Solvent Extraction in Production and Processing of Uranium and Thorium

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Solvent Extraction in Production and Processing of Uranium and Thorium

Harvinderpal Singh a; C. K. Gupta a
a
Materials Group, Bhabha Atomic Research Centre, Mumbai, India
Online Publication Date: 01 September 2000
To cite this Article Singh, Harvinderpal and Gupta, C. K.(2000)'Solvent Extraction in Production and Processing of Uranium and
Thorium',Mineral Processing and Extractive Metallurgy Review,21:1,307 349

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Solvent Extraction in Production

and Processing of Uranium
and Thorium
HARVINDERPAL SlNGH and C. K. GUPTA
Materials Group, Bhabha Atomic Research Centre, Mumbai 400085,
India
Solvent extraction plays a vital role in the production and processing of uranium and
thorium for use as fuels in the front-end of the nuclear fuel cycle. The development of
solvent extraction technology in the nuclear field in the last five decades has contributed
to advances in the non-nuclear hydrometallurgy. In turn the large scale applications in
the field of base metals such as copper have led to development of new equipment and
techniques as well as better understanding of the process chemistry and hydrodynamics.
Advances in the field of solvent extraction of relevance to the nuclear fuels, are reviewed
in this paper. The significant results from the research and development work in India
are also included. Various aspects discussed include chemistry of process flowsheets for
uranium and thorium recovery and refining including recent improvements, diluents for
use in the processes, thermal effects in extraction, process instrumentation including
on-line measurements, solvent loss by entrainment, purification of feed streams prior to
extraction, solvent-in-pulp processing, separation of uranium and thorium, binary extractants and application of solvent extraction in uranium enrichment.
Keyu'ords: Uranium; thorium; solvent extraction; nuclear fuel; processes; chemistry;

instrumentation; loss; diluent; enrichment
INTRODUCTION
The high purity required for production and processing of uranium and
thorium for use as fuels in the nuclear reactors, with concentration of
some of the specific elements (called as nuclear poisons) limited to less
than a fraction of ppm, can only be achieved by use of highly selective
extracting agents used in the liquid or immobilised forms such as
membranes o r impregnated resins. Developments in the nuclear field
308
H. SlNGH AND C. K. GUPTA
have led to maturing of solvent extraction technology which finds

application today in diverse fields such as hydrometallurgy for recovery of base metals, environmental engineering for removal of pollutants, analytical chemistry for separation and determination of metals
in trace concentrations and organic industry, among others. There has
been an inter-dependent growth among these areas in last few decades, whereby advances made in one field find application in others. In
particular there has been a better understanding of process chemistry,
hydrodynamics of processes operated in large scale equipment and the
interface of solvent extraction with related fields. Some of the recent
developments in these areas, of interest to the nuclear hydrometallurgy, are discussed in this paper. The data from the Indian research
investigations has been highlighted. The discussion essentially pertains
to the 'front-end' of the nuclear fuel cycle, but it is also recognised that
there are related developments in the 'back-end' of the cycle which are
equally relevant.
Uranium and thorium processing by solvent extraction essentially
involves two steps. In the first step processing of leach solutions obtained by acid o r alkali leaching of lean ore/crude concentrate is
carried out with the objective of produing a chemically pure concentrate that is free of gross impurities such as silica and iron. In the
second step, referred to as refining, purification is carried out by separation of elements that are regarded as nuclear poisons. There is a
related area where uranium and thorium are separated from the solutions where they occur simultaneously. The separation processes for
the two steps are discussed first in this paper, and then specific fundamental phenomenon, common to all solvent extraction processes are
discussed with reference to uranium and thorium.
URANIUM EXTRACTION AND REFINING PROCESSES

Extraction of uranium from ore leach solutions is carried out by
solvent extraction, o r by ion exchange or by a combination of the
two processes. The leach 'solutions are generally acidic in nature.
Amine extraction has replaced the extraction by di-2-ethyl hexyl
phosphoric acid (DZEHPA) which has poor selectivity with reference
to iron.
URANIUM AND THORIUM SOLVENT EXTRACTION
309
Amine Extraction from Ore Leach ~olutions

High molecular weight amines are widely used for uranium recovery
from sulphuric acid ore leach solutions on industrial scale [I]. Tertiary amines are known to be efficient extractants [2], as are branched
aliphatic amines. The mechanism of extraction has been a matter of
study by several investigators [3-51. Reactions between sulphuric acid
and amine, equilibria between amine sulphate/bisulphate and uranium
complexes has been difficult to explain. In particular the observed
exponential dependence of the uranium-VI distribution ratio on the
amine sulphate concentration is difficult to correlate with the apparent ratio of amine to U-Vl in the extracted species [4]. Mechanism
based on parallel competing reactions and the law of mass action
yields results consistent with the observations [5]. The sulphuric acid
extraction can be described by the reactions
The reactions involving uranyl sulphate extraction are:
UO, SO4 = uo;+ + so:-
(6)
Parallel reactions (3) and (4) occur in the stoichiometric ratio, x, while
(7) and (8) are described by the ratio, y. By mass balance the distribution ratio D can be expressed in terms of x and y. A t high initial amine
310
H . SlNGH AND C. K.GUPTA
and free amine concentrations x 1, while a t lower values x is lower

and a proportion of amine bisulphate is formed. The D value for acid
shows a maxima in the pH range 1.25-2.25, with the peak shifting to
higher value as the initial amine concentration increases. The extraction of uranium shows similar trends, except that initial uranium
concentration is too small to saturate the organic phase. Hence D falls
only a t the lowest conditions, at pH 1.25.
P r o c e s s I m p r o v e m e n t s in t h e Amine Solvent
Extraction P r o c e s s
Improvements in amine process flowsheets include the use of strong
acid for stripping of uranium, and precipitation from the strip solution
by hydrogen peroxide, thereby completely eliminating the use of ammonia [6,7]. The conventional ammonium sulphate stripping of uranium can lead to crud problem and loss of solvent. Besides ammonia
limits for effluent disposal are stringent and difficult to achieve continuously on plant scale. The chloride strip is free of the crud problem,
but again there are environmental discharge limits on chloride ion.
Strong sulphuric acid strip, 400 g/l, yields a pregnant solution containing upto 125 g/l uranium. After peroxide precipitation, the solution can be recycled o r safely sent to the effluent treatment plant.
Reactions involved are:
Free acid level of 275 g/l was found necessary for efficient stripping,
with barren organic containing less than 0.1 g/l uranium. Degradation
of the organic by strong acid becomes high a t high temperatures, and
stripping must be done below 35C. At this temperature the degradation is significantly lower than the entrainment loss rate. The acid
concentration also needs to be kept lower than 450g/I. High oxidation
potential of the leach solution and the presence of molybdenum in the
feed are other causative factors for crud formation.
311
In India we have carried out batch and pilot plant solvent extraction tests on leach solution of Domiasiat uranium ore [8-131. The
feed was obtained by two stage counter-current leaching. It was purified by activated carbon. The feed analysis is given in Table 1. Batch
kinetics were studied for extraction with 3.5% AIamine 336 and
1.75% iso-decanol in refined kerosene at 29C. Results on kinetics
show complete extraction in 10 seconds. A continuous mixer however
requires more time, 30-60 seconds. Pilot plant flowsheet is shown in
Figure I. Four stage counter-current extraction showed a loading of
1.7g/l in the extract with raffinate analysing 0.005g/l, showing over
99% extraction. Distribution ratio of 24 and saturation loading of the
organic phase of 2.241 were determined. The mixer-settler used for
test runs were operated at a feed rate of 1000-1500l/h. The mixer
hydrodynamic data is given in Table 11. Stripping with ammoniacal
ammonium sulphate as well as strong acid was equally effective. Acid
strip results are given Table 111. During operation, slight crud formation was observed. The average rate of crud of generation was 39 g/m3
of feed processed. The crud accumulated in the settler solvent, which
was processed periodically in a solid bowl centrifuge a t a feed rate of
1200 l/h. Crud recovered was 145 g/m3 or solvent. The amine entrainment losses were measured a t various points in the process. The raffinate was passed through a parallel plate separator and then through
a flotation cell. Results are given in Table IV. The solvent recovered in
the parallel plate separator was measured and found to be 40 rnl/rn3
of feed solution processed. Similarly the recovery from the flotation
TABLE1 Analysis of the Domiasiat uranium leach solution
used as reed lor solvent extraction by alamine
Species
U38
Fe-Ill
Fe-I1
P A
Ca
dl
0.93
0.85
0.1
0.13
0.27
H. SINGH AND C. K. GUPTA

pregnant
feed
1 : AQUEOUS FEED TANK

4 : EXTRACTION UNIT
7 : AIR FLOTATION CELL
9 : SOLVENT
REGENERATOR
raffiate
2: SAND FILTER
%CARBONCOLUMN
5: STRIPPING UNTI 6 : PARALLEL PLATE
8 : SOLVENT TANX
10 : mm FILTER
11:CARBON COLUMN
12 : STRIP FEED TANK
FIGURE 1 Schematic flowsheet for uranium extraction.
cell was 0.2 ml/m3. A final effluent sample was treated with carbon
and it was round that complete removal was achieved. In a parallel
test, the final effluent was neutralised with lime and filtered and in the
filtrate the amine level was found to be 2 ppm, which is much below
the toxicity limits. Air-borne hydrocarbon levels in the working environment were measured with Kitgawa gas detector tubes. It was
313
TABLE 11 Mixer-settler for solvent extraction

I. MIXER
1.1 SlZE
1.2 VOLUME
1.3 IMPELLER (D)
1.4 NO. O F BLADES
1.5 WIDTH (W)
1.6 TYPE
1.7 SPEED (N)
1.8 N3D2
1.9 INFLOW ORIFICE
1.10 CLEARANCE
2. SEITLER
2.1 SlZE
2.2 INLET
2.3 RECYCLE
500 x 500 x 410 (mm)

100 Litres
240 mm, D,T = 0.48
6
40(W/D= 116, WIT= 1/12)
T O P SHROUDED TURBlNE
250 RPM = 4.17RPS
45 (it2 rps3)
100 mm
15 mm
500 mm x 1200mm (0.6 m2)
PICKET FENCE BAFFLES
ORGANIC 1:4
TABLE 111 Strong acid stripping ofamine extract of uranium

S. no.
CffPOJ
M
Strip U30,
(910
% Stripping
TABLE IV Entrainment levels in pilot plant (ppm)

S. no.
I
2
3
4
Raffinare
P P S efluent
Floated
efluent
13
26
22
21
3
II
13
12
3
6
6
6
PPS = Parallel Plate Separator. Levels given in ppm.
found that the concentrations were in the range 50-100 ppm near the
unit and below detection limit at three metres distance. The concentration inside the vapour space below the mixer cover and above
liquid level was about 200 ppm. All these are below the T.L.V. limits
for hydrocarbon vapours.
314
H . SlNGH AND C. K. GUPTA
Recent developments, which are a matter of intense study, include

the use of hollow fibre type liquid membranes for uranium extraction
[14-161. A pilot plant plant was operated for extraction of uranyl
nitrate Tri-n-octyl phosphate (TOP). T O P was preferred over T B P to
cnsure low solubility in the water and increase its retention in the
membrane pores. A counter-current flow of the feed and strip phases
was maintained. Reactions at the feed-membrane interface are:
UO, (NO,),
HNO,
+ 211T O P = UO, (NO,),
(n TOP),
+ n T O P = HNO, (n TOP)
( I 1)
(12)
The extracted complex diffuses across and at the membrane-strip interface are:
= Na,U02(C0,)
+ 4 n T O P + H,O + CO, + 4 N a N 0 ,
(13)
2 HNO, (n TOP) + N a z C 0 3 = 2n T O P
+ H 2 0 + CO, + 2 N a N 0 ,
(14)
Operating flux of 100 miro-gram U/mz.sec was observed. Studies

have been reported [17] on uranium extraction from ground water
using phosphinic acid carrier in a polypropylene membrane [16]. The
process was found to be very erective in separating uranium at
pH = 2. Pilot plant uranium recovery on extraction by tertiary amine
in kerosene with a polysulfone membrane has shown [17] operational
costs lower than the conventional extraction or ion exchange. Studies
in BARC have shown uranium Rux value of 4.8 micro-moles/m2.s for
T B P in silicone membranes, while the value for DZEHPA is lower to
a third the value [18, 191. The separation based on hollow fibre type
units, which provide large surface area, and can hence be economical
for use with expensive agents, can be expected to play an important
role in future [20].
315
P r o c e s s Improvements in t h e TBP Refining P r o c e s s

