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Effect of oxidation-reduction on the extraction of uranium from wet

phosphoric acid by DEHPA/TOPO

Article in Journal of Radioanalytical and Nuclear Chemistry · November 1995

DOI: 10.1007/BF02038261

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Jointly published by Journal of Radioanatytical and Nuclear Chemistry, Articles,
Elsevier Science S. A., Lausanne and Vol. 198, No. 1 (1995) 237-245
Akad#miai Kiadr, Budapest

E F F E C T O F O X I D A T I O N - R E D U C T I O N ON T H E E X T R A C T I O N
OF U R A N I U M F R O M W E T P H O S P H O R I C ACID BY DEHPA/TOPO

Y. KOUDSI,* S. KHORFAN, H. SHLWEIT, A. DAHDOUH, M. SWEID

Atomic Energy Commission, P.O. Box 1169, Damascus (Syria)

(Received June 16, 1995)

Uranium is recovered from wet phosphoric acid by DEHPA/TOPO in kerosene. Uranium is present
in wet phosphoric acid in the tetravalent and hexavalent states but DEHPA/TOPO extracts uranium in
the hexavalent state only. The ratio of U4+/U6+ depends on several factors such as the origin of the
phosphate rock, the method of preparation of phosphoric acid and the ~resence of other impurities.
Therefore it is important to oxidize the wet acid to convert all uranium to U~+ before extraction. Uranium
is stripped from the solvent by a reverse process where a concentrated phosphoric acid is used under
reducing conditions. This paper studies the oxidation of wet phosphoric acid from Homs plant/Syria by
H202 oxidant and the effect of oxidation on extraction Coefficient K. It also studies the reduction by
iron and its effect on back extraction of uranium from the solvent to phosphoric acid.

Several authors studied the effect of oxidation-reduction on the extraction of

uranium from phosphoric acid by DEHPA/TOPO.
SPILLIARD 1 mentioned that the solvent DEHPA/TOPO extracts uranium in the
hexavalent state U 6+ and not in the tetravalent state U4§ So it is necessary to oxidize the
acid before extraction.
KOULEHERIS 2 stated that the oxidant used should have no corrosion or pollution
effect on phosphoric acid. The use of NaCIO 4 is satisfactory for extraction but the
precipitation of Na2SiF6 causes troubles. In the same way the use of CI2 or nitric acid
as oxidants causes severe corrosion or pollution problems during the concentration
process of the acid. As for reduction by iron the method of reduction and the quantity
of iron should not lead to a big increase in the concentration of iron in the acid. Iron is
present in wet phosphoric acid in concentrations in the range 2-2.5 g/l. Any additional
iron should not exceed 8-20 g/l. Iron is used during stripping operation of uranium.
The reduction 3 is carried out by reaction of iron and acid at low temperatures.
Hydrogen is liberated at high temperatures instead of reduction of iron. The reduction
is carried out by contacting the acid with iron in the form of scraps or rings in a rotating

*Author for correspondence: Department of Chemistry, AE.C.S, P.O. Box 6091, Damascus, Syria.

0230-5731/95/US $ 9.50
Copyright 9 1995 Akad~miai Kiadr, Budapest
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Y. KOUDSI et al.: EFFECTOF OXIDATION-REDUCTIONON THE EXTRACTION

drum. The time of contact is 3 minutes and the ratio of Fe3§ 2+ gives the percent of
reduction.
LONG4 stated that reduction depends on temperature and quantity of iron present
originally in the acid and on the quantity and quality of iron added. Several experiments
were done using iron turnings which contained 90-98% iron. Theoretically it is possible
to reduce ,all Fe3+ according to:
2Fe 3+ + Fe0--~3Fe2+

But there is a side reaction taking place:

Fe ~ + 2H~+--~Fe2+ + H2]"

This reaction has a negative effect on the reduction. So it should be avoided to reduce
loss of iron and generation of hydrogen gas. Reduction of temperature is one of the
important factors in reducing the release of hydrogen.
It was stated5 that the increase in oxidation potential increases extraction but the
increase of FeSO 4 and F- decreases the extraction of uranium. The increase in
oxidation leads to reduction in the use of iron in stripping and reduction in
contamination of yellow cake with iron.
Consumption of iron is 2 moles Fe 2§ to every mole uranium stripped according to
the reaction:
U 6+ "t- 2Fe2+---~U4§ + 2Fe 3+

It is possible to take 4 moles of Fe z+ for 1 mole of 02 according to:

