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INTRODUCTION
Several uranium occurrences have been discovered in various localities in the Egyptian terrains.
These include mainly the different uranium mineralization associated with younger granites of the
basement rocks in the Eastern Desert or else those associated with the sedimentary Carboniferous
rocks of the Um Bugma Formation in West Central Sinai. Among uranium mineralization of the
former type, that occur in Gabal Gattar younger granite pluton at about 40 km NW Hurghada City is
greatly promising due to its relatively wide distribution in a number of occurrences. In the north
eastern part of Gable Gattar, the younger granites host several small uranium occurrences that have
been discovered along various factors, fault planes and joints that distributed in strongly sheared zones
(1)
. The uranium mineralization is essentially manifested in the form of secondary uranium minerals
with uranophane as the most abundant (2).
Solvent extraction (3-7), ion exchange resin(8) liquid membrane(9) and direct precipitation(10)
methods are commonly employed in the nuclear industry as techniques for the recovery of uranium
from leach solutions. To carry out this operation, special equipment was used such as mixer settlers
and ion-exchange columns. The used leach solutions must be prepared and clarified since fine solids
may produce stable emulsions or columns blocking which prevents phase separation and the presence
of severe operational problems. However the clarifications (or filtration) operations required are
expensive. According to Campbell et al.(11) the capital and operating costs for clarification processes
are estimated to be 30% and 10-20% respectively of the nuclear industry. Consequently, if these
operations can be eliminated by using slurries, significant investments should be achieved. This
method of processing has been termed solvent-in-pulp(12) (SIP). If dilute slurries were used in SIP
processing, the filtration operation would be removed.
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
An extensive economic study was carried out by Ritcey et al.(13). The authors compared
processing characteristics and economics of resin-in-pulp and solvent-in-pulp operations as applied to
uranium extraction, and runs were carried out with continuous aqueous and organic phases. Although
the process was easier to operate with the continuous organic phase, operation with the continuous
aqueous phase resulted in much lower solvent losses and was consequently recommended as the
favored mode of operation. Solvent losses were found to be the serious factor influencing the
economics of the process. Some further investigations have been carried out to determine the factors
influencing solvent losses. Ellis et al.(14) found that losses could be substantially reduced by the
addition of hydrophilic surfactants. By avoiding high losses of solvent to the particles, and removal of
possibilities for crud formation, extraction and recovery of uranium directly from the leach slurry is
thus proved feasible (14). Once uranium is in the solvent, the second operation step starts by stripping
uranium from the loaded solvent. Several reagents were tested in this regard such as H2SO4, Na2CO3,
HCl, HNO3 and H2O.
The main objective of this study is uranium recovery from Gattar granite GII by SIP
technique. To achieve this purpose the effect of various factors affecting uranium extraction by the SIP
technique from GII leaching slurry such as, solvent concentration, slurry dilution, shaking time,
solid/liquid phase ratio, diluent type and solvent consumption (surfactant type and surfactant/ slurry
ratio) were studied. The second part of the study focused on the uranium stripping from the working
solvent. In this regard, several factors were studied such as stripping agent type, stripping agent
concentration, shaking time and organic/ aqueous phase ratio
EXPERIMENTAL
2.1. Materials
The chemical reagents that have been used in this study were of high purity Tributylamine
(TBA) ≥ 98% (Riedel-deHaen), kerosene (Misr. Co.), uranylacetate (UO2(CH3COO)2.2H2O, (BDH
Chemicals Ltd. Poole, England) and Molasses (Misr. Co.), and Sulfuric acid (BDH) 98%.
The representative sample was collected from Gabal Gattar, with the chemical composition of
1310 mg/l U, 2.11% SO42-, 1.61% PO43-, 71.51% SiO2, 0.42% CaO, 7.01% Fe2O3 and 0.06 % TiO2.
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
80 Solvent loss, % 80
Solvent loss, %
U. ext. eff., %
60 60
%
40 40
20 20
0 0
0 5 10 15 20 25
Solvent (TBA) conc., %
Fig. (1): Effect of solvent concentration on uranium extraction efficiency from Gattar Granite GII
sample (dilution factor of 230 g solid/l, shaking time of 15 min., solvent/liquid phase ratio
of 1/1 and slurry pH of 1.1)
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
respectively (Fig. 2), and the solvent loss increased from 5 up to 17 % of solvent by increasing the
solid content. The decrease of uranium extraction efficiency with the increase of the solid content
could be attributed to the increase of solid particles which inhibit the free motion of the solvent
molecules in the matrix. On the other hand, the increase in solvent loss could be attributed to
absorbing the solvent molecules on the surface of the thick gangue of mineral particles.