The crude concentrates produced from the ores, by-products of phosphate industry and from the monazite processing are refined by separation of nuclear impurities using TBP. Fundamental studies [21] of
the extraction of U and HNO, by T B P have been carried out. The
extraction is found to be stepwise in nature and initially involves the
extraction of HNO, alone. Subsequently, U enters the organic phase
by displacing extracted HNO, molecules until the equilibrium is
reached. Similarly the fundamentals of hydrodynamics in a mixersettler have been examined [22]. The Sauter mean diameters and
droplet distributions were measured using photographs of the dispersions. Overall extraction efficiencies were measured. Settler behavior
was determined by measurement of dispersion band heights. It was
characterized by a normalized band height corresponding to a specific
throughput of 0.144 cm3/cm2/s. Normalized band heights depend on
solution composition and stirrer speed. Crud formation was studied,
but solid characteristics were such that dispersion band heights were
reduced, i.e., coalescence in the settler was enhanced.
In the refining of uranium by TBP, ammonium uranyl tricarbonate
(AUC), (NH,),UO,(CO,),
can be produced directly by contacting the
loaded organic with strong solution of ammonium carbonate [23].
The solubility limit of AUC, 200g/l, can be exceeded by optimising
the process parameters. Reactions involved are:
4 NH:
+ [UO,
(CO3),I4- = (NH,), UO, (CO,), (solid)
(16)
AUC is a crystalline product and has excellent physical properties for

subsequent processing to the nuclear fuel grade oxide.
T B P has also been used for purification of recycled material, particularly those containing fluoride [24-271. In the Canadian plant,
digested slurry containing 18% solids by weight, with 150 g/l uranium
and 20 g/l fluoride at 2N free acidity was processed in 15 nos. of
MlXCO columns at 50C by 22% T B P in Isopar M with solvent/feed
316
H . S l N G H A N D C . K . GUPTA
ratio of 3:l. Raffinate analysed <0.5 g/l uranium. Stripping of the

loaded organic in 2 columns with water at 70C in 1:l ratio gave a
pregnant liquor containing 35 g/l uranium and 0.1 g/l fluoride. In the
Indian plant, high fluoride in the plant feed was found to lead to
stress-corrosion cracking a t weld joints of steel impeller to the shaft. A
separate circuit was built to handle fluoride solutions in a polypropylene mixer settler. Fluoride solutions result from leaching of uranium
slag in nitric acid. Typical leach solution analyses (g/l): U = 10-15,
F = 1-3; Mg = 7 and Fe = 0.5-1. The free acidity is 2-2.5 N. A five
stage mixer-settler battery operating a t a n overall phase ratio of
O/A = 114 yields an extract containing 40-60gU/l. The unit has an
internal recycle from settler to same mixer stage to maintain a ratio of
O / A = 1.5/1. Loading of extract is below saturation to ensure raffinates are below 0.5 g u l l . This does not affect the purity since the feed
solution is already pure with regard to nuclear poisons and the only
separation required is for F. The extract contains only 0.05-0.1 gF/I
and free adidity is 0.1 -0.2 N.
Other advances in the field of refining in India [25,28] include: (a)
improvement in settling rate by use of 0.05 N acid for stripping instead of dimineralised water. Tests also showed coalescence rate doubled by an increase of temperature from 30C to 50C, (b) Entrainment
loss in alkaline processing of solvent was 9-15 ml/l, into the raffinate
was 0.7-2 ml/l and the pure strip solution was 0.5-3 ml/l. A dual
knit mesh packing of steel/polypropylene installed in the settler reduced the losses by a factor of five and reduced the dispersion band width
by a factor of 2, (c) solvent degradation over a period of two years
reduced the settling rate 15 times. Regular processing was found
necessary. Used solvent could be subjected to vacuum distillation in
the range 40C-130C and a residue separated for discarding as
waste, (d) slurry extraction as described subsequently in this paper.
Uranium from Phosphates
In India by-product uranium from indigenous phosphorites is estimated at 1695 tonnes [29]. As India imports bulk of its 2.5 million
tonnes of P,O, requirements of phosphates from Morocco, Florida
Jordan, Senegal etc. - all of which are uraniferous, the potential for
recovery is much greater. Research has been carried out in India o n
317
various aspects of uranium recovery from phosphoric acid [30-411.

Initial studies were carried out on the pyrophosphates as extractants.
However since the pyrophosphates were found to be unstable, further
studies were carried out on phenyl phosphoric acids. These had been
earlier considered as inefficient extractants by the researchers at
O R N L in USA. Based on systematic work with octyl phenyl acid
phosphates (OPAP), a process was finalised in India, which was later
developed in ORNL and used in Canada. A highly sensitive dye
method was developed for solvent loss determination. In 1987, a n
on-site pilot plant was operated to demonstrate the process feasibility
and study the requirements for feed purification. Subsequently, a large
scale pilot plant was operated on-site for technology demonstration.
Currently processes have been developed for simultaneous separation
of rare earth elements and cadmium. Industrial operation a t a large
fertiliser plant is under consideration. The environmental aspects of
radioactivity have been also investigated [42].
The pre-treatment to remove 'humic' matter has been studied. It has
been shown by IR spectroscopy that the humic matter present in the
acid can be separated by (a) clariflocculation with appropriate flocculant, (b) contacting the acid with a viscous D2EHPA solution to
precipitate the impurities as 'gunk', which can be subsequently separated in a centrifuge or a filter, and (c) adsorption on activated carbon.
The efficiency of separation as measured by the optical density (OD)
a t 408 nm, was found to be good. In a typical plant trial a t 1000 I/h,
the feed acid had a O D 1 1 . 5 , the O D of flocculated and aged acid
was 0.4, and after gunk generation it was < 0.35. N o carbon treatment
was necessary. About 440 gram of gunk was generated from a cubic
metre of acid. The uranium concentration in the gunk was low,
-0.0045%. Solvent loss with gunk was about 2/3rd weight of the
gunk. The acid oxidation study in 10 m3 reaction vessel showed that
the hot acid could be oxidised to an e m f . of above 450 mV by sparging of air. Oxygen sparging was needed for oxidation to > 550 mV. In
either case, heating of the acid was essential for effective oxidation.
The extraction tests showed that as the e.m.f. increased from 453 mV
to 571 mV, the distribution ratio increased from 9 to 29. The entrainment loss was found to be uniformly low, < 30ppm. The operation of
equipment such as clarifier, oxidation reactor, carbon column, phase
separation settler, froth flotation was found to be highly sensitive to
318
H. SlNGH AND C. K . GUPTA
the specific characteristics of the acid, attributed to the rock source

e.g., Florida, Morocco, Jordan or Senegal. In all cases however, the
plant could be tuned for optimal performance.
SELECTION OF DILUENT
Selection of a diluent for solvent extraction is important in the process

technology. Diluent selection depends on physical properties such as
flash point, viscosity, density, boiling range, evaporation rate and
solubility; on chemical properties such as influence on the distribution
ratio, selectivity, reaction with the extractant; hydrodynamic factors
such as third phase formation, crud formation, entrainment loss; and
safety factors such as the flammability hazard, toxicity rating and
effluent control limits; besides the economic factors. Diluent selected
to dissolve the extractant(s) may be aromatic, aliphatic or a mixture of
the two types of hydrocarbons. The nature of diluent has a significant
effect on the kinetics of process, including extraction and phase separation. A diluent which strongly solvates the extractant (for example a
diluent high.'in aromatics) will not allow it to be present at interface
for equilibration, while a diluent with low solvation (such as a mixture
of aliphatic hydrocarbons) may .not dissolve adequate concentration
of extractant for efficient extraction [43]. Hence it is necessary to have
a compromise. Often a mixture of the two types of hydrocarbons is
used, or a third component such as a phase modifier is added to
prevent formation of a third insoluble phase.
The effect of raw and sulfonated kerosene-type diluent has been
investigated in detail with reference to solvent extraction of uranium
and co-extractable impurities from both nitric acid solutions and wet
process phosphoric acid [44,45]. Kerosene as obtained from the
petroleum distillation contains a mixture of paraffinic aromatic and
napthenic hydrocarbons. Stability of the diluent to chemical attack
depends on the presence of double bonds which are the sites for
oxidation reaction and irreversible extraction of metals. In the study
reported, the effect of chemical treatment involving several washings
with 98% H,SO,, neutralisation with 5% Na,CO, and final washing
with water was studied by IR spectroscopy and experimental measurement of extraction performance. A comparison of treated kerosene
URANIUM AND
THORIUM SOLVENT EXTRACTION
319
(TK) and untreated kerosene (NK) showed that the treatment procedure decreased the unsaturated compounds, especially the
aromatics, from 16% to 6%, reduced the density and viscosity,
reduced the phase disengagement times by a bctor of two, and increased the distribution ratio. In the case of TBP extraction from
nitrate media, the saturation loading increased by 13%, and for a
six-stage extraction followed by eight stage stripping it was found that
there was reduction in raffinate level from 670 mg/l to 90 mg/l and
improvement in pregnant concentration from 64 g/l to 97.4 g/l. The
barren organic concentration also decreased from 2.75 g/l to 0.03 g/l.
There was greater inhibition of extraction of impurities. Similarly the
results on extraction from wet process phosphoric acid showed that
the treatment procedure improved the recovery of uranium by 30%
while reducing the co-extraction of Fe and Al by about 25% and 15%
respectively. Co-extraction of thorium and rare earths was also reported.
In a similar study [46,47] on the inter-phase transfer of U-VI from
phosphoric acid to kerosene solutions of D2EHPA-TOPO, it was
found that a sample with aromatic hydrocarbon content of 0.5%
(Ker.-A) gave higher distribution ratio and faster transfer rate than
sample with aromatic content of 18.3% (Ker.-B), particularly at lower
temperatures. The activation energy was also higher, at around 12.23
kJ/mol for transfer from aqueous to organic for Ker.A as against 9.04
kJ/mol for Ker-B, indicating the role of diffusional processes. The
activation energy for transfer in reverse direction was higher at 46.1
kJ/mol, indicating that the rate was chemically controlled. The effect
on the distribution ratio was correlated by log D = - AHl(2.303RT).
The value of AH was found to be -42.49 kJ/mol for Ker.-A and
-39.86 kJ/mol for Ker.-B. The behaviour of distribution ratios is
different for the two kerosenes. A plot of A log D vs T shows a
negative trend. The values of D rapidly decrease with acidity, nonaromatic kerosene always giving higher values. The results are consistent with the fact that the dominant species is UO;' at low acidity and
UO,(H,PO:-")n
a t higher acidity [48]. Performance of diluents for
uranium extraction from a n Australian ore leach solution has been
reported [49]. It was found that for uranium extraction with Adogen
364, an aromatic diluent, led to an interfacial crud formation, while a
purely aliphatic diluent gave a lower distribution ratio. Optimum
320
results were obtained with a solvent having 16% aromatics, density of

