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Deep liquid-chromatographic purification of uranium extract from technetium

Article · January 2013

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 DEEP LIQUID-CHROMATOGRAPHIC PURIFICATION OF URANIUM EXTRACT FROM TECHNETIUM
Volk V., Dvoeglazov K., Podrezova L., Vidanov V., Pavlyukevich E.
OAO State Research Center “VNIINM”, Moscow, Rogov str., bld. 5, RUSSIA Tel. +7-499-199-8227,
Fax. +7-499-196-6451, E-mail: march@bochvar.ru
In order to improve the grade of uranium extract
purification from technetium the method of liquid
chromatography and apparatus for its performance have
been developed. Process of technetium extraction and
concentrating in aqueous solution containing reducing
agent has been studied on simulated solutions (U-Tc-
HNO3-30% TBP-isoparM).
The dynamic tests of the method have been carried
out on the laboratory unit. Solution of diformylhydrazine
in nitric acid was used as a stationary phase. Silica gel
with specific surface of 186 m2/g was used as a carrier of
the stationary phase.
It is shown that the volume of purified extract
increases as the solution temperature increases,
concentration of reducing agent increases and extract flow
rate decreases. It is established that technetium content in
uranium by this method could achieve the value less than
0.3 ppm.
Some variants of overload and composition of the
stationary phase containing the extracted technetium have
been offered and tested.
It is defined that the method provides reduction of
processing medium-active wastes by more than 10 times
during finish refining process.
Recycling of uranium in the nuclear fuel cycle get
through sublimation (production of UF6) and separation
(enrichment by 235U) stages, that requires deep purification
of uranium from a number of radioactive and stable
impurities [1] like 99Tc, that forms volatile hexafluoride.
Such deep purification not always could be reached during
radiochemical spent nuclear fuel reprocessing [2]without
additional retreatment of uranium reclaim (mostly
extraction is used [3])that significantly rises up the
recycling cost.
Earlier [4] the ability of uranium extract purification
from trace quantities of technetium in the liquid
chromatography column (LCC) has been demonstrated.
Aqueous phase used in the liquid chromatography process
contained reducing agent of Tc(VII). Different reducing
agents are used for reduction of Tc(VII). By results of
comparing properties of organic derivatives of hydrazine -
carbohydrazides, formylhydrazide and diformylhydrazide
(DFH), DFH has been selected for further elaboration
[4,5,6].
Authors of the work [7] have demonstrated the
perspective of DFH application in the radiochemical
technology by the example of plutonium reduction.
The proposed finish purification process of uranium
extract from technetium includes reductive re-extraction
by water solution of reductant, which is contained in pores
of hydrophilic checker with high volume porosity. The
Global 2013, Salt Lake City, Utah, September 29-October 3, 2013
aqueous phase containing the reducing agent is held in the
pore space of the checker during the whole reductive re-
extraction process. The high degree of uranium extract
purification from technetium is attained by the fact that the
uranium extract contacts with fresh portion of re-extracting
solution before flowing out from the LCC.
1. METHODICAL PART
Silica gel of ASKG grade has been used in our
experiments as an active checker (carrier). As known, the
silica gel has good chemical and radiolysis stability, as
well as high specific surface and is widely applied in the
chromatography. Column with silica gel for re-extraction
and concentrating of plutonium from solutions of
trilaurilamine was used in the work [8]. In the work [9] it
is proposed to add oxidizing agents or reducing agents in
gels to separate substances by their oxidation-reduction
potentials. The silica gel was preliminary dispersed and
fraction of 0.315÷0.5 mm was selected for experiments.
Then the fraction was washed with water and dried under
vacuum at temperature of 120 ºС to stationary mass. The
mass of prepared powder was 0.457 g/ml; volume porosity
- 63% vol; specific surface - 186 m2/g.
DFH was synthesized from hydrazine hydrate and
formic acid as per the methods [10]. Hydrazine hydrate
with formic acid in 1:2 mole ratio was heated with return
condenser for 30 minutes. Crystals were separated from
mother solution by filtration through a paper filter under
vacuum. Diformylhydrazine cleaning was performed in
two stages. Firstly recrystallization in hot water was
carried out. Then filtered crystals were washed on the filter
with ethyl alcohol and dried in the air. The synthesized
product contained not less than 99% of basic substance.
Product purity was confirmed by measurement of the
melting point (156 – 158 °C) and by the X-ray
crystallographic analysis.
Uranium extract with technetium was prepared as
follows. The batch with crystalline uranyl nitrate
hexahydrate was dissolved in 30 % tributyl phosphate in
isoparaffin diluting agent. After full dilution the solution
was filtered through a paper filter and added with HTcO 4
solution (2 g/l by Тс) in 30 % tributylphosphate.
Concentration of nitric acid in the extract was 0.02 mole/l.
The laboratory unit (Fig. 1) comprising liquid
chromatographic column, thermostat and peristaltic pump
was assembled for performance of experiments. The
uranium extract was supplied to the glass column and then
the extract flows out through the outlet to a receiver.
The procedure of experiment was as follows. The
aqueous solution containing the reducing agent was
supplied by the peristaltic pump to the column from the
bottom upwards until full filling. Then the pump was
356
 switched off and the solution was held for 1 hour for
saturation of silica gel pores with the solution. The
receiver(4) was filled with the uranium extract. 10 minutes
after switching-on the thermostat uranium extract
containing technetium was supplied. Purified extract was
collected into the receiver (5). Through equal gap of time
were selected portions of the purified extract for
determination of technetium concentration.
During the experiment was observed gas evolution,
that is an indicator of oxidation-reduction reaction between
Tc(VII) and DFH. It also was indicated by change of
checker color from transparent to deep-brown. As most
hydrazine derivants DFH reduces the technetium(VII) to
low-extracting technetium (IV) form, which goes to
aqueous phase in silica gel pores. In the course of
2
1 – Thermostat; 2 – Column with silica gel containing aqueous solution; 3 – Dosing pump; 4 – Receiver with initial
extract; 5 – Receiver with purified extract
Fig. 1. Laboratory unit diagram
Global 2013, Salt Lake City, Utah, September 29-October 3, 2013
experiment saturation boundary continuously moved
upwards. In some experiments sedimentation in silica gel
pores was observed. After full saturation of volume of the
column determined by the color boundary, the supply of
the extract was stopped and supply of the regenerating
aqueous solution was started. Composition of the
regenerating aqueous solution was selected so that Tc(IV)
was oxidized to Tc(VII) and removed from pores of the
silica gel. In all experiments, the solution was supplied
from the bottom upwards. After full decoloration of the
checker, “fresh” regenerating solution was supplied to the
column and the extract purification procedure was
repeated. Fig. 2 illustrates different stages of the
experiment.
4
3
357
 a b c d
a – Purification of uranium extract from technetium; b – saturation of the column befor technetium breakthrough; c
– regeneration (removal of technetium) of the column; d – full release of the column from technetium and loading of
new aqueous solution of reducing agent.
Fig. 2. Different stages of the procedure of uranium extract purification from technetium
1

