Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
of the Less-Common
Metals,
106
(1985)
COEXTRACTION
OF PERTECHNETATE
TRI-n-BUTYL
PHOSPHATE
J. GARRAWAY
Research
Cumbria
183
- 192
AND ZIRCONIUM
BY
and P. D. WILSON
and Development
(Gt. Britain)
(Received
183
February
Department,
24, 1984;
in revised
British
Nuclear
Fuels
Ltd.,
Sellafield,
Seascale,
Summary
The effect of added metals on the extraction of pertechnetate by 30%
tri-n-butyl phosphate-odourless
kerosene (TBP-OK)
from HNO, solution
was investigated.
Eight metal ions (strontium,
cerium(IV),
magnesium,
palladium, cobalt, zinc, calcium and scandium) were found to enhance the
extractability
of pertechnetate,
in addition to the known uranium, thorium
and zirconium.
Zirconium
is the most effective and has therefore
been
studied in most detail. This enhancement is considered to be due to the formation and extraction
of a pertechnetate-zirconium
complex,
which is
considerably
more extractable than zirconium or pertechnetate separately.
The basic solvent extraction properties of this complex were determined.
The outline equation for the extraction of the complex is considered to be
Zr4+ + 3NO,-
+ Tc04-
+ TBP----+
Zr(NOs)s(Tc04)TBP
1. Introduction
Technetium
is a high yield (6.1% from 235U) long-lived (t* = 2.12 X
10 years) fission product in irradiated nuclear fuel. Technetium may present
two problems in the reprocessing of this fuel: (1) it can catalyse the oxidation of hydrazine, which is used as a nitrite scavenger in the reductive separation of plutonium from uranium [ 11; (2) it can contaminate the uranium
and plutonium
products.
In addition, technetium will constitute a major
fraction of the radioactivity in long-cooled
(1000 years) waste products from
reprocessing.
The importance of these problems will depend inter aliu on the solventextraction behaviour of technetium during reprocessing. Here, technetium is
present essentially only as pertechnetate
Tc04,
i.e. technetium(VI1).
The
intrinsic extractability
of this into tri-n-butyl phosphate-odourless
kerosene
(TBP-OK)
is low [2] but is enhanced by the presence of uranium, thorium
and zirconium [3 - 71. However, the results presented in this paper indicate
0022-5088/85/$3.30
@ Elsevier
Sequoia/Printed
in The Netherlands
184
2. Experimental
details
Technetium,
as ammonium pertechnetate,
was supplied by Amersham
International.
This solution was heated to dryness, redissolved in 8 M HNOs
and refluxed for several hours before being diluted to about 1 M HNOs. This
procedure
is considered to condition technetium
completely
to pertechnetate [S].
Zirconium exists in solution as an equilibrium mixture of species such
as extractable
Zr4+ and ZrOH3+ and inextractable
Zr3(0H)48+. Further,
these species polymerize
to inextractable
species on aging, a process which
is accelerated
by heating [9, lo]. In consequence,
the solvent extraction
behaviour of zirconium depends on the history of the solution. In this work
solutions were normally prepared using zirconium nitrate, although zirconyl
chloride was occasionally
used, and were refluxed for 3 h partly to ensure
complete dissolution and partly to ensure a consistent equilibrium mixture
of zirconium species in solution.
95Zr, which was supp lied in a mixture of formic and oxalic acids by
Amersham International,
was evaporated to dryness, redissolved in a solution
of inactive zirconium in 3 M HN03 and refluxed for 3 h as described above.
This solution was used in experiments
on the molar ratios in extracted
species, and the activity was determined by y radiometry.
Solutions containing HN03, pertechnetate
and zirconium as required
were prepared, brought to the desired temperature
and contacted with 30%
TBP-OK which had been pre-equilibrated
with the appropriate
acid. The
phases were vigorously mixed with an electric stirrer for 10 min, although
equilibrium of pertechnetate
between phases was found to occur within 30 s.
The concentration
of technetium
in the separated phases was determined by
liquid scintillation counting using Packard Instagel. Similar procedures were
followed using the other elements listed in Tables 1 and 2, except that prolonged refluxing was unnecessary for most of them.