0.808 g/l, viscosity of 1.97 cst @ 2 5 T , boiling range of 200-240C and
a flash point of 80C. An excellent study on the selection of diluent for
practical application in treatment of wet process phosphoric acid is
presented with regard to cadmium extraction [50]. Wet process phosphoric acid (WPA) is a complex solution containing a large number of
inorganic impurities present both in solution and in suspension. The
large number of ions present lead to numerous chemical equilibria. The
formation of complexes between anions (F, C1, SO,) and cations (Fe, Al,
My) results in a complex system. The source of phosphate rock
(Morocco or Florida) leads to additional complications. WPA acid
made from Morocco rock has Cd level of 16 ppm, while that from
Florida it is 7 ppm. The purification level of 1 ppm is desired. In-depth
investigations showed that only an aromatic diluent Shellsol-A (flash
point 5WC, i.e., 15C above operating temperature) could be used. Its
main component is I,2,4-tri-methylbenzene and water solubi-lity is
59ppm [51] as against the solubility of 0.85 ppm for n-octane [52]. The
Florida acid gives a C1- level of 0.022 M but has high organic content
while that from Morocco gives 0.035 M CI but organic content is much
lower. Both CI- and organic level influence the extraction. The diluent
with high aromatic content has higher toxic rating.
In India over the years kerosene, purified kerosene, normal heavy
paraffin (NHP)-also called as Petrofin and n-dodecane have been
used as diluent for T B P in liquid-liquid extraction of uranium. N H P
of required quality is now produced indigenously by a process developed jointly by the Indian industry and BARC. The properties of
locally produced N H P for re-processing are: n-paraffin content
> 99%; aromatic and water < 100ppm; specific gravity: 0.75 a t 2WC;
flash point > 70C. Use of N H P has the advantage of greater stability
due to presence of > 99% normal chain compounds, and avoidance of
viscous red oil formation. While the products of T B P degradation are
removed readily by carbonate treatment, degradation products of the
diluent are not easily removed and get accumulated in the solvent
rendering it ultimately unusable, as also observed during refining.
Refined kerosene has the advantages of high flash point and higher
fire safety, lower evaporation loss, low vapour concentration in air,
permitting safer working environment without undue ventilation costs
and improved phase separation.
URANIUM AND THORIUM SOLVENT EXTRACTlON
32 1
The specifications of N H P have been modified for economical use

in uranlum recovery from phosphoric acid, Table V. Based on the
experience gained, N H P is now in use for uranium separation from
ore leach liquors, separation of rare earths and for uranium refining. It
may be noted that as per the hazardous substance notification of
Government of India [53], three classes are defined: 1) Flammable
gases with boiling point below 20C, 2) Highly flammable liquids with
flash point below 21C and boiling point above 2WC, 3) Flammable
liquids with flash point below 55C. The paraffin does not fall in
above classes. Similarly as per IATA regulations only liquids with
flash point upto 60.5"C classify as flammable.
HEAT EFFECTS IN SOLVENT EXTRACTION
Enthalpy changes accompanying solvent extraction have been a subject of interest from fundamental as well as applied considerations.
Thus, for example, in the extraction of uranium by tri-n-butyl phosphate diluted with an aliphatic diluent, it has been found that the
transfer of solute (both uranium and nitric acid) between the two
liquid phases is accompanied by significant change in temperature. Several published data for heat of reaction involving TBP under standard
TABLE V Characteristics of the Indian heavy normal paraffin for extraction

ITEM
TESTMETHOD
TYPICAL
SPECIFIC GRAVITY (15/4"C)

COLOUR (SAYBOLT)
VISCOSITY (cst)
FLASH POINT ("C)
REFRACTIVE INDEX
DISTILLATION ("C, at 760 mm Hg)
IBP
BP
TOTAL AROMATICS (%)
TOTAL NON-NORMAL (%)
C-I0
C-l l
C-12
C-13
C-14
ASTM D-1298
ASTM D-156
ASTM D-445
ASTM D-93
ASTM D-I216
ASTM D-1160
0.74-0.76
430
1.62 1
> 65
1.4358
> 175
UOP-495
Capillary GC
< 245
<I
> 98
18-30
20-35
20-35
10-25
<I5
322
conditions are available [54-581. The enthalpy change for uranium

extraction by TBP, which involves a solvation mechanism, is -54.5
kJ/mol. The heat effect for acidic extractant D2EHPA is lower,
- 30 kJ/mol. This may be because in the reaction with acidic extractant no major amount of electrostatic energy is gained when
U O i C exchanges for 2 H + , in contrast to the solvation mechanism
with TBP which involves association or UO;' with 2NO;. Additional differences arise due to bonding with four P - 0 groups in the
case of DZEHPA, compared to the two P - 0 groups and two nitrate
groups for TBP. Differences of the heat of hydration of UO;+, 2H'
and 2NO; are also significant. The data obtained under standard
conditions can be extended to cover the variations observed in practice [59,60].
The temperature profile across a cascade can be correlated with
concentration profile by mathematical modeling of the heat and
mass balance processes. Since the temperature profile is easier t o
measure on-stream in practice, it provides an inexpensive technique
for automatic process control [54-571. A computer program based
on these principles [60] has shown that, in the case of a reprocessing
flowsheet, temperatures can vary by over 10C at various stages and
these correlate with concentration successfully. The transient processes can be successfully simulated. A sensitivity analysis showed
that rt: 1% error of temperature measurement at each mixer settler
stage (i.e., k0.3"C for 30C) does not lead to any serious errors in
the estimation of concentration profile. The process control strategy
for changes in solvent flow rate, scrub acid concentrations, T B P
concentration, feed uranium concentration, feed flow rate can be
successfully implemented.
Heat effects are equally important when the ambient temperatures
difler significantly from the optimum process conditions. Thus for
example in the case of uranium recovery from Domiasiat ore in India,
the ambient temperatures can go down as low as 3"C, and insulation
of mixer-settlers as well as heaters Tor the start up are essential in the
extraction circuit. In the case of separation from phosphoric acid, the
stripping of uranium from the extract requires temperatures above
50C. In addition the strip acid is very viscous and forms an emulsion
if temperatures fall below 40C. Hence it was found necessary to
install graphite heaters in the mixer itself.
H.SlNGH AND C. K.GUPTA
323
PROCESS INSTRUMENTATION AND CONTROL

The efficient operation of solvent extraction plants is very strongly
dependent on the level of process instrumentation and control. While
much of the items are standard in the chemical industry, specific items
of interest to the uranium extraction are discussed.
An important requirement for automatic process control of solvent
extraction is the development of techniques for sensing the concentration levels of the extracted metal in the organic phase. Several
methods, depending on the metal of interest and the accuracy required, have been reported. An interesting method involves laser-induced thermal lensing effect [61] as demonstrated for uranyl nitrate in
30% TBP solution [62]. A pulsed dye laser excites uranyl ions so as
to create a local temperature gradient which changes the refractive
index. A probe beam from He-Ne laser passing through the sample
diverges. A fast Fourier transform spectral analysis helps determine
the absorbance of the sample solution, and detect concentration difference of 0.0001 M of uranyl ion. Normal absorption spectroscopy is
unable to resolve such low differences.
On-line analysis by X-ray fluorescence is becoming important for
automatic control and process optimisation. In India installations
have already been made in the ore concentrators of Hindustan Zinc
Limited, Hindustan Copper Limited and Indian Rare Earth Limited.
Similar application for solvent extraction are under consideration.
The system uses a n energy dispersive solid state detector and
radio-isotope energy source for the X-ray analysis. Each element in
the solution stream emits fluorescent X-rays of a n energy that is
characteristic of the element. The signals are processed for resolution
into concentration measurements. Elements in the range of atomic
numbers 16 to 92 (sulphur to uranium) can be measured besides
measuring p H and temperature. Typical accuracy is 2-8% in the
concentration range 0.001-1 g/l, and 1-2% for > 10 g/l.
ENTRAINMENT
Successful industrial operation of solvent extraction processes requires
that the loss of solvent into the aqueous raffinate should be minimised.
324
The solvent loss is due to soluble loss as well as entrainment loss. The
soluble loss, which is generally low, depends on the physico-chemical
characteristics of the system selected for operation and is beyond the
control of an operator. The entrainment loss is due to mechanical
factors and can be significantly high. Experimental investigations have
been conducted world-wide for understanding the mechanism of entrainment loss and development of equipment for its minimisation
[63-711. In a commercial plant operating with large flows, even a
ppm level loss can be unacceptable either in terms of the economics o r
toxicity load on the environment if released as effluents o r lead to
downstream technical problems.
Primary reason for entrainment from mixer-settlers, which are the
preferred equipment for large scale operation of solvent extraction, is
secondary liquid-liquid phase dispersion. The secondary dispersion
consists of extremely fine droplets which do not coalesce in the conventional gravity settlers [64]. Secondary droplets are formed which
are stable and their distribution depends on several factors such as:
droplet-film particle size, curvature of the droplet film interface, density differences between the phases, viscosity ratio of the phases, impedance ratio of the phases, interfacial tension, interfacial potential,
temperature effects, mechanical vibration effects, presence of third
phase, mutual solubility, external electric field, external magnetic field,
internal electrical field.
The aqueous raffinate needs to be passed through equipment such
as post-settlers, flotation cells, absorption columns, centrifuges and
electrical settlers for overcoming the limitations of ordinary gravity
settlers in coalescence of secondary droplets. We have carried out
investigations in a 1000 litreslhr pilot plant having a lamellar parallel
plate coalescer as well as a flotation cell. The applications include (a)
uraniferous phosphoric acid contacted with an organophosphorous
synergistic mixture in aliphatic diluent, and (b) sulphate leach solution
containing uranium contacted with 0.5 M tertiary amine in aliphatic
kerosene and an alcohol as phase modifier. The details of the lamellar
settler are shown in Figure 2. The entrainment levels were measured
by a dye technique [33] and also confirmed by infra-red spectrometry.
The efficiency of the lamellar settler was found to be > 90% and that
of the flotation cells to be 80%. The secondary dispersion resulting
from the last settler can be measured by laser size analyser. Droplets
CLEAN ACID
OUTLET
SLUI
PLATE PA
FIGURE 2 Parallel Plate Separator for recovery of entrained solvent.
of the dispersed phase diffract the incident laser beam due to differences
in the refractive index of the organic phase and the aqueous phase. The
emergent beam is detected by a multi-channel detector and the angle of
dfiaction is correlated to the droplet size. The data is analysed on-line
to obtain the size distribution. Typical results are shown in Figure 3. The
fine droplets in the settler approach the corrugated parallel plate, get
adsorbed on the hydrophobic surface, the intervening film between two
droplets ruptures and coalescence takes place, as shown in Figure 4.
Large coalesced drop rises to the surface where it is skimmed off.
The data obtained on droplet size distribution of the entrained
phase can be used to model the performance of the lamellar settler by
a population balance approach. The desired inclination of the plate
separator has been reported to be 15". At this slope the fouling capacity of the unit is reduced and the load of dispersed phase is acceptable [71]. Solutions with higher solids and scaling tendency need
higher slope, -45".
The performance of the primary settler in the mixer-settler battery
has been the subject to considerable research over the years [65,72-751

