J Radioanal Nucl Chem (2011) 287:239–245
DOI 10.1007/s10967-010-0857-1
Determination of optimum process conditions for solvent
extraction of thorium using Taguchi method
M. Eskandari Nasab • A. Sam • S. Alamdar Milani
Received: 18 June 2010 / Published online: 10 October 2010
Ó Akadémiai Kiadó, Budapest, Hungary 2010
Abstract Solvent extraction of thorium was studied using
Taguchi method. The effect of various parameters such as
acid types (sulfuric, nitric, hydrochloric, sulfuric ? nitric)
and their concentrations from 0.001 to 4 M, initial thorium
concentration (0.0001, 0.001, 0.01, 0.1 M) and solvent type
(TBP, D2EHPA, Cyanex921, Cyanex272) in the ranges of
0.001 to 1 M on thorium extraction efficiency were
investigated. The maximum extraction of thorium was
obtained while 0.001 M hydrochloric acid, 0.001 or
0.01 M thorium and Cyanex272 were used. Under these
optimum conditions, the extraction percent and distribution
coefficient of thorium were 98.7% and 73.8, respectively.
Compared with the hydrochloric aqueous solution, the
nitric acid system showed less variation in the extraction of
thorium. The proposed process has been applied for the
separation of Th(IV), U(VI), La(III), and Ce(III) from
synthetic solution same as thorium ores (monazite).
Keywords Thorium  Solvent extraction  Cyanex272 
D2EHPA  TBP  Cyanex921
M. Eskandari Nasab (&)
Faculty of Mineral Processing Engineering, Bahonar University,
P. O. Box 14579-73869, 7616914111 Kerman, Iran
e-mail: mahmoodeskandari2010@yahoo.com;
meskandarim@yahoo.com
A. Sam
Faculty of Mineral Processing Engineering, Bahonar University,
7616914111 Kerman, Iran
S. Alamdar Milani
Jaberebne Hayan Research labs, P. O. Box 14893-836,
Tehran, Iran
Introduction
Thorium has great importance in the nuclear energy field.
Also, there is a worldwide belief that thorium fuel will be one
of the most important fuels for the world in the future. Thus,
purity requirements for thorium and its compounds, espe-
cially in nuclear technology, have much significance.
Among the major processes for extraction and purification of
thorium, solvent extraction offers one of the cleanest tech-
nologies [1]. Continuous efforts have been made to develop
new extractants for the extraction and separation of thorium.
The conventional processes for thorium purification were
Amex and TBP/HNO3 ones [2]. Using a combination of
different amines in three successive cycles is the basis of the
Amex route. In the TBP/HNO3 process 4 M nitric acid
solution containing 200 g/l thorium has been contacted
counter currently with 40% vol. TBP in kerosene and the
distribution coefficient of thorium was only 1, which remains
thorium in the aqueous solution with some of impurities. The
most important disadvantages of these technologies are the
large consumption of chemicals and then large numbers of
extraction steps to obtain highly purified of thorium. The
disadvantages of these processes could be largely decreased
if it were practicable for thorium extraction.
Over the years, various kinds of organophosphorus
extractants, both acidic and neutral ligands, were investi-
gated for thorium extraction [3–8]. Among them the acidic
extractants have shown very large distribution coefficient
from nitrate media in the pH region. For example, Karve
and Gaur reported that the distribution coefficient of tho-
rium in 0.001 M HNO3 was 110.1 [4]. Also El-Hefny and
Daoud found that Cyanex302 is more effective than Cya-
nex301 for extraction of thorium from nitrate media [5]. For
the neutral extractants, in spite of TBP process [2], using of
Cynex923 by Gupta et al. [3] resulted high extraction and
123
240 M. Eskandari Nasab et al.

