2nd International Workshop in Geoenvironment and 85

Geotechnics, September 2008, Milos island, Greece

Extraction of Th4+ from industrial effluents by liquid emulsion membrane

J.Z. Cheng
Resources and Safety Engineering College, China University of Mining and Technology, Beijing and
Baogang Research Institute of Ming, Inner Mongolia, Baotou Iron & Steel (Group) Co., LTD., China

Y.B. Hou
Resources and Safety Engineering College, China University of Mining and Technology, Beijing,
China

L.P. Che
Baogang Research Institute of Ming, Inner Mongolia, Baotou Iron & Steel (Group) Co., LTD., China,
Email: liping_che@yahoo.com.cn

ABSTRACT nology (LMET) with lower cost, higher effi-

ciency and good selectivity was used to recover
The extraction of thorium from industrial radi- and treat Thorium from one certain deposit; this
oactive wastewaters discharged from Rare Earth approach achieved the goal of both comprehen-
(RE) plants was studied by the liquid membrane sive exploitation and rational use of Th re-
emulsion technique using P507- sources, as well as the protection of the Th re-
Span80-sulphonating kerosene-HCl. The emul- sources and the environment from radioactivity
sion conditions, the technological factors such as pollution.
ratios of oil to the internal aqueous phase and
water to emulsion, and the extraction time etc.
were investigated. 1. THE CONDITION TESTS
The test sample is industrial radioactive
INTRODUCTION wastewater discharged from RE plants contain-
ing 21.83 mg/L ThO2.
The total prospective reserves of ThO2 in one The extraction of thorium from this RE in-
certain deposit of China, are very large and could dustrial wastewater was studied by the liquid
meet the needs of China's nuclear energy pro- membrane emulsion technique using
duction for many years. However, exploitation of P507-Span80-sulphonating kerosene-HCl. The
the deposit, has created radioactive contamina- conditions of making emulsion as well as the five
tion. factors such as fluid carrier P507, Surfactant
The Liquid Membrane Emulsion (LME) sys- Span80, internal aqueous phase HCl, the ratios of
tem is an extremely dispersive system which is oil to internal aqueous phase Roi and water to
characterized by the provision of large specific emulsion Rwe etc. were investigated.
surface area and large area of phase interface,
flux of Th4+, high speed for transfer, directional Table 1: The test designs of the L16 (45)
transference for Th4+; it is not restricted by ex-
factors
traction balance and coefficient of distribution, levels
including extraction and reverse-extraction into A B C D E
one step, and has very efficient, highly selective 1 4 1 2 0.5 5
and good applicability etc. 2 8 3 4 1.0 10
In this paper, in accordance with the charac-
teristics of the Liquid Membrane Emulsion 3 12 5 6 1.5 15
Technique (LMET) and Thorium, a new tech- 4 16 7 8 2.0 20
86 2nd International Workshop in Geoenvironment and
Geotechnics, September 2008, Milos island, Greece

Table 2: The results of the L1645

Extraction
Number A B C D E Rate of
Th4+
1 1 1 1 1 1 71.73
2 1 2 2 2 2 98.37
3 1 3 3 3 3 98.82
4 1 4 4 4 4 88.75
5 2 1 2 3 4 89.36
6 2 2 1 4 3 99.01
7 2 3 4 1 1 87.94
8 2 4 3 2 2 98.33
9 3 1 3 4 2 98.99
10 3 2 4 3 1 99.28
11 3 3 1 1 4 98.87
12 3 4 2 2 3 99.06
13 4 1 4 2 3 99.19
14 4 2 3 1 4 98.56
15 4 3 2 4 1 89.04
16 4 4 1 3 2 90.60
1 89.42 89.82 90.05 89.28 87.00
2 93.66 98.81 93.95 98.74 96.57
3 99.05 93.67 98.68 94.52 99.02
4 94.35 96.19 96.29 93.95 93.89
Ri 9.63 6.15 8.63 9.46 12.02