4Fe 2+ + 02 + 4H+~4Fe 3+ + 2H20

DELEON6 studied the reduction of phosphoric acid which has a potential of

440-460 mV. This means that uranium is mainly in the hexavalent state. The reduction
to tetravalent state can be achieved by optimising the following parameters:
concentration of reducing reagents, time of reduction, temperature of reduction.
Iron powder was used for reduction at temperature of 60 ~ and 20 minutes. A
convenient reduction potential of the order of 160 mV was obtained using 8 g/1 of iron
in acid solution. Time of reduction was varied from 10--160 minutes but the most
convenient time was of the order of 20 minutes. The temperature was varied from
20-75 ~ but room temperature was convenient to reduce EMF to 160 mV.
SURBER 7 stated that the green acid resulting from purification is oxidized by adding
50% H202. The oxidation degree can be controlled by measuring the EMF. This is
proved by the presence of all U in the U6+ state and all the Fe in the Fe 3§ state. The

238
 Y. KOUDSI et al.: EFFECT OF OXIDATION-REDUCTION ON THE EXTRACTION

shipping acid is prepared by adjusting the concentration of the acid to 30-32% P205 and
adding iron to reduce Fe 3+ to Fe z§ Iron is added also between stages to keep a high
percentage of Fe2§ 3+. The dark colour of the acid indicates the presence of uranium
in the U 4+ state.
BERRY 8 mentioned several oxidation agents such as air, oxygen, H202 and others.
But H202 is the oxidant frequently used for ease of operation, simpficity of apparatus
and non-pollution of acid. There are many oxidants cheaper than H202 but it is
important as far as manufacturer is concerned not to add any contaminants. So NaCIO 4
is not desired because of CI 1- and so is nitric acid which despite its oxidation strength
adds NO~ to the acid. There are methods to decompose the nilrates but this adds new
steps to the process. The amount of oxidant varies according to operating conditions. It
is important to know the concentration of Fe z+ continuously so as to use less quantity of
oxidant. Because DEHPA/TOPO tendency of U 4+ is negligible, the presence of Fe 2+ in
the acid is necessary to reverse the extraction process which leads to shipping of
organic phase and loading of aqueous phase. Stripping is important for the operation of
the first cycle since the returning organic solvent loses its strength if it is loaded with
uranium.

Experimental

Oxidation of H3PO4 by H202: This experiment was carried out to determine the
optimum concenration of H202 required for oxidation and the best time needed. The
experiment was done on Syrian phosphoric acid with a concentration of 29% wt. P205.
Table 1 shows the properties of this acid.

Table 1
Properties of Syrian wet phosphoric acid

P205 29 % wt
EMF 310 mv
Density 1,26 g/tool
Solids 1.5 % wt
Chlorides 0.125 %
Fluorides 1.64 %
AI203 0.11%
MgO 0.66 %
CaO 0.92 %
Fe§ 1210 ppm
Fe+2 150 ppm
U 60 ppm
SO~,2 2,8 %

239
Y. KOUDSI et al.: EFFECT OF OXIDATION-REDUCTION ON THE EXTRACTION

Table 2
Oxidation of phosphoric acid by H202

Concentration of H202/acid, vol/vol

Time, hr
1/1200 E.M.F. 1/600 E,M.F. 1/300 E.M.F.

0.0 262 262 262

1/12 380 575 620
1/2 360 660 687
1 356 690 718
2 350 695 735

Table 3
Effect of oxidation by H202 on extraction

H202/H3PO4' Fe+2/Fe+3' E.M.F. K

voUvol mV

0.0000 0,250 308 1.17

0.0006 0.124 370 2.37
0.0013 0.113 400 2.57
0.0015 0.116 485 3.10
0.0020 0.090 620 3.6

Table 4
Properties of iron powder

Assay 97 %
Insoluble HC1 0,5 %
Sulfide(s) 0.02 %
Ni 0.05 %
Mn 0.05 %
Cu 0,02 %
Zn 0.01 %
Pb 0.002 %
As 0.0005 %

The H202 used was of 30% concentration obtained from Merck. The temperature
was fixed at 25 ~ The results o0tained are shown in Table 2.
Effect of oxidation on extraction: Several samples of wet phosphoric acid from Horns
plant were taken. The acid was purified from solids and organics. Different quantities

240
 Y. KOUDSI et al.: EFFECT OF OXIDATION-REDUCTION ON THE EXTRACTION

Table 5
Effect of time on E.M.F.

Time, hr E.M.F., m V

0.0 353
1.0 165
2.0 150
3.0 130
4.0 125
24.0 105

Table 6
Effect of reduction by iron on stripping

Iron added, E.M.F.,

K
g~ mV

0,0 233 7.9O

1.0 190 2O.40
3.0 150 26.00
5.0 100 50.00
7.0 80 79.00

of H20 a were taken and added. The uranium was extracted by DEHPA/TOPO in
kerosene at a concentration of 0.5M DEHPA/0.125M TOPO. The ratio of
aqueous/organic was 2. The temperature was fixed at 40 ~ The results are shown in
Table 3.
Reduction of phosphoric acid by iron: This experiment was carried out to determine
the optimum quantity of commercial iron powder needed and the time needed for
reduction. The properties of the iron powder used are listed in Table 4.
The temperature was fixed at 25 ~ The E M F was measured after a period of
2 hours. The results are shown in Table 6 which shows the effect of iron quantity on
EMF.
The effect of time on reduction by ironpowder was studied by fixing the quantity of
iron powder added at 5 g/l and temperature at 25 ~ and measuring the EMF at different
time intervals. The results are shown in Table 5.
Effect of reduction on stripping: For this experiment wet phosphoric acid with
concentration of 37.5% P205 wt. was prepared. Samples of DEHPA/TOPO solvent
loaded with uranium were also prepared. Iron powder was added according to Table 6.
The two phases were mixed in :the ratio O/A = 10/6. The mixing and settling were
performed at 50 *C.