0.9

0.8
Concentration of Тс

0.7

0.6
In OPh, mg/l

0.5

0.4

0.3

0.2

0.1

0
0 100 200 300 400 500
Volume of passed organic phase, ml

Fig. 3. Dependence of technetium contents in the extract on volume of organic phase passed through the column with
[DFH]=1 mole/l at temperature 45 °С.
aqueous phase volume) the residual concentration of
technetium in the organic phase was less than detection
2. RESULTS OF THE EXPERIMENT AND
limit of ≤0.01 mg/l. Breakthrough by technetium was
THEIR DISCUSSION
observed at proportion O:A≈(92÷95):1.
Experiment with absence of uranium was carried out
Regeneration of aqueous phase composition was
as efficiency test of the proposed method of technetium re-
performed in two stages: one column volume was filled (by
extraction in the extraction chromatography column. The
void volume) with 6 mole/l of nitric acid and held in the
prepared extract contained the following components:
column for 90 min, then two column volumes was supplied
[HNO3] = 0.12 mole/l, [Tc] = 6.2 mg/l. Aqueous phase in
of the reducing solution for removal of oxidized re-extract
pores of the carrier - [DFH] = 1 mole/l in mixture with
of technetium and impregnation with new portion of the
[HNO3]=1.0 mole/l. Volume of operating chamber of the
reducing agent. Thus it has been shown that application of
column was 12 ml. Volume of aqueous phase in the checker
this method provides re-extraction of technetium (taking
was 4.4 ml. The extract was supplied to the column by
into account sums of volumes of regeneration solution and
upward flow. Specific section load of the checker was 2
washing solution) at proportion О/A≈30/1, that is
m3/(m2∙h). Column contents were heated up to 45 °С.
unachievable for extractors of mixer-settler type or
Results of the experiment are given in Fig. 3.
centrifugal extractors applied in PUREX-process.
As seen from Fig. 3 to the value of proportion
O:A≈90:1 (in equivalent of proportion of extract volume to