18.00
12.00
8.00
VOLUME (%)
4.00
0.00
FIGURE 3
&
5.00
10.00
15.00
DIAMETER (ym)
20.00
25.00
&
Laser size analysis ofentrained solvent drops.
Coalescence
Heavy phase
droplet Heavy phase
continumn
/
Inclined d a c e
FIGURE 4 Coalescence of secondary droplets in a Parallel Plate Separator.
as it is the source of the formation of entrained droplets. It has been

shown that the data on settling can be correlated by a power law:
H = K ( Q , / A ) q ,where H =thickness of the dispersion band, Q, =flowrate of the dispersed phase, A =settling area, K and q =empirical
327
constants. The scale-up based on this approach suffers from the limitations that the K and q values are highly variable, depending upon
mixing intensity, phase continuity, temperature, phase ratio, impurities present in the aqueous and organic phase etc.
Hydrodynamic studies have shown that the droplet size is independent of the dispersed phase flow rate, the thickness of the dispersion
band is a function of the specific flow rate of the dispersed phase but
independent of the total flow of the dispersion and there are both
vertical and horizontal zones of coalescence. In the horizontal zone
the dispersion is uniformly spread with little variation in the drop size.
In the vertical direction, the droplet size changes very significantly.
Dramatic reductions of the aqueous entrainment in the organic phase
have been reached by using an externally applied pulsed D C electrical
field across coated electrodes [67,68,75,76]. Field tests in the US have
shown for amine extraction of uranium, the conventional loading rate
can be increased six times by using a n electrostatic coalescer.
Fibre bed coalescers provide another technique to reduce entrainment [76,77]. Modelling studies show how the inertial interception
leads to coalescence as a function of internal pore properties, shape,
area and hydraulic diameter. Fibre coalescer media have high surface
area and rather large pore cross section which help enhance efficiency
without increasing the pressure drop. Polypropylene fibres are
superior media for promoting coalescence.
Structural factors influencing phase separation rates, and consequently the entrainment level, have been systematically investigated
for systems employing tertiary amine extractants [78]. The extraction
of uranium has also been evaluated. It was found that in the case of
organic continuous (OC) mode, increasing the number of carbon
atoms per chain (n) reduced the phase separation rate, whether the
chain was linear or branched. For a constant value of n, the branched
chain amines were found to separate faster than linear chain in the
O C mode. A key structural factor for the O C separation was found to
be the backbone chain length i. e., the longest chain in each alkyl
group. Aqueous continuous (AC) dispersion separated fast, but was
very sensitive to presence of colloidal silica as well as the use of actual
leach solution instead of the synthetic one. Stabilisation of AC dispersion by silica and crud formation was explained by a model. Larger
molecular weight amines with n z 10 were found to give faster settling
328
H. SINGH AND C. K. GUPTA
rate, less emulsion stabilisation and crud formation as well as higher

uranium extraction and lower tendency for formation of a third phase.
Solubility losses can also be expected to be lower. Results showed
that uranium ore processing plants based on the amine process could
improve performances by using branched chain extractants of higher
molecular weight.
PURIFICATION O F AQUEOUS AND ORGANIC PHASES

Aqueous solution containing the metal value of interest must meet
stringent requirements with regard to impurit& before it is considered
suitable for industrial operation of solvent extraction. Presence of
colloidal silica can lead to deleterious process performance, as discussed earlier with regard to the entrainment levels. Impurities in the
commercial extractants, solvent degradation products, presence of
solids and humic acids in the ore and their build-up over time can
have a marked effect on the process performance [79,80]. Actual
process testing is essential for each specific system. Mere measurement
of physical parameters can lead to misleading conclusions. Higher
interfacial tension can thus be expected to increase the phase separation rate since it can be expected to increase the thermodynamic
instability which favours coalescence. But the opposite trends have
been reported from the plant experience [79] and research studies
[80]. The effect of impurities in the commercial extractants is pronounced on phase separation in the case of aqueous continuous dispersions
when ore leach solutions containing silica are used. Purification can
lead to dramatic improvements. Similarly the effect of recycling water
from a tailings pond back into the solvent extraction circuit in a mill
is known to have caused emulsion problems [78].
Crud formation involving build-up of a film like solid phase at the
interface of the aqueous and organic phases is a serious problem in
the industry [81,82]. The interfacial layer of crud stabilises organic
droplets and prevents their coalescence. A large amount of solvent
gets trapped, leading to high losses and in extreme cases it can cause
expensive shut-down. Crud formation is enhanced not only by Si, but
also by Fe and to lesser extent by alkali metals. lncorporation of a
scrub.stage before the stripping, apart from any benefits in terms of
329
purity, helps to improve the system hydrodynamics by isolating the

crud to extraction stages only. Addition of fluoride is one of the
methods of dealing with a siliceous crud problem [83]. Crud formation
is also affected by the nature of diluent, aliphatic diluents like Exsol D
100 (aromatics < 0.9%, flash point 102"C, distillation range 235-262"C,
non-flammable) producing less crud than aromatic diluents when contacted, for example, with wet process phosphoric acid [84].
Purification of a solvent by contacting with another extractant has
been reported in a novel application [85]. Solvent containing
25%TBP in lsopar M was contaminated with tributuxyethyl phosphate (TBEP) leading to reduced extraction of uranium and higher
phosphorous levels in the uranium product. Conventional sodium
carbonate wash gave an organic containing 100 ppm uranium, higher
than the required limit of 5 ppm. The strong complexing power of
IONQUEST 201 (I-hydroxyethyl-1, 1-diphosphonic acid) and its ability to form metal complexes which are soluble in water was utilised
for purification of the contaminated solvent. The IONQUEST 201
product stream was decomposed by hydrogen peroxide into phosphoric acid and carbon dioxide for subsequent treatment.
Electrodialysis techniques have been investigated [86] for purification of uranium leach solutions to remove anionic impurities such as
molybdates.
In our pilot plant test work, purification of feed solution has been
found essential when organic impurities are present in the form of
dissolved 'humic' matter and insoluble oils, greases, etc. due to leakages
into the process fluid from gear-boxes etc. As solvent is repeatedly
recycled, these impurities can accumulate. Once poisoned, there is little
possibility of solvent purification. The humic matter resulting from dissolution of organic impurities under strong lixiviation conditions has
been recognized as a major problem in many plants. Harmful affects
are (a) poor phase separation in settlers, lowering capacity (b) stable
emulsions leading to solvent loss and plant shut-downs (c) aggravated
problems in stripping, especially with 10% (NH&SO,. A detailed
Chinese study on sandstone-type ores (using IR Spectroscopy, electron
microscopy) used in acid leach and amine extraction has shown [87]
following: (a) Organic continuous dispersion inseparable at humate
level about 39 mg/l. Upto 30 mg/l the separation time increases linearly,
from 30 sec to 300 sec., (b) Nature of crud varied from 100 nm spherical
330
H. SlNGH A N D C. K. GUPTA
particles to fibrous forms. (c) Decrease in uranium loading was to

two-thirds of normal value. (d) Pre-treatment with activated carbon
adsorption o r coagulation with higher molecular weight flocculant,
removed organics. (e) The accumulated humus in organic phase could
be removed by sodium carbonate scrubbing of solvent.
SOLVENT-IN-PULP PROCESSING
In the front end of the nuclear fuel cycle, extraction of uranium from
ore leach solutions commonly uses solvent extraction. Mixer-settlers
are the preferred choice of equipment. The mixer-settlers are however
prone to failure if the feed solutions are not adequately clarified. The
clarificati'on of the feed slurry is an expensive operation, accounting
for nearly a third of the capital costs and 10-20% of the operating
costs. Solvent in pulp (SIP) technology is under development for direct extraction from slurries without prior filteration [88-911. It also
increases the overall recovery by reducing the soluble uranium losses.
The equipment to be used for contacting needs to have the capacity to
handle solids. An 'internal mixer-settler' has been tested for extraction
by the DZEHPA solvent from sulphate leach solutions [88]. In this
apparatus mixer and settler are combined in a single tank. Settling
takes place in the bottom and top sections. Internal recycle of organic
phase provides an O/A ratio of over 10 which helps in treating dense
slurries, having solids in the range of 40-55% w/w. From the mixer
tank, the aqueous is pumped from the bottom while the organic overflows by gravity. The losses of organic could be reduced by varying
parameters such as mixer speed, dilution of the effluent with water or
addition of surface active agents such as organic sulfonates to levels of
0.03-0.06 m3/tonne of solids. High levels of entrainment were observed to be due to free standing droplets ranging in size from 15-150
micron. Slurry extraction with amine solvents was considered less feasible since the amines are preferentially adsorbed on the solid surface.
Alternatively pulsed columns have been tested [91,92]. When treating solids, the flow rate, amplitude and frequency need to be decreased
by a factor of two compared to operations with clarified solutions.
Under these conditions, uranium extraction from 20% solids by
Alamine 336 could be achieved at a solvent loss of < 50 ppm. However
331
the throughput was low and the inventory of solvent high [92]. The
ralfinate from uranium was processed for recovery of copper and
nickel and by slurry extraction using LIX63 and D2EHPA. Feasibility
of slurry extraction was demonstrated in a 250mm column at a
throughput of 13.5 T P D solids in a slurry containing 35% solids with
amine loss limited to 35 gmltonne [90]. The loaded organic was
filtered through a plate and frame filter and the solids were repulped
for solvent recovery and recycle. Acidification of the solvent after
stripping was carried out to pH of 0.5 to prevent crud formation,
which occurred at higher pH. The amine loss was of the order of 15
gmltonne of solvent for each settler [93]. A more extensive investigation [94] showed that aqueous continuous phase gave much lower
solvent losses, even though the operation in organic continuous mode
was easier. Effect of the plate material was also reported. In a recent
study [91] it was found that the presence of solids reduces the dispersed phase hold-up, increases drop sizes and leads to loss of the organic
phase by formation of stable emulsions or adsorption of the solvent
on the solid surface. The erosion of the pulsing stator can be expected
to be high. The occluded solvent needs to be recovered by an additional
step. A recent study on hydrodynamics of Rotating Disc Contactor has
shown [95] that it can handle solids of the order of 20% by weight.
Solvent in pulp is a potential technology for economical uranium
extraction and is a logical extension to proven technologies of resinin-pulp and carbon-in-pulp [96].
In India, air-mixed slurry extraction units have been developed [97]
and have been in operation in three plants in the country. It has
helped to eliminate three stages of filtration and cake-repulping when
conventional units based on clarified feed were in use. The unit is
schematically shown in Figure 5. It has no moving parts and is without control valves. Air lift pump is used for inter-stage transfer of the
aqueous phase and for mixing the two phases. Organic flows by gravity from stage to stage, with an overall level difference of 300 mm for
seven stages..A large recycle of the organic, controlled by flow regulation of air used for air lift, is maintained to ensure operation in the
aqueous dispersed mode and minimise the loss of solvent. Slurries
containing 15% solids could be handled. The air is separated from the
liquid-solid phases at the end of air lift in a disengagement chamber. It
passes through mist eliminators and is exhausted through a header. At
332
H . SlNGH A N D C. K. GUPTA
FIGURE 5 Solvent in Pulp(S1P) for uranium refining.
the raffinate end, the aqueous phase is drawn by air metering. Mixing efficiency of the order of 85-90% has been achieved during the
contacting in the air lift zone with a residence time of the order of
seconds. The organic flow to subsequent stages is through the settler
downcomer, which is s o sized that there is upward flow of organic
and downward flow of the aqueous. The recycle rate of organic at
each stage is very important and an automatic control system has
been developed.
EXTRACTION OF URANIUM AND THORIUM
Solvent extraction plays a vital role in the recovery and separation of