100 100
Uranium extraction efficieny, %
80 U.extraction % 80
Solvent loss, %
Solvent loss, %
60 60
40 40
20 20
0 0
80 100 120 140 160 180 200 220 240
Solid conc., g/l
Fig. (2): Effect of solids concentration upon uranium extraction efficiency from Gattar
Granite GII sample (Solvent conc. of 20% in benzene, shaking time of 15 min.,
solvent/liquid phase ratio of 1/1 and slurry pH of 1.1)
3.1.3. Effect of Shaking Time
To study the effect of shaking time upon uranium extraction efficiency from Gattar GII granite
sample, series of extraction experiments were performed by contacting fixed slurry portions (20 ml) of
uranium conc. of 1280 mg/l with the solvent using time intervals ranging from 1 up to 120 min. Other
conditions were fixed namely, solids conc. of 102 g/l, phase ratio of 1/1 and solvent concentration of
20%. The obtained results could indicate that uranium extraction efficiency increases with increasing
shaking time (Fig.3) while solvent loss was nearly unaffected. Accordingly, it was decided to choose
60 minute as the optimum shaking time.
100 100
Uranium extrction efficiency, %
Solvent loss, %
80 U. ext. eff., % 80
Solvent loss, %
60 60
40 40
20 20
0 0
0 20 40 60 80 100 120 140
Skaking time, min.
Fig. (3): Effect of shaking time upon uranium extraction efficiency from Granite GII
sample (Solvent conc. of 20% in benzene, solids conc. of 102 g/l,
solvent/liquid phase ratio of 1/1 and slurry pH of 1.1)
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
100
Uranium extraction efficiency and
80 U.extraction %
Solvent loss, %
solvent loss, %
60
40
20
0
Molase Glue Crud sugar Vegitable oil
Surfactant type
Fig. (4): Effect of surfactant type on uranium extraction efficiency and solvent loss
(Solvent conc. of 20% in benzene, solids conc. of 102 g/l., shaking time of
60 min., solvent/liquid phase ratio of 1/1 and slurry pH of 1.1)
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
100 100
Uranium extraction efficiency, %
U.extraction %
80 Loss of solvent % 80
Solvent loss, %
60 60
40 40
20 20
0 0
0 50 100 150 200 250
Surfactant amount, g/l
Fig (5): Effect of surfactant amount upon uranium extraction efficiency and solvent loss
(Solvent conc. of 20% in benzene, solids conc. of 102 g/l., shaking time of 60 min.,
surfactant type of glue and slurry pH of 1.1)
80 80
Solvent loss, %
60 U. extraction 60
%
Solvent loss
40 40
20 20
0 0
0 1 2 3 4 5 6
Slurry/Organic phase ratio
Fig. (6): Effect of aqueous/organic phase ratio upon uranium extraction efficiency and
solvent loss (Solvent conc. of 20% in benzene, solids conc. of 102 g/l., shaking
time of 60 min., surfactant type of glue, surfactant amount of 100g/l and slurry
pH of 1.1)
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
100
Uranium extraction efficiency, %
80 U.extraction
Solvent loss
60
40
20
0
Benzene Toluene Cyclohexane Kerosene
Dilluent type
Fig. (7): Effect of diluent type on uranium extraction efficiency from Gattar granite GII
composite sample (Solvent conc. of 20% in benzene, solids conc. of 102 g/l.,
shaking time of 60 min., solvent/liquid phase ratio of 4/1, surfactant type of glue,
surfactant amount of 100g/l and slurry pH of 1.1)
3.1.7. Choice of the Preferred Conditions of Uranium Extraction from Gattar Granite GII
Sample
From the previous study of relevant factors of uranium extraction, it would be possible to attain
comparable extraction efficiencies by different combinations of the studied relevant factors. Careful
selection of the conditions would depend primarily on economic considerations. In the light of the
studied relevant factors, it would seem economically to select the following extraction conditions,
solvent concentration of 20%, extraction time of 60 min, solid content of 102 g/l, glue as surfactant of
100 g/l, slurry/organic phase ratio of 4/1 and using kerosene as the diluent substance.
When considering amine extraction systems, the amine salt should be regarded as the extracting
agent, rather than the free amine itself. The amine is firstly converted to the appropriate amine salt:
RH2N + HX = RH2N+H.X- (1)
The amine is forms with an acid (HX) – in the organic phase – amine salt (or polar ion-pair),
RH2N+H.X--. On contacting this solvent with an aqueous solution of an ionic metal species (MY-), the
exchange occurs according to the following equation(18-20);
RH2N+H.X- + MY- = RH2N+H.MY- + X- (2)
Thus the amine salt, and not the free amine, should be considered as being the extracting agent.
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
In the acid sulfate systems, the importance of pH becomes more pronounced than in the nitrate
or chloride systems due to the dibasic character of sulfuric acid, a character which gives it the ability
of forming sulfate-bisulfate equilibrium, i.e.,
H2SO4 = H+ + HSO4- (3)
- +
HSO4 = H + SO42- (4)
The aqueous speciation distribution of uranium was calculated in the sulfate leach slurry and
represented in Fig. 8. The results showed that the complexes of UO2SO4, UO2(SO4)2- were the
predominant species in the pH range 0 – 6. At near neutral and alkaline pH conditions, U-hydroxide
complexes start to dominate the aqueous phase. At pH 7, the UO2(OH)2.H2O(C) became the main
species. At pH 12, UO2(OH)3- became the predominant species. The formation of UO2(OH)42- species
started to grow after pH 10.
