Purification of uranium from zirconium-

rich crude sodium di-uranate using

counter-current solvent extraction

Aswin Pradeep & Sujoy Biswas

Journal of Radioanalytical and

Nuclear Chemistry
An International Journal Dealing with
All Aspects and Applications of Nuclear
Chemistry

ISSN 0236-5731

J Radioanal Nucl Chem

DOI 10.1007/s10967-017-5291-1

1 23
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1 23
 Author's personal copy
J Radioanal Nucl Chem
DOI 10.1007/s10967-017-5291-1
Purification of uranium from zirconium-rich crude sodium
di-uranate using counter-current solvent extraction
Aswin Pradeep1 • Sujoy Biswas1
Received: 6 February 2017
Ó Akadémiai Kiadó, Budapest, Hungary 2017
Abstract Solvent extraction studies on the purification of
uranium from zirconium rich sodium diuranate (SDU) feed
was carried out using n-tri butyl phosphate (TBP) as
extractant and n-decanol as phase modifier. The presence
of Zr in SDU leached solution leads to the formation of
third phase during liquid–liquid extraction of uranium
which was successfully prevented by addition of n-decanol
in 30% (v/v) TBP/n-dodecane mixture. A seven stage
counter current extraction of SDU feed solution followed
by five stage stripping were carried out using optimum
concentration of phase modifier 15% n-decanol-30% TBP
in n-dodecane as solvent. Based on the findings a process
flow-sheet has been developed for the purification of SDU
to nuclear grade ammonium diuranate.
Keywords Uranium
Zirconium
Sodium diuranate

