Journal

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,

form June 17, 1984)

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
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184

that the extractability

of technetium
is also enhanced by a considerable
number of other elements, including major fission products such as palladium
and strontium. Under reprocessing conditions the most effective of these is
zirconium, which will be discussed in some detail.

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

and has been

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-

Fig. 2. Effect of technetium

on the extraction
of zirconium
TBP-OK;
0.0088 M zirconium;
temperature,
35 C).

(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,

less the amount

that

30% TBP-

would

be ex-

The effect of acidity on Drc in the absence and presence of zirconium

(0.0088 M) is shown in Fig. 3. Figure 4 shows the effect of rising temperature in enhancing DrC in the presence of 0.0088 M zirconium or diminishing
it when zirconium is absent.
The variation of II,, with percentage TBP is shown in Fig. 5; the gradient of 1.6 is similar to that of 1.5 reported by Pruett [ 71. Despite the wellknown non-ideality
of mixtures containing high proportions
of TBP in kerosene, at lower proportions
such gradients are commonly taken to indicate
approximately
the number of TBP molecules in the extracted complex, e.g.
three for pertechnetic
acid itself [6]. Even in the presence of zirconium, DTC
must include a contribution
from pertechnetic
acid alone, for which in principle a correction should be made. From the relationship shown in ref. 6, it
seems reasonable to take the correction as proportional
to the third power
of TBP concentration
and to the distribution
ratio for pertechnetic
acid in
30% TBP; it then proves scarcely significant in 20% TBP or less, while above
30% it is increasingly vitiated by non-ideality until at 100% it exceeds the
observed distribution
ratio. The correction is therefore disregarded, and the
Zr-Tc complex is simply taken to extract mainly with one or two TBP
molecules.
5. Discussion
The data presented in this report indicate that the extraction of pertechnetate
into 30% TBP-OK from HNOs is enhanced by a considerable
number of elements, in addition to the previously known uranium, thorium
and zirconium.
The enhancement
by uranium has previously been most studied, and is
attributed to replacement by pertechnetate
of a nitrate group in the extracted
uranyl-TBP
complex, i.e.

189

Fig. 3. Effect of acid on the extraction

of technetium
(solvent, 30% TBP-OK;
TcOd-; temperature,
35 C): 0, no zirconium; A, 0.0088 M zirconium.

UOz2+ + NO;

+ Tc04- + ZTBP F

0.0028

UOz(NOs)(Tc04)-ZTBP

instead of the normal

UOz2+ + 2NOs- + 2TBP e

UOB(NOS)z+2TBP

Clearly this coextraction phenomenon may occur whenever the enhancing

species associates with pertechnetate and is extracted in sufficient quantities,
e.g. uranium, cerium(IV) and thorium.
However, zirconium significantly enhances the extractability of pertechnetate, although it is itself poorly extracted in 30% TBP-OK (DZ, =
0.1 - 0.2 from 3 M HN03 [lo]) and is present in only slight excess over
technetium. The effect is evidently more than the mere substitution of pertechnetate into an already organophilic complex. With zirconium, the association produces a complex which not only is more extractable than either
component alone but also has the following other distinctive properties.

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

Fig. 5. Effect of TBP concentration

on technetium
extraction
(3 M HNO,;
technetium;
0.0088 M zirconium;
temperature,
35 C; slope, 1.57).

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

ments in the mixed complex.

cess may thus be written as
Zr4+ + Tc04although
complex.

+ 3NOs- + TBP e

The equation

representing

the extraction

pro-

Zr(N0s)s(Tc04)TBP

no reason can yet be offered

for the particular

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,

and P. D. Wilson, J. Less-Common

Radiochim. Acta, 28 (1981) 153.

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.

Sci. Technol., 15 (1980) 959.

10 A. A. Siczek and M. J. Steindler,

At. Energy Rev., 16 (1978)

575.