At the working leach slurry pH (1.1), the expected uranium species are UO2(SO4)2- and
UO2SO4. Accordingly the predictable extraction mechanisms of uranium by use Tri-butyl amine
(TBA) were anionic or neutral as follows: (18-20);
(R4NH)2SO4 + UO2(SO4)22- = (R4NH)2UO2 (SO4)2 +SO42- (5)
or
(R3NH)2SO4 + UO2SO4 = (R3NH)2UO2(SO4)2 (6)
4. Uranium Stripping
Uranium stripping from the working solvent (TBA) which was obtained by applying the above
mentioned conditions and an assay of 0.978 gU/l. The effects of the following factors, namely,
stripping agent, concentration of the stripping agent, shaking time and organic/aqueous phase ratios
were investigated.
4.1. Effect of Stripping Agent
The following stripping agents, namely; H2SO4, Na2CO3, HCl, HNO3 and H2O were studied.
The latter mentioned stripping agents (1 M each) was shacked with the working solvent with
aqueous/organic phase ratio of 2/1 for 30 min. shaking time. From the obtained results plotted in Fig.
(9) it was found that, sulfuric acid could be choiced as a suitable stripping agent.
772
M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
50
Uranium stripping efficiency, %
40
30
20
10
0
H2SO4
H2SO4 Na2CO3
Na2CO4 HCl
HCl HNO3
HNO3 H2O
H2O
Stripping agent type
Fig. (9): Effect of some stripping agents upon uranium stripping efficiency from the working
solvent (stripping agents conc., 1 M, aqueous/organic phase ratio of 2/1 and 30 min.
shaking time)
90
80
70
60
50
40
0 1 2 3 4 5 6 7 8 9 10
H2SO4, M
Fig. (9): Effect of sulfuric acid concentration upon uranium stripping from the working solvent
(stripping agents type H2SO4, aqueous/organic phase ratio of 2/1 for 30 min. shaking time)
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
100
90
85
80
75
0 5 10 15 20 25 30 35 40 45 50 55 60
Shaking time, min.
Fig (10): Effect of shaking time upon uranium stripping from the loaded solvent (stripping
agents type H2SO4, stripping agents conc. 9M aqueous/organic phase ratio of 2/1)
4.4. Effect of O/A Phase Ratio upon Uranium Stripping Efficiency, and Construction of McCabe
Thiele Stripping Diagram
In order to study the effect of the phase ratio on uranium stripping efficiency from the uranium-
loaded TBA a sample was prepared by SIP extraction of uranium from Gattar granite GII diluted
leaching slurry and a series of stripping experiments were performed using O/A ratios ranging from
4/1 down to 1/4. In these experiments, the other stripping conditions were fixed at 9 M sulfuric acid
for 30 min shaking time. The obtained data (Table 1) were used to construct the equilibrium isotherm
in the McCabe Thiele diagram (21, 22), (Fig.11). The latter was used to calculate the theoretical stages
required for almost complete uranium stripping from the uranium-loaded solvent sample of Gattar
granite GII diluted leaching slurry. From the constructed diagram, it is obvious that an almost three
theoretical stages are required for the removal of almost all uranium from the working solvent sample
obtained from sample of Gattar granite GII diluted leaching slurry at the operating line slope of 1.
Table (1): Effect of O/A phase ratio upon uranium stripping efficiencyfrom the
uranium loaded solvent of Gattar granite GII diluted slurry sample
U Conc., mg/l
O/A
Sao Stripping eff.., %
Ratio
Org. Aq.
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M. M. Ali, et al. Arab J. Nucl. Sci. Appl, Vol 50, 3, 217-228 (2017)
900
800
700 1
Uranium concentration in
600
aqueous phase, ppm
500
2
400 1
300
200
3
100
0
0 100 200 300 400 500 600 700 800 900 1000
Uranium concentration in organic phase, ppm
Fig. (11): McCabe-Thiele Diagram of uranium stripping from the working (TBA) solvent
CONCLUSION
Considering the preferred conditions for extraction of uranium from Gattar granite GII leaching
slurry by applying solvent-in-pulp (SIP) deduced from the present work, about 91% of uranium could
be extracted using a solvent (TBA) concentration of 20% in kerosene, extraction time of 60 min., solid
content of 102 g/l, using glue as non-ionic hydrophilic surfactant with concentration of 100 g/l and
slurry/organic phase ratio of 4/1. About 96% of the loaded uranium on the working solvent could be
stripped using 9 M sulfuric acid as an effective striping agent at an aqueous/organic phase ratio of 4/1
for 30 min. contact time. Based on the stripping results the McCabe Thiele, uranium stripping diagram
was drawn and most of the loaded uranium could be stripped after three stripping theoretical stages.
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