Third layer
Solvent extraction
Introduction
Tummalapalle ore is the single largest reserve of uranium
in India with an estimated 63,269 tonnes equivalent of
U3O8 deposits [1]. Together with Rachakuntapalle, the
Tummalapalle–Rachakuntapalle reserve constitute to about
44.7% of the total uranium reserve in the country [2]. The
host rock of Tummalapalle ore is classified as phosphatic
siliceous calcitic-dolostone (PSCD) with a uranium con-
centration of 0.042% on U3O8 basis [3]. The uranium
& Sujoy Biswas
sujoy1980@rediffmail.com
1
Uranium Extraction Division, Materials Group, Bhabha
Atomic Research Centre, Trombay, Mumbai 400 085, India
leaching from such ore is carried out by alkaline pressure
leaching technique as the ore comprises of 60–65% dolo-
mite and calcite [4]. The recovery of uranium from alka-
line, carbonate leach solution, is carried in the form of
sodium diuranate (SDU) by the addition of NaOH at 60 °C.
The SDU obtained from this process is crude and needs
further purification before putting its nuclear grade appli-
cations. The purification of crude uranium to nuclear grade
is generally carried out using HNO3–TBP solvent extrac-
tion route. For refining, crude uranium has to be first dis-
solved in nitric acid followed by solvent extraction using
Tri-n-butyl phosphate (TBP) in kerosene as diluent, this
follows subsequent precipitation of nuclear grade uranium
in the form of ammonium di-urante (ADU) in the presence
of ammonia after the stripping [5, 6]. There have been a
number of identified generic issues associated with the
nuclear grade purification of Tummalapalle ore specific
crude SDU, mainly due to the added poly-acrylamide
(PAM) flocculants, presence of excess carbonates and
significant zirconium contamination [7]. Initial processing
of crude SDU is marred by slow filtration rate attributed
with the formation of slimy cyclic-imides during acid
digestion of poly-acrylamides in nitric acid accompanied
by effervescence due to carbonates present in SDU [8].
This is followed by third layer formation during the solvent
extraction stage of SDU purification. Zirconium present in
Tummalapalle ore specific crude SDU has been identified
in this work as the root cause of third layer formation
during the solvent extraction stage of SDU purification.
Third layer formation of tetravalent metal neutral solvates
in TBP such as that of Zr(IV), Pu(IV), Th(IV), U(IV) etc.
has been one of its well-known drawbacks [9]. The third
layer formation occurs due to the limited solubility of the
extracted species in the organic phase [10]. When the
concentration of a particular species in organic layer
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crosses a certain limit, termed as limiting organic
concentration (LOC), the organic layer splits into two
phases, a thin heavy organic layer (near the interface)
containing most of the ionic species and a light organic
layer containing majority of the diluent [11]. The third
layer formation not only causes operational problems in
mixer settlers, but also in particular to nuclear industry, it
can cause criticality hazards as in the case of plutonium
where the critical mass is less [12]. A zirconium rich third
layer formed during extraction of Zr(IV) in TBP-HNO3
system is believed to contain approximately 80–90%
Zr(NO3)4(HNO3)(TBP) acidic solvate in the heavy organic
phase [13]. Major work on the supra-molecular structure
zirconium rich third layer formation was carried out by
Chiarizia et al. [14]. It was highlighted that a typical
micelle formed during solvent extraction of Zr(IV) consists
of small spherical reverse micelles containing 2–3 TBP
molecules associated with Zr(NO3)4 HNO3 and water, with
the sphere size believed to be ranging from 12 to 14 Å.
Thus a polar core is formed within the TBP molecules
midst the structure’s existence in the non-polar medium.
Further increase in the metal ion, water or nitric acid
concentration causes its incorporation into the polar core of
the reverse micelles, causing their subsequent swell up. As
more and more ions are incorporated into the polar core the
shape changes from small hard spheres to relatively large
ellipsoidal shape ranging up to a few hundred Angstrom in
length [14]. Different polar organic phase modifiers have
been tried in similar systems to address the zirconium third
layer formation. Chao Xu et al. measured the parameters
affecting the LOC values of Zr in TRPO-kerosene mixture.
The work cemented the fact that when more polar phase
modifiers such as TBP is added in organic phase the con-
ductivity of the system is increased thus rapidly shooting
up the LOC values [15]. Long chain aliphatic alcohols
ranging from n-heptanol to n-decanol have been tried in
similar systems addressing the third layer formation suc-
cessfully [16–18]. Apart from organic phase modifiers,
aqueous zirconium complexing agents or masking agents
such as tartrates, hydrofluoric acid, phosphoric acid etc. are
added to uranyl nitrate feed (UNF) to prevent the extraction
of zirconium into organic phase [19–22].These, sometimes
not only introduces new process constraints related to its
disposal and corrosion but also makes the solvent extrac-
tion raffinate unfit for nitric acid recovery at the later stage.
On the other hand, using polar organic phase modifiers in
extraction stage causes the carryover of zirconium into
organic phase which later has to be selectively scrubbed to
attain ADU of nuclear grade purity. EDTA has been used
in the back end fuel reprocessing for the selective removal
of Th(IV), Zr(IV) etc., with zirconium forming a
stable complex with EDTA at pH 1–3. Zirconium forms
[Zr(EDTA)]
4H2O chelate with EDTA which gets
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J Radioanal Nucl Chem
hydrolysed at pH 5–6 with dimerization, also its complex
below pH 1 is found to be unstable [23, 24]. The current
work evaluates the effectiveness of using aliphatic long
chain alcohol such as n-decanol to address the zirconium
rich third layer formation during the solvent extraction of
zirconium rich Tummalapalle ore specific SDU. n-decanol
was selected as the phase modifier based on its commercial
viability and reliable operational data.
Experimental
Reagents and chemicals
SDU powder was obtained from Uranium Corporation of
India Limited (UCIL) plant, Tummalapalle, India. Nuclear