3. Results
Table 1 lists those species which were found to enhance the extractability of pertechnetate
into 30% TBP-OK from 3 M HNOa. Except where
otherwise specified, the distribution
ratio DrC for pertechnetate
is given in
the presence of 0.1 M species. Table 2 lists those species which were found
not to affect the extractability
of pertechnetate;
none diminished it significantly. Apart from cerium(IV), which is not the form of cerium in process
185
TABLE
Elements
enhancing
the
extractability
Element
DTC
3 M HNOs only
Sr
Zr (0.088
M)
U (250 g I-)
CeIV 1(0.05 M)
Mg
Pd
co
Zn
Ca
SC
0.10
0.63
1.38
0.26
0.62
0.15
0.40
0.15
0.15
0.43
0.33
of pertechnetate
All experiments
were performed
under
the following
TBP-OK,
2.8 x lop3
M Tc and S/A (solvent/aqueous)
other species
is 0.1 M unless otherwise
specified.
TABLE
conditions:
3 M HNOs,
35 C, 30%
= 1.0. The concentration
of the
Elements
not
enhancing
Ad
extractability
Crm
Al
Y
Mn
Ce
La
cs
Rua
As nitrosyl
the
ruthenium
of pertechnetate
Rb
Nd
Ni
Pr
Cd
Ba
Sn
Mo
cu
Fen
nitrates.
solutions, zirconium
is clearly
investigated in some detail.
the most
effective
enhancer
4. Effect of zirconium
The effect on the distribution ratio of zirconium at various levels up to
0.088 M is shown in Fig. 1. As long as the molar concentration
of zirconium
exceeds that of technetium, it alone determines D,, at constant acidity and
temperature (Tables 3 and 4); however, when the concentration
of technetium is greater, D,, falls. Technetium also enhances the extraction of zirconium (Fig. 2 and Table 5). The substitution of zirconyl chloride for zirconium
nitrate seems to make little difference.
Dibutyl phosphoric acid (HDBP)
similarly has little effect.
CZrl
I
.os
Fig. 1. Effect of
TBP-OK;
0.0028
chloride.
TABLE
Effect
@I)
.1
zirconium
on the extraction
of technetium
(3 M HNOs; solvent, 30%
M TcO4-;
temperature,
35 C): 0, zirconium
nitrate; A, zirconyl
3
of [Zr]
and [Tc]
on DT,=: [Zr]/[Tc]
ratio constant
at 3.5
[Zrl CM)
[Tel W
DTC
8.8
4.4
8.8
1.8
2.5
1.3
2.5
5.0
0.20
0.38
0.57
0.82
x
x
x
x
10-4
10-s
10-s
1O-2
All experiments
were performed
OK, 35 C and S/A = 1.0.
x
x
x
x
1O-4
10-s
10-j
10-s
under
the following
conditions:
3 M HNOs,
30% TBP-
187
TABLE
Effect
4
of [Zr]/[Tc]
ratio on
DTc ([Zr]
constant
at 8.8 x 10.
3 M)
DTC
7.8
3.9
8.2
1.6
2.4
3.0
4.2
x
x
x
x
x
x
x
1O-4
10-s
10-s
lop2
1O-2
10-2
1O-2
11.2
2.2
1.07
0.55
0.36
0.29
0.21
All experiments
were performed
OK, 35 C and S/A = 1.0.
0.57
0.55
0.57
0.46
0.43
0.38
0.32
under
the following
conditions:
3 M HNOs,
30% TBP-
(3 M HNOs;
solvent,
30%
188
TABLE
Solvent
phase concentrations
Total concentrations
(M)
[Tel
[zrl
7 x 10-4
1.4 x 10-s
3.0 x 10-s
1.7
2.2
2.5
3.3
5.0 x 10-s
of technetium
and zirconium
Corrected
concentration9
(M)
Ratio
[Tcl/[Zrl
[Tel
[zrl
10-a
10-s
1O-3
10-3
6.2 x 1O-4
9.8 x 10-4
2.1 x 10-s
5 x 10-4
8 x 10-4
1.6 x 1O-3
1.24
1.23
1.31
5.2 x :.O-3
3.4 x 10--s
3.5 x 10-s
0.97
x
x
x
x
Mean
All experiments
were performed
under the following
OK, 35 C and 8.8 X lop3 M aqueous zirconium.