uranium and thorium from monazite mineral concentrate of monazite
333
produced from beach sand minerals. It is also important when mined

ores containing both uranium and thorium minerals are processed
[98,99].
Extraction by TBP
Selective extraction of uranium, in the hexavalent form, from the tetravalent thorium from nitrate leach solutions by neutral organophosphorus compounds such as T B P has been practiced on commercial
scale world-wide [loo-1021. The separation by TBP generally uses a
low concentration of TBP, say 5-lo%, for selective extraction of
uranium over thorium. From the raffinate, free of uranium, thorium
extraction requires a higher T B P concentration, about 40%. Here
care has to be taken to avoid formation of a third phase due to lower
solubility of the extracted Th(NO,),. T B P in the non-polar diluents
used. The selectivity of TBP is rather low. It can be improved by use
of other phosphates and phosphonates, particularly by incorporating
branched alkyl groups [102-1031. Fundamental studies on the TBPnitrate system have been carried out for better understanding of the
process [104-1061. The extraction rates of uranium and thorium increase with increasing nitric acid concentration and with saturation
appearing a t nitric acid concentration higher than about 2.0 M. The
rates increase linearly with NO; ion concentration, but decrease with
H' ion concentration. Apparent activation energy of 16 kJ/mol for
uranium and 43 kJ/mol for thorium was obtained from the temperature
data. It suggests that the extraction rate of uranium and thorium is
controlled by chemical reaction at lower temperature and by diffusion
process at higher temperature. The thorium nitrate extraction by trialkyl phosphates is by solvation with 3 number of molecules as well as
by 2 numbers. Uranium forms only di-solvates with TBP.
Separation by Carboxylic Acid Amides
Extractants of the carboxylic acid amides, N-alkyl type (R.CO.NHR'),
developed as alternatives to organophosphorus extractants in the
back-end of the nuclear fuel cycle, are of interest in the front end as
well [107]. The effect of extractant structure on the selectivity of
separation and stoichiometry of the extracted species has been studied
334
by varying the alkyl groups R and R'. Also studied are the N,Ndialkyl amides (R.CO.NR,') and non-substituted amides (R.CO.NH,).
Studies were carried out by solutions of the amides in toluene.
Increasing steric bulk of the alkyl groups R and R', for N-alkyl
amides, was found to cause a marked decrease in the extraction of
thorium with the effect on uranium being lower. This significantly
increases the selectivity between the two metals. The effect of group R'
becomes strongly evident for tert-alkyl groups, or if both R and R' are
branched. The alkyl group R has greater steric effect than R'. The
structure of U-VI complex [lo81 can explain these differences as the
amide ligands are coordinated to the metal ion by the carbonyl oxygen
atoms. The significantly greater steric effect observed in the extraction
of Th-IV are apparently due to the difficulty of assembling four nitrate
ions and the required number of amide ligands around the central
cation. Comparison with the separation factor for neutral organophosphorous compounds shows amides are capable of superior separation
to both 1M TBP, having a factor of 1.89, and 0.15M di-n-butyl
n-butylphosphonate, having a factor of 1.51.
The separation factors for the extraction from 2M sodium nitrate
by O.SM N,N-Dialkyl Amides R.CO.NR, have been evaluated and
results show that the separation factor for branched chain compounds
are much higher. Thorium is appreciably extracted only by a compound containing R=CH,.
Extraction by amides is generally by solvation type mechanism
[lO8-1 lo].
Where M n f denotes Th4+ or U O i f . The relation for the distribution

ratio D follows:
log D = log Kex + n log[NO;]
+ plog[Amide]
(18)
Experimental data [lo71 showed that values of p were in the range

i.98-2.09 for uranium and to 2.75-3.37 for thorium, with the n values
being 2 and 4 respectively. At lower amide concentrations, the value of
p for thorium has been reported to be two [108].
335
Separation by Tri-sec-Butyl Phosphate

The steric effect on the differential extraction by phosphate or phosphonate is the basis for using extractants with the introduction of
branching at the first carbon atom of the alkyl group attached to the
oxygen atom. The extraction of uranium is not affected but that of
thorium is reduced due to the higher number of extractant molecules
(3-4) in the thorium solvate.
Experimental studies have been reported on extraction by tri-secbutyl phosphate (TsBP) [ l l 1-1 121 and tri-iso-butyl phosphate (TiBP)
[113]. Results on uranium show that for low acidity, say upto 3 M,
the differences in the three cases of TBP, TsBP, and TiBP are not very
significant. The extraction of thorium decreases very significantly at
high loading and high acidity when T B P is replaced by TsBP. Thus at
5M HNO,, from a feed containing 1 g/l U-VI and 50g/l Th-IV, the
separation factor using 1.1 M for T B P is 6.8 while that for TsBP is six
times better at 41.2. The selectivity can be further improved by lower
loading and by using lower extractant concentration. An additional
advantage of TsBP is the significantly higher, by a factor of 1.3 to 1.5,
the limiting organic concentration for third phase formation in comparison with TBP. The higher solubility of the thorium solvate with
TsBP also makes it a better choice for extraction of macro levels of
thorium in the second cycle.
Separation by DZEHPA in a Carboxylic Acid Diluent

DZEHPA is generally used in a diluent in which the extractant is
generally aggregated as a dimer. Extraction of uranium and thorium
from an aqueous mineral acid using D2EHPA in a dimerising diluent
yields very high distribution ratios [I 14-1151. An alcohol can be used
as a monomerising diluent [I161 but it yields very low distribution
ratios. An alternative is to use carboxylic acid as a monomerising
diluent [117]. Extraction behaviour for U-VI and Th-IV using 2-ethyl
hexanoic acid as a diluent for DZEHPA has been reported for an
aqueous chloride phase [118]. It is found that the extraction reactions
correspond to
H. SINGH A N D C. K . GUPTA
where HY represents the monomer of D2EHPA. With H Z representing the monomer of 2-ethylhexanoic acid, the extracted species are
postulated to be Th(HY),(HYZ), and UO,(HY,)(HYZ). The distributions ratio K in terms of formality F (defined as the number of formula weights of solute per litre of solution), acidity [HC], and a
constant K , is K = K,, F 3 / [ H f I 4 for thorium and K = K,, F Z / [ H + I z
for uranium.
The value for K , are 70000 for thorium and 200 for uranium. Selectivity with respect to trivalent rare earths which have K , values
0.01-7, is excellent. The extracted metals can be stripped into an
aqueous phase by 6 F HCI. I n fact the extractant scheme has been
proposed for extraction of thorium from low-grade resources while
purifying from rare earth contaminants. During the extraction by
D2EHPA, regeneration of organic solvent can be achieved completely
by contacting with aqueous solution of oxalic acid [I 191.
Similarly extraction with bis para-octylphenyl phosphoric acid, denoted as HDO+P, has been investigated from chloride medium [I201
and it is found that the K, ratio T h 4 + / U O i + is nearly 2.0 x lo5, and
the selectivity w.r.t. Eu is over a million. O n the other hand if the
extractant is bis-diisobutyl methyl phosphoric acid (HD(DIBM)P),
then the K, ratio is reversed to 2 x lo-' and uranium extraction is
favoured. The latter extractant has adequate selectivity in the nitrate
medium also to be useful [121]. Thus the liquid-liquid extraction
system can be selected to extract the minor component selectively,
whether uranium or thorium.
Selectivity of uranium extraction over thorium from hydrochloric
acid solutions using diphenyl sulphoxide (DPSO) has been investigated with respect to parameters such as concentration, temperature
and acidity [122]. Sulphoxides containing the S - 0 group, in contrast to the P - 0 group of organophosphorous compounds, are
simple compounds having a pyramidal molecular structure coordinating by donating of the electron pair on the oxygen. Their stability is
good and viscosity much lower than TBP. Uranium can be preferentially extracted from 5 M HCI with a neutral salting out agent at a low
temperature using a higher concentration of thorium than uranium.
The separation factor is 3690 and virtually all the uranium is extracted,
337
leaving thorium in the aqueous phase. Benzene is used as diluent and

the method is appropriate for laboratory work.
Comparative extraction by di(2-ethylhexyl)sulphoxide and T B P from
nitrate media has shown DEHSO is superior 11231. Use of binary
mixtures for simultaneous recovery of Th and rare earths in nitrate
medium has been recently patented [124]. The process comprises contacting a nitrate solution with an organic extractant compound containing two extractants, one from the group OP(OR1)(OR2)(OR3),
OP(OR1)(OR2)R3, O P ( O R ' ) R 2 ~ 3 , and OPR1R2R3 [R1-R3 =
hydrocarbon radical.]; and second from the group P(OR4)=(OR5)
0 , H [R4,RS = hydrocarbon radical]. The solvent mixture has a high
separation coefficient.
Use of dialkyl dithiophosphoric acids for thorium extraction has
been reported [125]. Studies on use of chelating extractants for uranium and thorium have been reported [126-130). LIX84 (2-hydroxy5-nonylacetophenone oxime) and its mixtures with other chelating
extractants or neutral donors showed very little extraction for thorium, although uranium was extracted. Extraction of uranium V1 from
nitrate solutions by 10% (v/v) LIX 622 in a benzene diluent was found
to increase with increasing equilibrium pH in the range 3-6. TBP acts
as a synergistic modifier upto 2%(v/v), beyond which antagonistic
effects are observed. Thorium-1V extraction by LIX 622 and its mixtures with Alamine 336 and Aliquat 336 was found to be poor in the
pH range 1-4. Separation of Mo-VI, which is undesirable in uranium
circuits, can be achieved at high acidity. The extraction corresponds to:
The dependence of distribution ratio D on the acidity is given as

log D
= log
+ log[NO;] + log[HL]
where K is the equilibrium constant.