grade U3O8 for preparing uranyl nitrate standard was
obtained from Uranium Extraction Division (UED),
Bhabha Atomic Research Centre (BARC). TBP used for
the current study was obtained from British Drug Houses
(B.D.H) (97% assay). Rest of the reagents used were of
Analytical Reagent (A.R) grade purity and were used
without any further purification. Unless or otherwise
mentioned distilled water was used for washing throughout
this work.
Instruments
Elemental purity of ADU was determined by Thermo
Fischer scientific make ICP-AES, Jobinyvon Emission
Model JY 328. The quantitative determination of U(VI)
and Zr(IV) was done using EDXRF (Jordan Valley, EX-
3600M). The particle size distribution is done using a
CILAS 1180 particle size. Surface area and porosity
analysis is done using a standard BET adsorption technique
in Thermo Fisher Scientific, Surfer Analyzer. The viscosity
and density of the organic phase was measured using a
digital SVM 3000 Stabinger Viscometer.
Processing steps for SDU purification
Dissolution of sodium di-uranate (SDU)
Taking into account the filtration and forming issues batch
size and acid concentration were adjusted. One kilogram of
SDU was dissolved in 4.4 L of 4 M HNO3 at the rate of
25 g/min.
The digested solution, crude uranyl nitrate (CUN), is
later filtered under vacuum filtration using Whattman 342
filter paper. The uranyl nitrate thus obtained is diluted to
110 g/L with free acidity adjusted to 2M. This forms the
basis of uranyl nitrate feed (UNF), which is a standard feed
for counter current solvent extraction studies.
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J Radioanal Nucl Chem
Solvent extraction
Batch simulation of counter current studies were carried
out using 15% n-decanol-30% TBP in n-dodecane as
extractant, keeping O/A ratio 1:1, in a standard separating
funnel stirrer system. The aqueous and organic phase was
mixed for period of 5 min. The 5 min mixing time was
found to be sufficient for achieving the equilibrium con-
dition [25]. Number of stages calculated on the basis that
aqueous raffinate from the extraction stage should con-
tain \0.1 g/L uranium content before proceeding to the
next processing stage. This is followed by scrubbing of the
organic phase in a single stage contact with Na2-EDTA at
pH 2 with O/A ratio 10:1 to minimize uranium loss in the
scrub solution.
Stripping
The saturated organic phase stripping was carried out using
distilled water with the phase ratio adjusted (O:A = 1: 1.6)
such that the stripped aqueous should have a concentration
of U(VI) close to 70 g/L. A 5 min mixing time of aqueous
and organic phase was decided for stripping of uranium
from loaded TBP-n-decanol/n-dodecane. This time is suf-
ficient to reach the equilibrium condition for stripping of
uranium from organic phase using water [25].
Ammonium di-uranate precipitation
ADU is precipitated by the addition of 40% ammonium
hydroxide (AR) drop by drop with constant stirring at
400 rpm and temperature 50 °C. Solution is slowly turned
alkaline by the addition of ammonia and the addition is
stopped when the solution reaches pH 8, indicated by the
solution colour change from bright yellow to orange yel-
low. Stirring is continued for half an hour more before the
solution is allowed to settle. ADU is later filtered using
vacuum filtration and the dry cake obtained is dried in an
air over at 100 °C for 6–8 h.
Preparation of standard uranyl nitrate solution
for generating equilibrium curve
A 300 g/L, 2N free acidity, standard uranyl nitrate solution
was prepared for generating extraction equilibrium curve
by dissolving nuclear grade U3O8 in nitric acid. Powdered
U3O8 was dissolved under constant stirring at 80 °C,
complete dissolution took place within 2 h.
Third layer formation
A 25 mL standard feed solution of 110 g/L Uranium–zir-
conium nitrate solution with free acidity 2M was shaken
vigorously with 25 mL of 30% TBP in dodecane ? x vol%
of the new phase modifier to find its effect on the third
layer formation. Each experiment was followed by incre-
ment of 1% (v/v) of dodecane in the organic phase until no
visible third layer formation was observed.
Results and discussion
Composition of crude uranyl nitrate (CUN)
Crude uranyl nitrate was analyzed for the major elemental
impurities and values are reported on weight basis of SDU.
It was observed that the digested liquor contained about
4.47–5.4% Zr with respect to uranium by mass. Even
though dissolution was carried out at room temperature, the
feed rate was controlled so that the temperature of resulting
CUN solution did not exceed 40–50 °C, as there is a
chance for the whole solution to get gelled due to zirconia
polymerization in nitric acid medium. Partially floating in-
soluble appearing like black muck were observed during
the dissolution of SDU due to reaction of poly-acrylamides
in nitric acid, resulting in the formation of cyclic-imides.
Table 1 gives the list of major elemental impurities in
CUN.
Third layer formation studies
The third layer formed during the first contact mixing of
UNF and 30% TBP/dodecane was isolated and analysed
using EDXRF. In UNF solution the Zr/U ratio was 0.05
which is increased to 1 in third phase indicating the
increase in Zr concentration. The increase in Zr concen-
tration in third phase/layer indicate that the presence of Zr
is responsible for third layer formation. The Zr(IV) forms
polar complex Zr(NO3)4(HNO3)(TBP) which is not soluble
in non-polar dodecane-TBP mixture. The organic phase is
split in to two separate phases one is rich in polar
Zr(NO3)4(HNO3)(TBP) complex and another in diluent
rich [13]. It was observed that a minimum of 12% (v/v) n-
decanol was needed to prevent the formation of third layer
during co-extraction of uranium and zirconium into the
Table 1 Major elemental impurities in CUN, SDU as weight basis
Element SDU (w/w)%
U 53.6–55
Zr 2.40–2.97
Fe 0.86–1.04
Al 2.16–2.27
Mg 0.72–0.75
Insoluble (PAM and silica) 6.0–7.0
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organic phase. Considering the alcohol loss due to nitration Table 2 Stage wise uranium and zirconium concentration profile
and solubility in aqueous medium 15% n-decanol-30% during 1:1 extraction of UNF using 15% n-Decanol in 30% TBP-
dodecane mixture
TBP in n-dodecane was used as extractant in the solvent
extraction studies. Stage [U]Org [U]Aq [Zr]Org [Zr]Aq Separation factor