Vorrected
[Tc] and [Zr] are total concentrations
tracted independently
of the other element.
conditions:
1.2 f 0.1,
3 M HNOs,
that
30% TBP-
would
be ex-
189
UOz2+ + NO;
+ Tc04- + ZTBP F
0.0028
UOz(NOs)(Tc04)-ZTBP
UOB(NOS)z+2TBP
190
3
fs
.7
.B
.5
.4
.3
.2
.1
Fig. 4. Temperature
effect on technetium
0.0028 M technetium):
0, no zirconium;A,
extraction
(3 M HNOJ; solvent,
0.0088 M zirconium.
30% TBP-OK;
(1) The Tc-Zr complex appears to extract largely as a 1:l adduct with
TBP, in contrast with a 1:3 adduct for pertechnetate and 1:2 or 1:3 adducts
for zirconium.
(2) The extractability
of the Tc-Zr complex is not affected by HDBP,
although this greatly enhances the extractability of zirconium.
(3) The extractability of the Tc-Zr complex increases significantly with
temperature over the range 15 - 50 C, in contrast with the behaviour of pertechnetate and zirconium separately.
The contrast in trends with rising temperature is indeed striking (Fig.
4). The increasing extractability
of the mixed complex is attributed to the
greater availability of TBP as the extraction of HNOs declines. With technetium alone, this effect is apparently outweighed by the exothermic nature of
the extraction [ 61.
The effect of acidity is more complicated (Fig. 3). The long falling sections of both curves probably reflect competition
by HNOs for TBP. The
191
X TBP
10
100
0.0028
later rising section for technetium alone may represent the formation of
more extractable species by protonation. The rise in extraction of the mixed
zirconium nitrate-pertechnetate
complex from 2 to 6 M HNO, is presumably
due to an increased degree of formation at the higher nitrate levels.
These interpretations are necessarily speculative, as verifying them
would be beyond the scope of this work. The small hooks at the low acid
end of Fig. 3 remain unexplained, except perhaps as activity effects.
In an attempt to elucidate the composition of the extracted Tc-Zr
complex, the total organic phase concentrations of both elements have been
corrected (Table 5) by subtraction of the amount of each that would have
been extracted in the absence of the other. These corrected concentrations
of technetium and zirconium are approximately equal in each case. Together
with the decline in DTC when the concentration of technetium exceeds that
of zirconium, this is taken to indicate equimolar proportions of both ele-
192
+ 3NOs- + TBP e
The equation
representing
the extraction
pro-
Zr(N0s)s(Tc04)TBP
extractability
of this
6. Conclusions
The extraction
of pertechnetate
into 30% TBP-OK is enhanced by several metal ions, but under conditions relevant to the reprocessing of nuclear
fuel, the effect is important only with zirconium. This forms a 1:l complex
with pertechnetate
which is more extractable than either component alone.
References
1 J. Garraway
2 D. J. Pruett,
Met., 97 (1984)
191.
3 F. Macasek, Radiochem.
Radioanal. Lett., 22 (1975) 175.
4 K. H. Lieser, A. Kruger and R. N. Singh, Radiochim. Acta, 28 (1981)
5 F. Macasek and J. Kadrabova, J. Radioanal. Chem., 51 (1979) 97.
6 D. J. Pruett, Sep. Sci. Zechnol., 16 (1981) 1157.
7 D. J. Pruett, Trans. Am. Nucl. Sot., 39 (1981)
144.
8
97.
R. A. Pacer, Investigation
of the analytical
chemistry
of technetium,
Ph.D. Thesis,
University of Michigan, MI, 1965.
9 J. C. Mailen, D. E. Horner, S. E. Don-is, N. Pih, S. M. Robinson and R. G. Yeats, Sep.
575.