In the process it was found that pH adjustment by addition of ammonia or caustic solution led to formation of turbidity and third phase,
and had to be carried out instead by the addition of pyridine. Extraction decreased with increasing concentration of CI and SO, ions.
338
H. S l N G H AND C. K. GUPTA
Supercritical fluid extraction of uranium and thorium from nitric acid

solutions with organophosphorus reagents is an exciting new area
which can lead to newer separation processes [131]. An organophosphorus reagent is dissolved in supercritical CO, by passing the fluid
through a reagent vessel placed upstream of the extractor. Using TBPO
or T O P 0 in supercritical CO,, effective extraction of uranyl and thorium ions can be achieved even from dilute HNO, solutions.
Plant Flowsheets for Uranium and Thorium Separation
Uranium ores of the Elliot Lake, Canada contain thorium and rare
earths, and process flowsheets have been practiced for their recovery
[132]. Ore containing'0.l WOuranium, 0.028% thorium and 0.057%
rare earth oxides were processed by sulphuric leaching, clarification
and uranium extraction by ion-exchange. Barrens containing (g/l) 0.13
thorium, 0.10 rare earths, 0.005 uranium, 0.04 titanium, 18.9 sulphate
ion are processed in 3180 litres/min. solvent extraction plant. Organophosphorus extractant is used at aqueous/organic ratio of 9-11:l in
a mixer with contact time of 1-2 min and settler with a surface area of
149 m2. Phase separation is rapid and is complete in 30 sec. Solvent is
stripped with ION H,SO, at organic/aqueous phase ratio of 4:l Strip
settler has a capacity of 6813 litres. Mixed solvent loss is 333 ppm of
barren aqueous. Solvent regeneration is carried out partially using HF.
Thorium is recovered as a sulphate. Rare earths are co-precipitated.
In India monazite is the main source of rare earths and thorium,
besides producing by-product uranium. A new process for separation
of these elements by a solvent extraction route is shown in Figure 6.
The composition of various streams is shown in Table VI.
BINARY EXTRACTANTS
Extraction of uranium by a binary mixture of Aliquat 336 and PC88A

from aqueous phosphoric acid has been studied recently [133]. In the
extraction studies using 5%(v/v) Aliquat 336 (trade name for tricapryl
methyl ammonium chloride:R,R'NH,PO,), 5% (v/v) PC88A (trade
name for 2-ethyl-hexyl phosphonic acid mono-2-ethyl hexyl ester:
(HA),) and their 1 : 1 binary mixtures in xylene, it was found that there
is a synergistic effect over the entire range of acid concentrations,
339
103'0 ALAMINE-336 INKEROSENE

I
Loaded Organic
.
,
U &Fe
STRIPPING
Ra&nate I
bJcous
O.lNHQ
Feed
1 M P C S A INKEROSENE
EXTRACTION
STRIPPING
5%
J-
Scmb
aEinate I1
RE. Th. Fc. Ti
FIGURE 6
Ti Strip
Th, Ti. F
RE,Th.Fe. Ti
Flowsheet for separation of U, Th and rare earths.
TABLE VI Typical composition of streams for separation of uranium, thorium and

rare earths by PC8BA/Alamine 336
Stream, gll- >
CeO,
RE0
Nd,O,
Tho,
U,O,
Fe,O,
TiO,
Aqueous Feed
Raffinate I
U-Strip
Raflinate I1
Scrub
Th-Strip
Alamine 336 Extract
PC 88A Extract
Stripped Alamine 336
Stripped PC 88A
Ti-Strip
Flouride concentration in strippcd PC88A can be in the range of 1-100 ppm and in the Ti strip
solution 5%. Streams correspond to the Figure 6 streams.
which was attributed to the formation of mixed adduct species,

UO,A,(R,R'N,)(H,PO,), in the extracted organic phase. The distribution ratio was found to decrease in the acidity range 0.4-1.4 M
H . SINGH AND C. K. GUPTA
340
H,PO,. Effect of diluent showed that there was a decrease in extraction by a factor of 1.15 when diluent was changed from xylene to
kerosene.
In a similar study, involving uranium extraction from phosphoric
acid solutions [134], it was found that there was antagonism in using
mixtures involving tri-isodecylamine (Alamine 310), TBP, di-n-pentyl
sulfoxide (DPSO). Maximum extraction was found in the higher acidity
range. Extraction was less by bis(2,4,4-trimethyl penty1)phosphininc
acid (Cyanex 301) and its mixtures in the range 0.2-1.0 M H,PO,.
Uranyl extraction by mixtures of Cyanex301/Alamine 308
(triisooctylamine) with TBP/DDSO(didecyl sulfoxide) from chloride
solutions has been reported [135]. Mixtures of Cyanex301 (RH) with
TBP, DDSO and Alamine308 show significant synergism by the solvation mechanism. Extracted species is of the type UO,R,.L where
RH is Cyanex 301 and L is for the synergistic neutral ligand TBP,
DDSO o r Alamine 308.
UO:&,
+ 2RH(org)=UO,R,(orgj + 2H + (aqj
(23)
It is to be noted that Alamine 308 behaves like a neutral donor in the

range 0.2 to 1.0 M HCI mixtures of Alamine 308 with TBP or D D S O
is
result in a synergism where a species of the type (R,'NH),UO,Cl,L
extracted, with R,'N being the amine and L = T B P or DDSO.
Mixtures of Alamine 308 and Cyanex 301 used for extraction from
aqueous phase at acidities above 2 M HCI were found to show strong
antagonism.
Quarternary ammonium compounds (such as Aliquat 336) have
better extractive power than the tertiary amines [136-1381 and the
extraction of uranium with mixtures of Aliquat 336 and PC88A, in
xylene diluent, from nitric-sulphuric acid medium has been investigated [139]. Aliquat 336 is a quarternary ammonium compound of
the type tricapyryl methyl ammonium chloride. Extraction from
0.5-6 M HNO, solution showed maximum synergism at 3 M. The
result is interesting since extraction with PC88A alone showed a
minima in extraction a t 3 M. The synergistic coefficient S C defined as
34 1
log ((D,,)/(D, + D,)), reached a value of 0.251 at 3 M. Extraction

from H,SO, medium is of interest from the point of view of application in the uranium ore processing, and both antagonistic and synergistic effects are important.
The effect at lower acid concentrations is attributed to the interaction between the extractants:
At high concentrations of the acid, the sulphate compounds of the

quarternary ammonium salt are formed which decrease the antagonistic effect [140].
Extraction using a binary mixture of benzoic acid and cinnamic
acid has been reported [141].
Synergism was reported in the solvent extraction of uranyl nitrate
by tetrabutylalkyldiphosphonates (TBADP) and tetrabutylalkylenediphosphonate-D2EHPA mixtures [143]. The TBADP tested included
both the methylene and ethylene varieties:TBMDP and TBEDP with
the structure as ((RO) 2(0)P - (CH)n - P(O)(OR)2) with n = 1 for
TBMDP. A synergistic effect was observed when mixtures of TBADPD2EHPA were used as follows:synergism is explained by the neutral
donor ligand property [144], which also explains the superiority of
TBEDP and TBMDP.
Extraction of thorium with binary mixture of PC88A and T O P 0
from an aqueous HCIO, media with various diluents has been investigated with regard to the synergistic effect [142]. Modelling of uranium and thorium extraction data has been carried out [145-1471.
LIQUID-LIQUID EXTRACTION AND URANIUM ENRICHMENT

Chemical exchange reactions leading to isotopic enrichment in two
immiscible phases have been used in the nuclear industry. Solvent
extraction systems have been the focus of intense research, especially
in France and Japan [148-1521. The uranium ions exist in aqueous
solution in forms of U-111, U-IV, U-V and U-VI. The precipitation as
hydroxyl complexes is prevented by controlling the proton concentrations. The stable oxidation states of uranium in aqueous solution are
H. S l N G H AND C. K. G U P T A
342
U-IV and U-VI as UO:+ due to oxidation-reduction potential and

disproportionation reaction of the five valency form of ion U 0 2 + .
The standard reduction potentials in HCI media are as given in
Table VII.
Since the potential between U-111 and U-IV is lower than that
between H2 and H', U-I11 is oxidised to U-IV with the evolution of
hydrogen gas. The U-V and U-VI strongly bond with oxygen to form
UO:' and U 0 2 + . The U disproportionation of U 0 2 + produces the
tetravalent and hexavalent ions. ths isotopic equilibrium between the
Uranus and uranyl ion is the basis for chemical exchange:
The equilibrium constant K = 1 2e, where e the enrichment factor, is

reported to be 1.0013. Early studies [I531 showed that either the
separation factor was too small or kinetics were very slow. Requirements of an economic chemical exchange process for isotopic enrichment of uranium were specified as (a) a single stage separation factor
preferably greater than 1.005 but certainly greater than 1.001, and an
exchange rate which is high enough to give an equilibrium in less than
60 sec per stage, (b) a n efficient method of product and waste reflux,
and (c) suitable means for continuously separating the two chemical
forms of the element. Process energy of the advanced chemical enrichment process, based on dynamic enrichment factor, has been found to
be much smaller than the value in the original process, both in the
laboratory and applied to pilot plant process [150]. The French results on the solvent extraction process for enrichment were announced
in 1977 [I521 Technical details were subsequently published
[149,154,155]. The originality of the French process lies in the choice
TABLE VII
Redox reactions lor enrichment by solvent extraction
Oxidation-reduction equlihrin
Potenrial, m V
URANIUM A N D THORIUM SOLVENT EXTRACTION
343
of the interacting species as trivalent and tetravalent uranium which