1 0.12 0.05 0.08 6.90 207

Counter-current extraction of uranium using 15%
2 0.18 0.05 0.42 6.88 58.97
n-decanol phase modifier
3 0.7 0.51 0.37 7.01 26.00
4 7.91 1.45 0.57 7.66 73.30
McCabe–Thiele diagram for extraction of uranium from
5 56.1 27.4 0.59 7.82 27.13
HNO3 medium was generated for 30% TBP-15% n-de-
6 100.4 81.9 0.57 7.64 16.43
canol in dodecane mixture using different concentration of
7 105.7 102.61 0.71 7.84 11.37
pure standard uranyl nitrate prepared by dissolving nuclear
Feed – 110 6.97
grade U3O8 in nitric acid. A total of six theoretical stages
were calculated for a feed concentration of 110 g/L and
raffinate tailing of 0.1 g/L as shown in Fig. 1. The counter
current batch simulation experiments were conducted with zirconium from organic phase. The selective scrubbing was
additional stage envisaging the efficiency of the separating followed by stripping and ADU precipitation.
funnel-stirrer system. A final uranium concentration in the
extract was 105.91 g/L and more importantly no third layer Counter-current stripping
formation was observed during the course of the experi-
ment. The raffinate concentration was 0.05 g/L. Table 2 Stripping was done using 0.01 M HNO3 solution.
shows the uranium and zirconium concentration profile A McCabe–Thiele diagram was constructed to calculate
obtained during the extraction process. There was a zir- the number of theoretical stages for stripping of uranium
conium carryover of 0.71 g/L to organic phase as com- with Uranium concentration of initial organic feed and
pared to 6.96 g/L in the feed which accounts for 87.9% of stripped organic to be 105.7 g/L and 0.1 g/L respectively
zirconium removal in the raffinate. as shown in Fig. 2. An additional stage was added to the
theoretically calculated to account of inefficiency of stir-
Selective scrubbing of zirconium from loaded ring system making the total number of stages five. Organic
organic phase to aqueous ratio was fixed at 1:1.6 so that the final solution
has a concentration close to 70 g/L, this ensures desirable
A portion of the uranium loaded extract from each batch ADU characteristics for further processing stages. The final
was given two single stage contacts with 0.05 N Na2- concentration of the uranyl nitrate pure solution (UNPS)
EDTA solution at pH 2 with O/A ratio 10:1 scrub out after the stripping process was 72.09 g/L with the stripped
organic concentration being 0.40 g/L. There were no