separation efficiency of thorium. These methods had certain
limitations such as, complex formation of TBP with fluo-
ride, sulfate, phosphate, and carbonate anions, emulation
formation of D2EHPA, poor selectivity of Cyanex921 and
need to multistage stripping for Cyanex923. Consequently
the search for better extractants and conditions continues. In
many of previous experiments, the aqueous medium was
nitric acid solution. Since the extraction efficiency is likely
to depend significantly on the aqueous phase conditions, it
is necessary to carry out a particular investigation on the
extraction behavior of thorium from different aqueous
media with various types of extractants.
In the present work, extraction behavior of thorium was
studied with organophosphorus extractants such as Cya-
nex272, D2EHPA, or Cyanex921 as an alternative for
conventional TBP process via Taguchi method. In addition,
this study was focused on the comparison of extraction
behavior of thorium through changing the acidic media
conditions and types; finally, the optimum condition was
used for separation of thorium, uranium, and lanthanides.
design method is one of the efficient means for evaluation
and improvement of the laboratory and continuous process
efficiency [9].
0
In this research, we used Taguchi L16 orthogonal array
design (i.e., five parameters and each parameter at four
levels). Investigating these numbers of parameters and
levels by using conventional factorial design would require
0
1024 experiments. But by using the Taguchi L16 orthogo-
nal array, the number of the required experiments is
reduced to only sixteen. In the Taguchi method, confir-
matory experiments are required if there is not a single
experiment with all of optimum levels in the proposed
orthogonal arrays. Table 1 shows the combinations of
variables and levels in our experiments. In the Taguchi
method, the signal to noise (S/N) ratio is used to determine
the best experimental conditions. Because of the purpose of
this work, the S/N ratio (the larger the better) was used to
evaluate the response of each experiments [10]. This
equation can be written as:
   !
S 1X 1
¼ 10 log ð1Þ
N i n i y2i

Experimental
Experimental design
Experimental design is the important tools for off-line and
experimental quality control. The Taguchi orthogonal array
.
Here, n is the number of tests and yi is the experimental
value in the Ith experiment. Distribution coefficient was
used as the most important index for determining the
efficiency of solvent extraction process and can be
expressed as:

0
Table 1 Taguchi L16 orthogonal array design for thorium solvent extraction
Test No Parameters Results
Solvent conc. (M) Solvent type Concentration (M) Acid type Thorium extraction (%) Distribution coefficient S/N ratio
Thorium Acid

1 10-3 TBP 10-4 10-3 HNO3 47.2 0.9 -1.1

-3 -3
2 10 Cyanex272 10 10-1 H2SO4 51.1 1.0 -2.3
3 10-3 Cyanex921 10-2 1 MIX* 26.3 0.4 -9.0
4 10-3 D2EHPA 10-1 4 HCl 42.2 0.7 -2.7
-2 -3
5 10 TBP 10 1 HCl 31.0 0.4 -7.3
6 10-2 Cyanex272 10-4 4 MIX 36.0 0.6 -6.0
7 10-2 Cyanex921 10-1 10-3 H2SO4 15.8 0.2 -14.8
8 10-2 D2EHPA 10-2 10-1 HNO3 54.8 1.2 1.6
9 10-1 TBP 10-2 4 H2SO4 27.7 0.4 -8.4
10 10-1 Cyanex272 10-1 1 HNO3 37.4 0.6 -4.6
-1
11 10 Cyanex921 10-4 10-1 HCl 72.5 2.6 8.1
12 10-1 D2EHPA 10-3 10-3 MIX 94.0 15.7 23.9
-1
13 1 TBP 10 10-1 MIX 22.4 0.3 -10.8
14 1 Cyanex272 10-2 10-3 HCl 98.7 73.8 37.4
15 1 Cyanex921 10-3 4 HNO3 76.4 3.2 10.3
16 1 D2EHPA 10-4 1 H2SO4 43.5 0.8 -2.6
* A mixture of sulfuric acid and nitric acid (voluminal ratio = 1:1)