has a n enrichment factor of 2e = 0.025 at 40C, about double of the
conventional U-IV/U-VI or U-V/U-VI exchanges. The exchange coefficient further increases to 0.027 at lower temperature of 20C. In the
solvent extraction process, aqueous hydrochloric acid phase (4.6-5.2
M) retains 1.5-1.8 mol/l of uranium consisting 94% of the trivalent
uranium while the organophosphorus phase (40% T B P in alkyl benzenes-Solvesso 150), retains the UCI,, 0.5-0.6 mol/l, enriched in the
U-235 isotope. The U-III/U-IV kinetics are very fast and the interfacial exchange kinetics control the overall kinetics. The isotopic
exchange is carried out in pulsed columns operating in the continuous
organic phase, designed upto 150 mm in diameter and 50 m in height.
Twin square cascades, each containing 20 large columns in series, can
yield 500000 SWU/yr for a tails of 0.18% and 90 T/yr product of
3.5%. The main advantages include (a) low specific energy consumption, (b) low inventory (c) handling of uranium in aqueous forms
which is safer, (d) modular system design (e) low sensitivity to fluctuations in the operating conditions and ease of control (f) small number of moving parts. Mixer-settler extraction system based on solvent
consisting of tri-n-octylamine in benzene and extraction from HCI
aqueous phase has been studied by British investigators [151,156].
The concentration level of the uranium in the organic phase containing upto 40% amine, was high, > 100 g/l. In 4 M HCI U-VI had good
solubility in the organic phase but the U-IV was almost insoluble.
Equilibrium data for U-VI correlates with a Langmuir isotherm:
y = 16.91 x / ( l 0.161 x), where x denotes aqueous concentration and
y the organic concentration. Cascade design of mixer settlers showed
that high aqueous recycle (of the order of several hundreds) and large
number of stages (few thousands) will be needed for enrichment to
2-3% levels. The solvent inventory is high. Diluents other than benzene gave third phase formation o r a cloudy organic phase containing
precipitates at high loading.
References
[I] Uranium Extraction Technology', I A E A Technical Report Series N o 359, IAEA,
Vienna. 1993.
[2] Bertocci, U. and Ronladi, G. (1961). J. Inorg. Nucl. Chem., 23, 323-332.
[3] Keder, W. E. and Wilson, A. S. (1963). Nucl. Sci. Eng., 17, 287.
345
[28] Meghal, A. M., Singh, H. and Koppiker, K. S., 'lmprovements in Process Technology for Uranium Metal Production'; pp. 750-755, --ibid-.
[29] 'Uranium 1995:Resources, Production and Demand'. Report by NEA-OECD,
1995, p. 194, 1996.
[30] Murthy, T. K. S., Pai, V. N. and Nagle, R. A. (1971). IAEA Symp, on Recovery of
Uranium, Sao Paula, Brazil.
[31] Murthy, T. K. S. (1971). Report o f l A E A Research Contract No 834/RB.
[32] Singh, H. and Mukherjee, T. K. (1995).'Hydrometallurgical Processing of Phosphate Rock by Eco-friendly Technologies: Current Trends and Future Challenges', Proc. Int. Conf on Mineral Processing, pp. 785-790, IIT Kanpur, India.
[33] Bhattacharya, K. and Murthy, T. K. S. (1975). Analgtical Chirnica Acta, 76,
91-96.
[34] Singh, H., Nagle, R. A., Giriyalkar, A. B., Fonseca, M. F. and Koppiker, K. S.
(1989). 'On-site Tests for Recovery of Uranium from Wet Process Phosphoric
A c i d Sym. on Uranium Technology, pp. 621-627, BARC, Bombay.
[35] Nagle, R. A., Giriyalkar, A. B., Fonseca, M. F. and Koppiker, K. S., pp. 628-634,
--ibid-.
[36] Singh, H., Mukherjee, T. K. and Rao, A. P. (1992). Technology Development far
Uranium Recovery from Phosphoric Acid, Annual Conference 1.I.Ch.E.. Suratkal,
India.
[37] Harindran, K. N.. Krishnan, V. N. and Singh, H. (1993). Analytical Methods
Manual for Phosphoric Acid Purification Plant for Uranium Recovery, Investigation Report UREDIOOZ, BARC, Trombay, Mumbai, India.
[38] Singh, H. and Mukherjee, T. K. (1993). Application of Process Separation Technology in the Production of Eco-friendly Fertilizers; Paper EVE-023, Proc. Indian Chemical Engineering Congress, IIT-UDCT, Bombay, India.
[39] Singh, H. (1993). 'Technology for Uranium Separation from Phosphoric Acid';
Proceedings DAE Conference, BARC, Trombay, Bombay.
[40] Sreekala, R. and Singh, H. (1994). "Application of Infra-red Spectroscopy in Process Evaluation of a Hydrometallurgical Plant", Proc. Sym. Organic Reagents:
Synthesis and Use in Extractiue Metallurgy, BARC. Bombay.
[4I] Giriyalkar, A.B., Singh, R., Singh, H. and Mukherjee. T.K. (1995).
"Management of Radioactive Wastes from Uranium Recovery Plants", Symp. on
Management of Radioactiue and Toxic Wastes. BARC. Bombay.
[42] Paul, A. C., Pillai, P. M. B., Kamalan Nair, S. and Pillai, K. C. (1984). J. Enuiron.
Radioactivity, 1, 51-65.
[43] Hudson, M. J. (1982). Hydrometollurgy, 9, 149-168.
[443 Boualia, A., Mellah, A. and Silem, A. (1990). Hydrometallurgy, 24, 1-9.
[45] Silem, A., Boualia, A. and Mellah, A. (1990). Hydrometallurgy, 24, 11-17.
[46] Fativic I., Meles, S., Polla, E. and Romano, J., Proc. Symp. 'Extraction ' 8 7 : n l e
Recovery of High Value Materials'; June 1987, Dounreay, Scotland, Insm. of
Chem. Engineers. Symp. Ser. No. 103.
r471 Brcic. I.. Fatovic. I.. Meles.. S... Polla. E. and Radosevic.. M. (1987).
,
. Hvdrometal,
lurgy; 18, l17-l22.
[48] Sato, T. (1962). J. Inorg. Nucl. Chem., 24, 699-706.
r491 Shellev. P. and Ouan. C.. Proc. Int. Solv. Extrn. Confr. (ISEC90).
Sekine. T. and
~
~ u s a c a b e S.
, (E~s.),~lse"ier,pp. 381-386.
[SO] Stenstrom, S. and Aly. G . (1985). Hydrometallurgy, 14, 257-276.
[5I] Sutton, C. and Calder, J. A. (1975). J. Chem. Eng. Data, 20, 320-322.
[52] Polak, J. and Lu, B. C. (1973). Can. J. Chem. Engg., 51,4018-4023.
[53] Ministry of Env. and Forests Notification 50227 (F) of 24.3.92 in G a z e t t e of
India. Extra Part 11, Sec 3(ii). pp. 6-1 1.
[54] Schmheder (1989). Radiochim. Acta, 48, 181-192.
[55] Munakata, K, and Nabeshima, M. (1991). Nucl. Tech., 96, 84-95.
- L
<

Mailen, J. C. (1981). Sepn. Sci. & 'I2ch., 16(10), 1373-1383.
Bagawade, S. V.. Vasudava Rao, P. R., Ramakrishna, V.V. and Patil, S. K.
(1978). J . Inorg. Nucl. Chem., 40, 1913-1918.
Ranlanujam, A,, Ramakrishna, V. and Patil, S. K. (1978). J. Inorg. Nucl. Chem.,
40, 1167-1171.
Marcus, Y. and Kolarik, Z. (1976). J . Inorg. Nucl. Chem., 38, 1069-1073.
Enokida, Y. and Suzuki, A. (1992). J . Nucl. Sci. Tech., 29(5), 461-471.
Gordon, J. P., Leite, R. C., Moore, R. S., Porte, S. P. and Whinenerry, J. R.
(1965). Appl. Phy., 36, 3-8.
Enokida.. Y... Kakudo. T. and Suzuki., A. 11992).
J . Nucl. Sci. Technol... 2913b
~,
~ ,
255-262.
Spasic, A. M., Djokvic, N. N., Babic, M. D., Marinko, M. M. and
Jovanovic, G . N. (1997). Clreniical Engng. Sci., 52(5), 657-676.
Spasic, A. M. (1992). Cltemical Engitg. Sci.. 47 (15/16), 3949-3957.
Padilla, R., Ruiz, M. C. and Trujillo, W. (1996). Hydroiitctallurgy, 42, 267-279.
Bailes, P. J. (1992). Hj~dromerallury!. 30, 417-430.
Bailes, P. J., Proc. Int. Solu. Extrtt. Conjr. (ISECYO), Sekine, T. and Kusakabe, S.
(Eds.), Elsevier, pp. 1313-1325.
Bailes, P. J. and Larkai, S. K. L. (1990). Proc. Inr. Solu. Exrrn. Conjr. (ISECYO),
Sekine, T. and Kusakabe, S. (Ed.), Elsevier, pp. 1411-1416.
Singh, H. (1996). 'Process Engineering Research or Uranium Recovery from
Domiasiat Ore', Divisional Reporr. BARC, Trombay, Mumbai, India.
Spasic, M. A. and Jokanovic, V. (1995). J. Colloid Inrerface Sci., 170, 229-240.
Rommcl, W. and Blass, E. (1992). Proc. Int. Solvent Exrern. Conjr. (ISECgO),
Sekine, T . and Kusakabe. S. (Eds.). Elsevier, pp. 1423-1428.
Golob, J. and Modie, R. (1977). Trans ltlsr Chem. Eng., 55, 207-21 1.
Eckert, N. L. and Gomerly, L. S. (1989). Chem. Eng. Res. Des., 67, 175-184.
Jeelani, S. A. K. and Hartland, S. (1985). A.I.CIt.E.J., 31(5), 71 1-720.
Warren, K. W., Prestridge, F. L. and Sinclair, B. A. (1978). M i n . Eng., 30,
355-357.
Fairclough, A. R. N. and Davis, G. A,, Proc. Syntp. 'Extraction '87:7he Recovery
oftfigk Value Marerials'; pp. 331-350, June, 1987. Dounreay, Scotland, Insrn. of
Chon. Engineers. Sgmp. Ser. N o . 103.
Xing, D. and Yajun, S. (1992). Proc. Inr. Soluent Extrn. Conjr. (ISECYO),
Sekine, T . and Kusakabe, S. (Eds.), Elsevier, pp. 877-882.
Moyer, 8. A. and McDowell, W. J. (1981). Sepn. Sci. and Tech., 16(9), 1261-1289.
Barnea, E. (1979). Ilydromemllurgy, 5, 15.
Ryan, A. D. and Lowrie, R. S., 'Experimental Basis for the Design of Mixer Settlers for the Amex Solvent Extraction Process', Report O R N L - 3 3 8 1 , Oak Ridge
National Laboratory, April 19, 1963.
Ritcey. G . M. (1980). Hydrometallurgy, 5, 97-107.
Ritcey, G . M. and Wong, E. W. (1985). Hydrometallurgy, 15, 55-61.
Fletcher, A. W. and Gage, R. C. (1985). Hydrometallurgy, 15, 5-9.
Stenstram, S. and Aly, G . (1985). Hydrometallurgy, 14, 257-276.
B a h t , B. H. and Beyad, M. H. (1995). H~~drometall~rrgy.
37, 11 1-1 16.
Lounis, A. and Gavach, C. (1997). Hydromerallurgy, 44, 83-96.
Cam~bell,M. C., Ritcev. G. M. and Gow, W. A, (1985). C I M Bull, 78, 139-144.
~llis;~
A.,. ~ o n gR.
, s and Byrne, J. B. (1958).
2nd Int. coif: on the PeaceJill Uses ojAromic Energy, UN, Geneva, 3, 499-501.
[89] Joe, E. G., Ritcey, G . M. and Ashbrook, A. W. (1966). J . ofMetals, 1, 18-21.
[90] Ritcey, G . M., Joe, E. G. and Ashbrook, E. W. (1967). Trans. Soc. M i n . Eng., 238,
330-334.
[91] Golding, J. A. and Koren, D. W. (1993). Hydromerallurgy, 33, 227-244.
roc.
347
Burger, J. C. and Jardine, J. M. (1958). 2nd I n t . Conf on Peaceful Uses of Atomic

3, 3.
~ n e r U.N.,
~ ~ Geneva,
,
Ashbrook, A. W. (1961). Anal. Chim. Acta, 24,504-508.
Ritcey, G. M., Slater, J. M. and Lucas, B. H. (1973). Proc. I n t . Symp. on Hydrometallurgy, Chicago, 4, 429-474.
Xiao-Xang Chen and Su, Y. F. (1992). Proc. I n t . Solu. Extrn. Confr. (ISEC90),
..
Sekine. T. and Kusakabe. S. (Eds.b Elsevier. Dn. 1351-1356.