120 180

1 160
100
140
2
80 120
[U]Aq (g/L)

O/A: 1:1
[U]org g/L

100
60 O/A= 1: 1.6
3 80

40 60

40
20
4 20
5
0 0
110
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120
[U]Aq g/L [U]org (g/L)

Fig. 1 McCabe–Thiele diagram for calculating the number of stages Fig. 2 McCabe Thiele diagram to calculate number of stages for
during extraction of U(VI) in 2M nitric acid using 30% TBP-15% n- 1:1.6 counter current stripping of uranium loaded 15% n-decanol in
decanol in dodecane as extractant 30% TBP-dodecane mixture with distilled water

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Table 3 Stage wise uranium and zirconium concentration profile results are summarized in Table 5. The particle size of
during 1:1.6 stripping of uranium 15% n-Decanol in 30% TBP-do- ADU is 18.19 lm with the specific surface area of 17 m2/g
decane mixture
whereas particle size of ADU obtained from other source is
Stages [U]Org [U]Aq [Zr]Org [Zr]Aq higher with lesser surface area. A high surface area of ADU
indicate a high quality of material for further processing
1 23.42 72.09 0.17 0.45
like conversion to UO3, UO2 and UF4 [26].
2 4.61 30.8 0.02 0.25
3 1.30 5.84 0 0.03
Physical properties of the solvents
4 1.07 1.99 0 0
5 0.40 0.24 0 0
The physical properties of the phase modified solvent and
Feed 105.7 – 0.71 –
pure solvent were measured using an SVM 3000 Stabinger
Viscometer are given in Table 6. The viscosity of 30%
instances of phase inversion or third layer formation during TBP-dodecane system is 1.73 mPa.s with a density of
the whole stripping cycle. Stage-wise concentration pro- 0.8112 g/cc whereas the viscosity of 30% TBP-15%
files of uranium and zirconium during stripping is listed in decanol-dodecane system is 2.25 m.Pa.s. Further there is
Table 3. no change in density of the solvents. It was found that
dynamic viscosity and density of the modified organic
ADU precipitation phase was 30.1 and 1.4% more respectively in comparison
to the 30% TBP/n-dodecane extractant system currently
Five batches of ADU were precipitated using AR grade used leading to a slightly slower settling rate in mixer
40% ammonium hydroxide solution. Later it was charac- settler units.
terized for its elemental purity after vacuum filtration. The
elemental purity of ADU is reported in Table 4, with Process flow sheet for SDU purification
reported nuclear grade purity in each batch. An exhaustive
literature survey indicated that zirconium is not a currently Based on the findings a proposed flow chart of SDU
listed nuclear impurity in most of the nuclear grade stan- purification at plant scale is given in Fig. 3. For pre-
dards. The physical characteristics of the obtained ADU are venting the foaming and filtration issues SDU has been
compared with the standard nuclear grade ADU obtained digested using diluted acid of concentration 4 N HNO3
for natural uranium fuel fabrication from various sources nitric acid instead of the conventional 8 N HNO3. The
like Uranium Metal Plant-Bhabha Atomic Research Cen- feed concentration produced would be 120–130 g/L
tre, Mumbai, and Indian Rare Earths Limited -Alwaye. The which corresponds to six ideal stages with O/A ratio of

Table 4 Elemental purity of ADU precipitated

Element Fe Zr Al Cr Mg Mn Ni Co Ce B, Cd Gd, Sm, Dy, Y, PSA Pore size
Eu Yb (l) (nm)