241
Y. KOUDS1et al.: EFFECT OF OXIDATION-REDUCTIONON THE EXTRACTION

Results

Effect of oxidation on extraction

The results from Table 1 are plotted in Fig. 1 which shows that:
It is sufficient to obtain the required EMF for oxidation by using H202 at 30% wt
concentration in water using the ratio of 1/600 vol/vol H202/acid.

&
800-
LL 113(30

"' 6oo7~176 . . . . . . . .

EMF= 600 mV
5OO

/~O0
1/1200
3O0
I I I I I p.
I 2 3 4 5
Time, h

Fig. 1. Effect of time and concentration of H202 on EMF

t
41 Temperature = 40 %:

30O 400 500 600

EM.E,mV
Fig. 2. Effect of EMF on the distribution coefficient

242
 Y. KOUDSI et al.: EFFECT OF OXIDATION-REDUCTION ON THE EXTRACTION

The oxidation of phosphoric acid by 1-[202 requires a period of 2 hours for sufficient
oxidation and for halt of 02 release. The oxidation reaches a saturation level after this
value. The accepted value of EMF for satisfactory extraction is above 600 mV.
As shown in Fig. 2, the distribution coefficient (K) increases by an increase in the
EMF and the oxidation state of the acid. The values of K are in close agreement with
those reported in the literature.

400
Temperoture = 25"C
u_.:
5g Fell H3PO4
hi

,
200 I E.M.E = 150mY

I0C I l ,I [
1 2 3 4
Time, h

Fig. 3. Effect of time on EMF

k
:~ 2 5 0 -

Temperclture = 25 *C
,ik

";2OO

150

100

5( I I I I
0 2 4 6 8
Fe,g.f ~
Fig. 4. Effect of Fe added on EMF

24.3
Y. KOUDSI et al.: EFFECT OF OXIDATION-REDUCTION ON THE EXTRACTION

Effect of reduction on stripping

The results in Table 5 on reduction of phosphoric acid by iron are plotted in Fig. 3.
This shows that a quantity of 5 g Fe]l is enough to reduce the EMF after a period of
2 hours to less than 150 mV at 25 ~ which is the maximum to ensure that uranium is
present in the tetravalent state. This also shows that the reduction is slow at the
temperature of 25 ~ and requires a period of 2 hours. Increasing the temperature will

8o!
K
60

2G-

O I Iz I 1
5O 100 150 200 250
E.M.E ,mV

Fig. 5. Effect of EMF on stripping

shorten the time needed for reduction but care should be taken not to generate H2 which
is dangerous in commercial application.
Figure 4 gives the effect of the quantity of iron added on EMF. It is clear that a
quantity of 5 g Fe/l is adequate for a temperature of 25 ~ to give the required EMF for
stripping.
Figure 5 is a plot of stripping coefficient (K) against EMF. It shows that the stripping
coefficient K increases with the decrease of EMF of the acid.

The authors wish to express their thanks to the general director of the Atomic Energy Commission of Syria
Dr. Ibrahim OUTHMAN for facilitating the work on this subject.

244
 Y. KOUI~SI et ,'d.: EFFECT OF OXIDATION-REDUCTION ON THE EXTRACTION

References

1. SPILIARD, Ind. Miner, Avril (1984) 342.

2. A. P. KOULEHERIS, Chem. Eng., 87 (1980) 82.
3. AUSTIN, Chem. Eng., (1982) 195.
4. R. S. LONG, Proc. Intern. Conf. on Peaceful Uses of Atomic Energy, Geneva, 1955., Vol. 8, New York,
1956, p. 77.
5. MSATEF, Apergu Sur l'Etat d'Avancement de la Recuperation de l'Uranium h Partir de l'Acid Phosphoric,
5e Congr~s Arabe sur les Resources Min6rales, Khartoum, 1985.
6. A. DELEON, Possibility for Recovery of Uranium as a Byproduct in the Production of Phosphate Fertilizers,
IAEA-SM-135, p. 39.
7. SURBER, Extraction of Uranium from Phosphate, AIChE, 74th Annual Meeting, New Orleans, Nov. 8-12,
1981.
8. BERRY, Chem. Eng. Prog., 77 (1981) 76.

245

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