous-phase: nitric acid; pH"2.1.
 
Fig. 3. Initial flux dependency on stirring speed for extraction of rare-
earth elements (La>, Ce>, Pr>, Nd>, Eu>) into D2EHPA (figure
shows Pr>). [(HX) ]"0.05 kmol m\; [Ln>] "10 mg l\ (each);
 R
n "n ; aqueous-phase: ammonium thiocyanate 1.0 kmol m\#ni-
 
tric acid; pH"2.1.
complexing agent over metal ions (Walter et al., 1993;
Geist, 1997).
3.2. Individual mass transfer coefficients
In the case of mass transfer limited by diffusion, the
flux j of a component A is given by its individual mass
transfer coefficient b and the driving concentration

gradient between bulk concentration, [A], and concen-
tration at the interface, [A]*:
j "b ([A]![A]*). (5)
1905
Fig. 4. Initial flux dependency on stirring speed for extraction of rare-
earth elements (La>, Ce>, Pr>, Nd>, Eu>) into D2EHPA (figure
shows Pr>). [(HX) ]"0.05 kmol m\; [Ln>] "10 mg l\ (each);
 R
n "n ; aqueous phase: (formic acid#sodium formate)
 
1.0 kmol m\#sodium nitrate 8 mol m\; pH"2.1.
If the diffusion of A is the limiting step, its interfacial
concentration [A]* is to be neglected and hence,
j "b [A]. (6)
Here, the diffusion of metal ions is the limiting step.
Hence, the y-axis values in Figs. 2—4 directly yield indi-
vidual mass transfer coefficients for metal ions, b .
*
3.3. Influence of aqueous-phase composition
Mass transfer coefficients normalized to stirring speed,
b /n , for all rare-earths examined are compared in
* 
Fig. 5. As can be seen, values are approximately constant
for La> to Eu> within a given system and no enhance-
ment of separation due to kinetic effects can be observed.
However, mass transfer coefficients in the formate system
are approximately 25% higher than that in nitric acid
and thiocyanate systems.
An influence of the nitrate concentration can be
excluded as it is maintained constant at [NO\]"

9 mol m\ in all systems (1 mol m\ from rare-earth
nitrates used#8 mol m\ from either nitric acid or so-
dium nitrate; see Section 2. Differences in mass transfer
coefficients have to be attributed to formate.
The mass transfer coefficient is dependent on the
diffusion coefficient, D , and residence time of volume
elements at the interface, q, according to Higbie’s pen-
etration model (Higbie, 1935).

D
b "2 . (7)
 nq
As D and q depend on viscocity, viscocities of aqueous
phases involved are measured. They are found to be
1906 A. Geist et al./Chemical Engineering Science 54 (1999) 1903—1907

Acknowledgements

D2EHPA was kindly supplied by Bayer AG, Ger-

many.

Notation

A interfacial area, m
D diffusion coefficient, m s\
D distribution coefficient, dimensionless
j flux, kmol m s\
» volume of half cell, m

Fig. 5. Comparison of mass transfer coefficients standardized on stir- Greek letters

ring speed for the extraction of several rare-elements into D2EHPA in
varying aqueous phase: (——) (䊉) nitric acid; pH"2.1; (2) (䊊) b mass transfer coefficient, m s\
ammonium thiocynate 1.0 kmol m\ # nitric acid; pH"2.1; (-----)
(䉲) (formic acid#sodium formate) 1.0 kmol m\#sodium nitrate
l viscosity, m s\
8 mol m\; pH"2.1; [(HX) ]"0.05 kmol m\; [Ln>] " q residence time, s
 R
10 mg l\ (each); n "n .
 
Subscripts

the same within $3% at l"1.02;10\ m s\. This aq in aqueous phase

excludes the possibility of a hydrodynamic effect (e.g. a
change in residence time of volume elements at the inter-
face) leading to different mass transfer coefficients.
An explanation can be given by multi-component dif-
fusion: Due to a much higher diffusion coefficient of
protons as compared to metal ions, the proton concen-
tration gradient is shallower and extends farther into the
aqueous bulk phase. As aqueous concentration gradients
of all ionic species are coupled by the requirement of
electroneutrality, an anion gradient is established. Effec-
tive diffusion coefficients for all species are represented by
the Nernst—Planck equation (Newman, 1991). They are
dependent on concentration gradients and diffusion coef-
ficients of all other ionic species including anions. This is
where aqueous-phase composition can have an influence
on mass transfer coefficients.
4. Conclusion
In reactive liquid/liquid extraction, kinetic factors can
contribute to separation, especially when countercurrent
column contactors are used. However, the results of the
presented experiments indicate that the separation of
rare earth is not kinetically enchanced by the aqueous
phases investigated, as mass transfer coefficients do not
differ among rare-earth elements in a given system. Their
separation will only be accomplished by differences in
equilibrium constants, i.e. the proper adjustment of pH.
It can be concluded that, as long as mass transfer is
limited by diffusion and no stable metal complexes exist
in the aqueous phase, aqueous-phase compostion has no
effect on extraction kinetics.
org in organic phase
t"0 initial value
[A] concentration of species A, kmol m\
* at liquid/liquid interface
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