[96] Ritcey,' G. M. (1985). ~ ~ d r o n ; e t a l l & ~15,
, 1-4.
[97] Swaminathan. N., Rao, S. M., Sridharan, A. K., Sampath, M., Suryanarayan, V. and
Kansal, V. K. (1987). Proc. 'Advances in Uranium Refining and Conversion', I A E A
Technical Committee Meetinu. Vienna 7-10 April 1986. IAEA-TECDOC-420.
Tunley, T. H. and Nel, V. W. (1974). Proc. jnt. ~ o l u i n rExrr. ConJ (ISEC74),
Society of Chemical Industry. London, 2, 1519.
Cavendish, J. H. (1987). In: Science and Technology of Tributyl Phosphate, Eds.:
Schultz, W . W., Burger, L. L. and Navratil, 1. D., CRC Process, Inc., 11. Part A,
pp. 1-38.
Garg, R. K., 'Status of Thorium Technology in India'. Proc. ' l n t . Conj. on Nucl.
Power and I t s Fuel Cycle', Salzburg, 2-13 May, 1977, 2, 457.
Karve, V. M. (1990). "A note on the New Thorium Plant in Orissa", In: Proc.
'7horium Fuel Cycle Actiuiries in India: A Decade of Progress 1981-1990',
Basu, T . K. and Srinivasan, M. (Eds.), BARC, Trombay, India.
Sato, T., (1965). J. Appl. Chem., IS, 489-495.
Preston. J. S., du Preez, A. C. and Jacobs, J. (1988). Proc. Int. Solu. Extr. ConJ
( I S E C 88), Nauka, Moscow, 3, 137.
Sun-Yongxia and Zhou-Zuming (1996). Chinese Journal of Nuclear Science and
Engineering. l q l ) , 62-67.
Srinivasan, T. G., Suresh, A.. Prasanna, R., Rao, P. R. and Jayanthi, N. (1996).
Solv. Extr. and I o n Exch., 14(3), 443-458.
Rozen A. M. (1992). Proc. I n t . Solvent Extr. Confr. ( I S E C 90), Sekine, T. and
Kusakabe, S. (Eds.), Elsevier, pp. 99-104.
Preston, J. S. and du Perez, A. C. (1995). Solu. Extr. and Ion Exch., 13(3),
391-413.
Codamines, N. and Musikas, C. (1992). Solv. Extr. and I o n Exch., 10(1),
69- 100.
[I091 Sidall. T. H. (1960). J. Phys. Chem., 64, 1863.
[I101 Gaspirini, G. M. and Grossi, G. (1986). Solu. Exrr. and I o n Exch., 4(6),
1233-1271.
[ I 1I] Suresh, A,, Subramaniam, S., Srinivasan, T. G. and Vasudeva Rao, P. R. (1995).
Solu. Extr. I o n Exch., 13(3), 415-430.
[I121 Siddall, T. H. (1960). J . lnorg. Nucl. Chem., 13, 151-155.
[I 131 Suresh, A,, Srinivasan, T. G. and Vasudeva Rao, P. R. (1994). Solu. Extr. and I o n
Exch., 12(4), 727-744.
[I141 Baes, C. F., Zingaro, R. A. and Coleman, C. F. (1958). J. Phys. Chem., 62(2),
~~
~~~
1296~
.
- - .1 7-.
[I151 Peppard, D. F., Mason, G. W. and McCarty, S. (1960). J. Inorg. Nucl. Chem., 13,
138- 150.
[I161 Mason, G. W., Lewey, S. and Peppard, D. F. (1964). J. Inorg. Nucl. Chem., 26,
227 1-2284.
[I171 Peppard, D. F., Ferraro, J. R. and Peppard, D. F. (1959). J. Inorg. Nucl. Chem.,
12,60-60.
[I181 Mason, G. W., Lewey, S. and Peppard, D. F. (1978). J. Inorg. Nucl. Chem., 40,
1427-1430.
[I191 Gruber, V. and Horacek, J., Czech. CS 274, 783 (CI.CO7 F9/11/1, 12 Nov. 1991,
Appl. 8913, 355,05 June 1989; 3 PP, Chemical Abstracts, 120, 54692s.
348
[I201 Mason, G. W., Bilobran, I. and Peppard, D. F. (1978). J. Inorg. Nucl. Chem., 40,
1807-1810.
[I211 Mason, G. W., Griffin, H. E. and Lewey, S. (1981). J. Inorg. Nucl. Cheni., 43,
191-195.
[I221 Mohanty, S. R. and Reddy, A. S. (1975). J. Inorg. Nucl. Chem., 37, 1977-1982.
[I231 Cao, Z., Bao, Y., Shen, C., Bao, B., Wang, B. and Jun Quian (1993). Hejishee,
16(6). 380-4, Chemical Abstracts: 119, 236166k.
[I241 Cailly, F. and Mottot, Y. Fr., Demande FR 2, 678, 644 (cl. L22B3/38), 05 Jan.
1993. Appl. 9118, 215,02 Jul. 1991; 17 PP. Chem Abs. 120:8225 11.
[I251 Curtui, M.. Haiduc, I. and lovanca Haiduc (1992). J. Radioanal. Nucl. Chem.
Lett., 165(2), 95-105.
[I261 Singh. S.. Panda, C. R., Chakravortty, V. and Dash, K. C. (1988). J. Radioanal.
Nucl. Chem. Art., 120(1), 65-73.
[I271 Singh, S., Chakravortty, V. and Dash, K. C. (1988). J. Radioanal. Nucl. Chem.
Art., 122(1), 137-142.
TI281- Sinah. S.. Chakravorttv.
.. V. and Dash. K. C. 11988).
.
. J. Radional. Nucl. Chem.
~ e c'127(5),
,
349-356.
[I291 Mohanty, R. N., Singh. S., Chakravortty, V. and Dash, K. C. (1989). J. Radional.
Nucl. Chcm.. 132. 359.
r1301
- - Sinnh, S., dhakkvortty, V. and Dash, K. C. (1988). J. Radional. Nucl. Chem.
LC;., 127(5), 349-356. .
[I311 Lin, C. M. Wai and Smart,-N. G. Preston (1995). Enuironmental Science and
Technoloav. 29rl0). 2706-2708.
[I321 vermeu~kn;L. ~.'(1966).J . ofMetals, 1, 22-25.
[I331 Mishra, S. and Chakravortty, V. (1997). Hydromctallurgy, 44, 371-376.
[I341 Behera, P., Mishra, R. and Chakravortty, V. (1993). J. Radional. Nucl. Chem.
Art., 173(1), 161-169.
[I351 Rout, K.C., Mishra, P. K., Chakravortty, V. and Dash, K.C. (1994). J.
Radioanal. and Nucl. Chem.. Art., 181(1), 3-10.
[I361 Bhandiwad, V. R., Swarup, R. and Patil, S. K. (1979). J. Radional. Chem., 52(1),
5-14.
[I371 Shabana, R. and Ruf, H. (1977). Radiochim. Acta, 24, 15-18.
[I381 Moore, F. L. (1964). Anal. Chem., 36(1 I), 2158-2162.
TI391 Mishra, S., Chakravortty, V. and Vasudeva Rao, P. R. (1995). J. Radional. and
[I421 Mishra, S. and Chakravortty, V. (1996). Indian. J. Chemical Technology, 3,

373-374.
[I431 Elias, A., Rodehuser, L., Auonz, A. and Attou, M. (1996). Hydrometallurgy, 40,
189-194.
[I441 Baes, C. F. (1962). J. Inorg. Nucl. Chem., 24, 707-720.
[I451 Singh, D. K., Mishra, S. L. and Mukherjee. T. K., Proc. Nuclear & Radio-chemistry Symposium. Calcutta, India, Jan. 1997.
[I461 Singh, D. K.. lyer, N. S., Mishra, S. L., Singh, H.and Bellary, M. P. (1997). Proc
' X I 1 ISAS Symp. on Analytical Techniquesfor Safety & Sujiciency of Natural
Resources/Products'; Kottayam, India, Feb. 20-22.
[I471 Singh, D. K., lyer, N. S., Mishra, S. L. and Singh, H. --ibid-; pp. 39-42.
[I481 Inada, K. and Takeda, K. (1980). Nucl. Tech., 50, 178-180.
[I491 Lerat, J. M. and Lorrain, C. (1985). "Uranium Enrichment by Solvent Extraction". In: 'Soluent Extraction and Ion Exchange in the Nuclear Fuel Cycle', Chap.
4. Logsdail, D. H. and Mills, A. L. Eds.
[I501 Takeda, K. and Saito, S. (1988). Nucl. Tech., 81, 421-428.
[151] White, D. A. and Fathurrachman, (1995). Nucl. Tech., 110, 220-227.

[I521 Frejacques, C., Gelee, M., Massignon, D. and Pluriun, P.: Proc. ' l n t . Con$ on
Nucl. Power and I t s Fuel Cycle', Salzburg, 2-13, May, 1997, pp. 203-213.
11531 Florence, T. M., Bartley, G. E., Ekstrom, A,, Fardy, J. J. and Farrar, Y. J. (1975).
J. Inorg. Nucl. Chem.,37, 1961-1966.
[I541 Jean-Hubert Coates (1982). In: 'Recent Developments in Uranium Enrichment',
Merriman, J. R. and Manson Benedict (Eds.), A.1.Ch.E. Symp. Ser., 221, 78,
3 1-40.
[I551 Chesne, A. and Germain, M. (1992). Proc. Inr. Soh. Extrn. Confr. (ISECPO),
Sekine, T . and Kusakabe, S. (Ed.), Elsevier, pp. 539-548.
11561 White, D. A. and Fathurrachman (1994). Hydrometallurgy, 36, 161-168.

Solvent Extraction in Production and Processing of Uranium and Thorium

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Mineral Processing and Extractive Metallurgy Review

Solvent Extraction in Production and Processing of Uranium and Thorium

Thorium',Mineral Processing and Extractive Metallurgy Review,21:1,307 349

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Min. Pro. Ex,. Ma. Rev.. Vol.21. pp.307-349

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Solvent Extraction in Production

Keyu'ords: Uranium; thorium; solvent extraction; nuclear fuel; processes; chemistry;

H. SlNGH AND C. K. GUPTA

have led to maturing of solvent extraction technology which finds

URANIUM EXTRACTION AND REFINING PROCESSES

URANIUM AND THORIUM SOLVENT EXTRACTION

Amine Extraction from Ore Leach ~olutions

The reactions involving uranyl sulphate extraction are:

UO, SO4 = uo;+ + so:-

H . SlNGH AND C. K.GUPTA

and free amine concentrations x 1, while a t lower values x is lower

URANIUM AND THORIUM SOLVENT EXTRACTION

H. SINGH AND C. K. GUPTA

1 : AQUEOUS FEED TANK

FIGURE 1 Schematic flowsheet for uranium extraction.

URANIUM AND THORIUM SOLVENT EXTRACTION

TABLE 11 Mixer-settler for solvent extraction

500 x 500 x 410 (mm)

TABLE 111 Strong acid stripping ofamine extract of uranium

TABLE IV Entrainment levels in pilot plant (ppm)

PPS = Parallel Plate Separator. Levels given in ppm.

H . SlNGH AND C. K. GUPTA

Recent developments, which are a matter of intense study, include

+ 211T O P = UO, (NO,),

Operating flux of 100 miro-gram U/mz.sec was observed. Studies

URANIUM AND THORIUM SOLVENT EXTRACTION

P r o c e s s Improvements in t h e TBP Refining P r o c e s s

(CO3),I4- = (NH,), UO, (CO,), (solid)

AUC is a crystalline product and has excellent physical properties for

ratio of 3:l. Raffinate analysed <0.5 g/l uranium. Stripping of the

URANIUM AND THORIUM SOLVENT EXTRACTION

various aspects of uranium recovery from phosphoric acid [30-411.

H. SlNGH AND C. K . GUPTA

the specific characteristics of the acid, attributed to the rock source

Selection of a diluent for solvent extraction is important in the process

THORIUM SOLVENT EXTRACTION

H. SlNGH AND C. K. GUPTA

results were obtained with a solvent having 16% aromatics, density of

URANIUM AND THORIUM SOLVENT EXTRACTlON

The specifications of N H P have been modified for economical use

HEAT EFFECTS IN SOLVENT EXTRACTION

TABLE V Characteristics of the Indian heavy normal paraffin for extraction

SPECIFIC GRAVITY (15/4"C)

conditions are available [54-581. The enthalpy change for uranium

H.SlNGH AND C. K.GUPTA

URANIUM AND THORIUM SOLVENT EXTRACTION

PROCESS INSTRUMENTATION AND CONTROL

H. SlNGH AND C. K. GUPTA

URANIUM AND THORIUM SOLVENT EXTRACTION

H. SlNGH AND C. K. GUPTA

Laser size analysis ofentrained solvent drops.

FIGURE 4 Coalescence of secondary droplets in a Parallel Plate Separator.

as it is the source of the formation of entrained droplets. It has been

URANIUM AND THORIUM SOLVENT EXTRACTION