Nuclear specification limit in 150 250 100 65 25 25 100 1.2 0.2 0.12 0.04 0.10 – –
ppm
DEC-ADU-1 4 15 2 \1 6 \1 \1 \1.2 \0.2 \0.12 \0.04 \0.10 24.65 0.31–0.99
DEC-ADU-2 5 13 1 \1 1 \1 \1 \1.2 \0.2 \0.12 \0.04 \0.10 15.93 0.31–0.99
DEC-ADU-3 6 18 2 \1 4 \1 \1 \1.2 \0.2 \0.12 \0.04 \0.10 18.19 0.31–0.99
DEC-ADU-4 4 18 2 \1 3 \1 \1 \1.2 \0.2 \0.12 \0.04 \0.10 18.12 0.31–0.99
DEC-ADU-5 4 18 3 \1 3 \1 \1 \1.2 \0.2 \0.12 \0.04 \0.10 22.03 0.31–0.99

Table 5 Particle size and

Standard nuclear grad ADU source Particle size (lm) Surface area (m2/g)
surface area of ADU
Current process 18.19 17.1
UED, BARC, Mumbai 24 11.64
IREL-Alwaye 38.73 6.74

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Table 6 Physical properties of the solvents at 25 °C

Solvents composition Dynamic viscosity (mPa.s) Kinematic viscosity (mm2/s) Density (g/cm3)

30% TBP, 70% Dodecane 1.7318 2.1349 0.8112

30% TBP, 55% Dodecane, 15% n-decanol 2.2541 2.7383 0.8232

1:1. It is followed by a two stage scrubbing with 100%
excess Na2-EDTA at pH 2 to scrub out the zirconium
present in the organic phase. The Zr-EDTA complex is
later broken by acidifying the solution with nitric acid and
the zirconium rich scrub solution is later recycled back
into feed. The precipitated H-EDTA is filtered and later
converted to Na2-EDTA by treating it with caustic lye and
reusing the solution for further scrubbing. Scrubbing is
later followed by a stripping stage using DM water where
O/A is kept as 1:1.6 to produce pure uranyl nitrate solu-
tion for concentration [50 g/L suitable for ADU
precipitation.

Fig. 3 Process flow sheet for

SDU purification SDU

Zr –U solution
Recycle Dissolution of SDU in
4M HNO3

Solvent extraction using (15 n- decanol

%-decanol&30 % TBP in makeup
dodecaneextractant

Zr rich
raffinate
Precipitation
Scrubbing using EDTA
ofH-EDTA
with Nitric
Acid

Extraction:
Na2-EDTA O/A ratio: 1:1
Regenerated Initial U conc.:110g/L
Using NaOH 6 stages
Scrubbing :
Stripping using DM O/A ratio: 10:1
Water pH=2
2 stages
Stripping:
O/A ratio: 2:3
5 stages

ADU Precipitation using

Ammonia

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Conclusions
It was found that an alcohol modified organic phase made it
possible to carry out extraction of uranium from nitric acid
medium using 30% TBP without any instances of third
phase formation due to the increased polarity of the organic
phase. The modified organic phase was 30% TBP-15% n-
decanol and 55% n-dodecane in which the long chain
alcohol n-decanol acted as the organic phase modifier.
Advantages of the process includes: maximum loading of
uranium in organic phase, *90% zirconium recovery in
raffinate which could be a good source of zirconium,
minimal changes in process parameters etc. The only dis-
advantage of the process over the existing uranium purifi-
cation system would be the appearance of slight yellow tint
in the organic phase due to nitration of alcohol phase
modifier that may lead to an increase in solubility of
alcohol in acidic aqueous phase increasing process losses
and an expected slower settling rate due to the increase
viscosity in the extract phase. The new process gave results
with good reproducibility demonstrating the reliability of
the process. It is to be noted that the Tummalapalle ore
specific zirconium rich crude SDU contains close to
4.47–5.4% Zr with respect to uranium by mass, which can
be considered as a good secondary source of Zirconium in
India. Any integrated process flow sheet addressing the
purification of Tummalapalle ore specific SDU cannot skip
the integration of recovery of zirconium along with the
process. Also, it has to be noted that zirconium is not a
currently a listed nuclear impurity in most of the nuclear
grade standards and it has be incorporated once a full-
fledged exploitation of Tummalapalle reserves starts.
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