The transfer mechanism is shown in Fig 1 and fixed so that increasing strength of membrane
includes: always corresponds to the volume fraction A of
liquid paraffin 1%, the pH value of industrial
- Diffusion of the complex and the chelating
wastewater is 2.5, the time of making emulsion is
agent in the peripheral oil layer of the emul-
15min, the temperature of tests is 2628.
sion drop.
The test results are seen in Table 2.
- Diffusion of the complex and the chelating
Table 2 illustrates that E1, E2, E3 and E4 are
agent through the interstitial oil membrane
phase
The orthogonal tests of four levels and five
factors are designed and studied. The factors
studied and the levels used are seen in Table 1).
Table 1 illustrates that factor A is the volume
fraction A of P507 %, factor B is the volume
fraction B of Span80%, factor C is HCl mol/L,
factor E is the ratio of oil to inner Roi and factor E
is the ratio of water to emulsion Rwe; the four
levels were selected based on test results of
simulated solutions containing different concen- Figure 1 The mechanism of P507 transfer Th4+ )
trations of Th. The other test conditions were
2nd International Workshop in Geoenvironment and 87
Geotechnics, September 2008, Milos island, Greece

mean values 1, 2, 3 and 4, respectively, and Ri is nal water phase after breakage of emulsion con-
the difference between the maximum and min- tained ThO2 > 0.43g/L.
imum value of the same factor.
It is seen that the optimal conditions for the
recovery of Th4+ from Rare Earth (RE) industrial 3. CONCLUSIONS
wastewaters are A3B2C3D2E3, (as shown in rows In this paper, it is seen that Th can be recovered
E1-E2 of Table 2) namely, A 12% P507 A, B 3% from industrial radioactive wastewaters dis-
Span80 B, C 6 mol/l HCl. D Roi 1:1, E Rwe 15:1. charged from RE plants containing 21.83 mg/L
If the internal aqueous phase is 6mol/L HCl, it is ThO2 using P507-Span80-sulphonating kero-
difficult to separate the emulsion and the HCl sene-HCl. The main factors in the tests carried
solution due to the fact that the specific gravity out are the volume fraction A of P507 and
emulsion is heavier than the aqueous solution. So Span80, the density of the internal aqueous
the internal aqueous water phase is fixed to phase, the ratio of oil to inner Roi, the time of
4 mol/L HCl. making emulsion, the ratio of water to emulsion
Rwe, pH value and the time of recovery Th4+.
2. THE SYNTHESIS TESTS The test conditions for the recovery of Th4+
from the RE industrial radioactive wastewater
Based on the previously mentioned test condi- are 12% P507, 3% Span80, 1% liquid paraffin,
tions as well the optimum conditions for the re- 84% sulphonating kerosene; inner water phase is
covery of Th4+ from the RE industrial waste- 4mol/L HCl; the ratio of oil to inner Roi is 1:1;
water, the synthesis tests were carried out in the the time of making emulsion 20 min. The ex-
laboratory. The synthesis tests conditions were ternal water (industrial radioactive wastewater)
12% P507, 3% Span80, 1% liquid paraffin, 84% contained ThO2 21.83 mg/L with pH 2.5, the
sulphonating kerosene; inner water phase ratio of water to emulsion Rwe was 10:1 and the
4mol/LHCl; ratio of oil to inner Roi is 1:1; time of time for recovery of Th4+ was 15min. It is seen
making emulsion 20 min. The industrial from the tests that extraction rate is 99%, the
wastewater contained ThO2 21.83 mg/L while its internal aqueous phase contains 433.46
pH value was 2.5, the ratio of water to emulsion 435.24 mg/L Th4+, while the remaining liquid
Rwe was 10:1 and the time for Th4+ recovery was contains Th4+ < 0.118 mg/L.
15min.
The synthesis tests included five batches un-
der the same conditions. The results of synthesis REFERENCES
tests are seen in Table 3. Che L.P and Y.F Yu, 2003. Synthetically Utilization of
It is obvious from Table 3 that the mean ThO2 Radioactive Waste Dregs, In: Leon Lorenzen and Dee
extraction rate from industrial radioactive Bradshaw, XXII International Mineral Processing
wastewater is 99.28%, while the obtained inter- Congress, Cape Town, South Africa. The South Afri-
can Institute of Mining & Metallurgy, 28 Sep-3 Oct,
Table 3: The results of the general test pp. 480-482.
Kulkarni, P.S., K.K. Tiwari and V.V. Mahajani, 2000.
internal Membrane stability and enrichment of nickel in the
Remaining extraction
serial num- aqueous liquid emulsion membrane process. Journal of Che-
liquid rate of Th4+ mical Technology and Biotechnology, 75(7), pp. 553-
ber of tests phase 560.
mg/L %
mg/L
1 0.151 433.58 99.31
2 0.068 435.24 99.69
3 0.157 433.46 99.28
4 0.120 434.20 99.45
5 0.096 434.68 99.56
average 0.118 434.24 99.46
88 2nd International Workshop in Geoenvironment and
Geotechnics, September 2008, Milos island, Greece