123
Determination of optimum process conditions for solvent extraction of thorium 241

ðC0  C Þ 0.0001–4 M. Also, equal volumes of organic phase

D¼ ð2Þ (10.0 ml) containing 0.001–1 M of Cyanex272, Cya-
C
nex921, TBP, and D2EHPA were prepared by dissolving
Where, D, C0 and C are distribution coefficient, the tho-
appropriate amount of these extractants in the kerosene.
rium concentrations in the aqueous phase before and after
The solvent extraction experiments (Table 1) were
equilibrium, respectively. The distribution coefficient,
conducted through shaking the equal volumes of two
extraction percentage and S/N ratio for each of the exper-
phases using a mechanical shaker. The temperature and
imental combinations are depicted in Table 1.
contact time of the two phases were adjusted to 25 °C and
15 min, respectively. With respect to the above mentioned
Chemical and reagents
references, these amounts of parameters would exceed the
required amount for optimum extraction of thorium [3, 7].
Thorium nitrate Th(NO3)4.5H2O, MW = 570 g/mol, Ura-
The two phases were allowed to be settled, and then they
nium nitrate, UO2(NO3)2.6H2O, MW = 502.18 g/mol;
were separated by separatory funnel. The thorium con-
Lanthanum chloride LaCl3.7H2O, MW = 371.38 g/mol,
centration of aqueous phase before and after extraction for
Cerium Chloride CeCl3.7H2O, MW = 372.59 g/mol, all
each experiment was determined using inductively coupled
from Merck; Kerosene, Cyanex272, Cyanex921, from Fluka;
plasma atomic emission spectrometer. An ICP-AES ana-
TBP, and D2EHPA, from Merck were used as chemical
lyzer from Liberty 220 Varian was used in this regard.
reagents. All of reagents were used at analytical grade.
Then the distribution ratio was determined through the
Eq. 2. The reproducibility of the experiments exhibits a
Experimental procedure and apparatus
variation coefficient of less than ±3%.
The stock solution of thorium was prepared by dissolving
appropriate amounts of thorium nitrate powder in the dis- Result and discussion
tilled water. Then equal volumes (10.0 ml) of the aqueous
phases (0.0001–0.1 M thorium ion) were provided by dis- Determination of optimum conditions
solving appropriate amount of thorium stock solution in the
hydrochloric, nitric, and sulfuric acid solutions. The final Figure 1 shows the average S/N ratio for distribution
acid concentrations of the aqueous phases were coefficient of thorium. From this figure, it is clear that the
Fig. 1 S/N graph for thorium
extraction

123
242 M. Eskandari Nasab et al.

optimal combinations were extraction of 0.001 or 0.01 M
thorium from 0.001 M hydrochloric acid solution by 1 M
Cyanex272 in kerosene. Under these conditions, a distri-
bution coefficient of 73.8 was obtained, which is about five
fold higher than that of experiment 12. Since this combi-
nation occurs in the experiment 14 there was no need to
perform confirmatory experiment.
Table 2 indicates that the acid concentration is the most
important parameter in the extraction of thorium. Fig. 2b
represent that the average distribution coefficient of tho-
rium for acidic organophosphorous extractants, especially
Cyanex272, was appreciably higher than that of neutral
types such as TBP and Cyanex921. Earlier investigations
on the extraction of thorium reported that the extraction
mechanism of thorium with acidic extractants is cationic
exchange [4, 5]:
m 
ðThþn Þaq þ ðHAÞ2 þ
$ ðThAn ðm  nÞHAÞorg þ nHaq
2 org
ð3Þ
Here, m is the number of extractant HA and n is the
charge of thorium aqueous complex.
Also, Christian et al. [11] showed that thorium forms
cationic complexes in the pH less than 3 (our studied pH
ranges). Therefore, in the studied acidic ranges, the
extraction with cationic extractants such as Cyanex272 and
D2EHPA predominate the system. Since neutral extractants
can only extract the neutral complexes through the solva-
tion mechanism [3], it is concluded that the extraction of
thorium with these extractants will be increased only at
acid concentration higher than 4 M.

Table 2 Range and degree of importance of parameters on thorium solvent extraction

Extractant Extractant type Initial thorium Acid Acid
concentration (M) concentration (M) concentration(M) type

Range* 15.1 13 14.4 17.2 15.9

Order 3 5 4 1 2
* Difference between the maximum and minimum result for each parameter

Fig. 2 Average distribution

coefficient graph for thorium
extraction

123
Determination of optimum process conditions for solvent extraction of thorium
Table 3 Stepwise instability constants of thorium complexes with
some anions [13, 14]
Number of anion Anion type
in complex
Chloride Nitrate Sulfate
Ionic strength(M)
0 2 4 0.2 2 5.97 2
1 0.04 0.83 0.59 0.2 0.16 0.35 6.3 9 10-3
2 10.5 12.05 12.1 0.48 2.03 3.5 9 10-4
3 1.4 0.5 1.4 1.3
4 5.5 – 5.6 1.8
Figure 2c indicates that as the acid concentration
decreases, the average distribution coefficient of thorium
increases. Since the cationic extractants predominate then
from Eq. 3 it is clear that with increasing the acidity of
aqueous phase, extraction equilibrium tends toward the left
and the extraction would gradually be stopped. The most
important point in Fig 2c is that the average distribution
coefficient in the low acid concentration was appreciably
high (about fifty times as much). However, Karve and Gaur
[4] have reported about 60-fold difference in the distribu-
tion coefficient of thorium extraction with Cyanex302 in the
0.001 M and 0.1 M nitric acid concentrations. Appreciable
increasing for the extraction of thorium at low acidity is due
to decreasing the complex charge in the aqueous phase at
this acidic area [12], which results in decreasing the dif-
ference between the aqueous complex and organic phase
properties. Therefore, if possible, the extraction process of
thorium must be maintained at low acidity.
Figure 2d shows that the average distribution coefficient
of thorium from hydrochloric acid medium is larger than
that of other acids. The complex stability constants in
Table 3 indicate that the order of complex formation ability
of thorium with studied ions is decreased in the order of
chloride \ nitrate \ sulfate. Therefore, the extraction from
sulfuric acid medium is smaller than other ones.
For further investigation of the results obtained from
Taguchi method, several experiments were performed with
changing only one parameter. From Fig. 3, it can be seen
that the extraction decreases with the increase of acid
concentration, and the ability of Cyanex272 and D2EHPA
for extraction of thorium is almost same. The results agree
with the Taguchi results since according to Table 2 acid
concentration and solvent type have, respectively, the most
and the least effect on thorium extraction.
Figure 4 shows that the extraction of thorium at low acid
concentrations (less than 0.1 M) for the three acids is nearly
same and constant, but it decreases at higher acid concen-
tration (Fig. 4a, b). Gupta et al. [3] showed that the
extraction behavior of thorium with Cyanex923 from nitric
and hydrochloric acid solutions versus acid concentration is
243
Fig. 3 Comparison of thorium extraction with Cyanex272 and
D2EHPA form sulfate solution
very similar to our results in Fig. 4, but unfortunately there
are no discussions about such extraction behavior. Also in
other researches, there is a lack of information about the
reasons of such thorium extraction behavior according to
acid concentration. For example, Maiorov el al. [7] reported
that the thorium speciation in the chloride systems is
complex. Figure 4c illustrates that the thorium extraction
from hydrochloric solution has a minimum point at 1.0 M
hydrochloric acid, while similarly this minimum point was
occurred at 2.0 M for thorium extraction with Cyanex923
[3]. These behaviors of extraction of thorium by acid con-
centrations are the result of reverse effects of hydrogen and
chloride ion concentrations on thorium extraction. With
increasing hydrochloric acid concentration up to 1 M, tho-
rium extraction is decreased. In this acidic range the effect
of hydrogen concentration is predominant and according to
Eq. 3 with increasing acidity, thorium extraction will be
decreased. Moulin et al. [12] reported that the average
number of OH in the hydrolytic complex of thorium in this
range is decreased from 3.0 to 0.0 by increasing acidity. It
means that the hydrolysis of thorium at the acid concen-
tration higher than 0.1 M is almost zero and because of the
increasing chloride ion concentration, the neutral chloride
complexes of thorium will be formed at higher acid con-
centrations. Therefore, the mechanism of thorium extrac-
tion will be changed from cation exchange into solvation
and then extraction will be increased. Also, the instability
constants in Table 3 indicate that complex formation of
thorium with chloride ions has a maximum value for
ThCl?22 which results in changing the extraction behavior
with acid concentration (Fig. 4c). While for nitrate system,
with increasing the nitrate ion concentration only slight
changing in the strength of thorium nitrate complexes is
occurred (Fig. 4a). Since the stability constant of thorium
with nitrate ions is higher than chloride, it gives higher
extraction than chloride from more concentrated acids.
Meanwhile, the strength of hydrochloric acid is higher than
123
244 M. Eskandari Nasab et al.

Fig. 4 Thorium extraction with

Cyanex272 versus acid
concentration for various acids,
other parameters were at
Taguchi optimum conditions

nitric acid and also this is another reason for such difference
between thorium extractions from these acid systems. Since
sulfate complexes of thorium are very hydrophilic then the
extraction of thorium in the high sulfuric acid concentration
is decreased higher than other acids.
Nature of extracted complex
partially will be solvated by the extractant HA. This
explains that the basicity of oxygen in Cyanex272 is more
compared to the reacting oxygen of water and replaced with
coordination water of thorium complex. El-Hefny and
Daoud [5] also confirm the presence of Cyanex301 and
Cyanex302 in the form of partially solvated during the
extraction of thorium.

To evaluate the nature of extracted complex, Th(IV) was Separations

extracted with different concentration of Cyenx272 at the
optimum conditions. The log–log plot of thorium distribu-
tion coefficient versus acid concentration in Fig. 5 shows
the slope of 1 then the molar ratio of thorium to the Cya-
nex272 was 1:1. Since Cyanex272 in the aliphatic diluents
forms the dimmeric species (HA)2 [15], it is concluded that
even in the cation exchange range, the thorium complex
Separation of thorium (IV) from a synthetic mixture con-
taining uranium (VI), lanthanum (III), and cerium (III) were
studied by 0.01 M Cyanex272 under the optimum condi-
tions (Table 4). These ions were studied to show the effi-
ciency of this process for separation of thorium from
thorium ores such as monazite and Zarigan (the largest
known reserve of thorium in Iran). The results in Table 4
indicate that uranium and thorium were quantitatively
extracted in the organic phase leaving behind large amounts
of lanthanides in the aqueous phase. Thorium was stripped

Table 4 Separation of thorium, uranium, and lanthanides from

mixed metal solution by Cyanex272 same as monazite
Feed Organic Stripping Products
Phase
Amount Extraction Thorium Uranium
(ppm) (%)

Lanthanide fractions 2 M HCl 0.5 M H2SO4

La (III) 14 4 Nil 0.03
Ce (III) 14 9 0.02 0.04
Th (IV) 23.4 99.9 23.2 0.12
Fig. 5 Logarithmic plot of thorium distribution coefficient versus U (VI) 24 99.6 0.1 23.8
Cyanex272 concentration; [HCl] = 0.001 M, [Thorium] = 10-4M

123
Determination of optimum process conditions for solvent extraction of thorium
from organic phase by 2 M HCl. Then 0.5 M sulfuric acid
was used for stripping of uranium (VI). The recovery and
purity of thorium and uranium into their concentrates are
more than 99%. Therefore, this route is applicable in the
real process. After stripping, the organic phase was regen-
erated by washing using double distilled water.
Conclusions
The present study used the Taguchi method to investigate
the effect of parameters on the solvent extraction of tho-
rium. The results showed that the optimum conditions for
extraction of thorium with distribution coefficient of 73.8
were obtained when the extraction from 0.001 M hydro-
chloric acid at 0.001 or 0.01 M thorium by using 1.0 M
Cyanex272 in the kerosene was carried out. Detailed
experiments on thorium extraction behavior showed that the
variation of thorium extraction with acidity for sulfuric and
hydrochloric system is relatively high and for nitrate system
is low. Separation studies showed that Cyanex272 provides
a good basis for a process of thorium purification from
thorium ores.
Acknowledgments The authors gratefully wish to thank Prof.
M. Ghannadi Maragheh for providing the possibility of these
researches. Thanks are also due to Prof. Khayatzadeh and Dr. Roshan
Zamir for reviewing this manuscript.
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