Global 2013, Salt Lake City, Utah, September 29-October 3, 2013 358
 Studying of temperature influence on effectiveness of dependence of technetium contents in organic phase on
the procedure of technetium extract cleaning was performed proportion O/A are given in Fig. 4.
at 30, 40 and 50 °С. The results of experiments as

Concentration of technetium, mg/l

O:A

Fig. 4. Dependence of technetium contents in the organic phase on proportion O:A during chromatographic
purification of the extract from technetium at different temperature, °С: 1 – 30 ; 2 – 40; 3 – 50 °С

As shown in Fig. 4, the process of separatory
purification of extract from technetium passes more
effectively at temperature of 50 ºС. At that breakthrough
of Тс occurs at proportion О:A≥90. Within the interval
from О:A=90:1 to О:A=123:1, at temperature of 50 ºС,
concentration of technetium in outgoing organic
solution increases from ≤0.01 mg/l (detection limit) to
0.52 mg/l. However, at temperature of the extract
purification process equal to 50 ºС formation of
technetium-contained sediments was observed on silica
gel surface. To dissolve this sediments is required long
time of column regeneration. At that, release of the
column from technetium is performed only at 98%.
At the final step of this work stage (without
uranium) the test of extraction-chromatographic
purification of the extract containing technetium in the
cyclic operation mode was performed. As a result,
during the experiment lasting for 12 hours of continuous
operation, 1200 ml of 30 % tributylphosphate solution
in dodecane containing 5.9 mg/l of technetium were
purified . 3 cycles of cleaning with unloading of the
column have been performed, at that volume of aqueous
phase was 39 ml, it corresponds to total proportion
О:A=31:1. Contents of technetium in mean aqueous
phase is 179 mg/l.
To study the influence of uranium on effectiveness
of cleaning from technetium, the extract containing
[U]=100 g/l, [Tc]=20 mg/l was used. Contents of
stationary phase and conditions of experiments
performance are specified in Table 1, and the results if
graphic form – in Fig. 5.

TABLE 1. Conditions of experiments on re-extraction of technetium from the uranium extract at 40 °С

Composition of Obtained ,%
solution for removal О/A for the
Loading
of technetium from full cycle
Contents of stationary phase during О/A before
Experiment the liquid
extract breakthrough
No. chromatography
supply, of Tc
column
m3/(m2∙h)
[DFH], [HNO3], [Glycine]*, [HNO3], [H2O2],
mole/l mole/l mole/l mole/l mole/l
1 0,5 0,2 0,5 1,9 60 6 0 7,85 70
2 0,5 0,2 0,5 0,98 60 3 0,2 23 85
3 1,0 0,2 0,5 0,98 > 120 3 0,2 19 92
* - as additional experiments have shown, addition of glycine prevents formation of deposits of reduced forms of technetium
and reduces the ratio of their dispensation [11]

Global 2013, Salt Lake City, Utah, September 29-October 3, 2013 359
 [Tc], mg/l
2
Fig. 5. Concentration of Тс in uranium extract at the outlet from the column depending on passed column
volumes. Numbers of curves correspond to numbers of experiments.
Results of this number of experiments have shown
that at high concentration of reducing agent in the solution,
quantity of volumes of cleaned extract increases at the
same volume of the aqueous phase, i.e. volume of
processing liquid radioactive wastes decreases. Presence of
uranium slightly decreases the proportion О/A, if there is
no breakthrough of technetium in the cleaned extract. In all
experiments the residual concentration of technetium in
the uranium extract has not exceeded 0.03 mg/l or 0.3
g/gU.
Regeneration of silica gel was performed in different
conditions after each of three experiments. After the first
experiment the uranium extract was forced out by nitric
acid of 6 mole/l concentration at 50 °С at the rate of 1.3
ml/min (1 m3/m2∙h). At that silica gel in the column gained
on violet brown color. At the outlet color of the solution
was not saturated . As a result of analysis of the
regenerating solution it has been found that total quantity
() of technetium removed from the liquid
chromatography column during reloading of the aqueous
phase was ≈ 70 % of its quantity extracted from the
uranium extract passed through the column. It is also
confirmed by visual observations, as the silica gel in the
column was darker than initial one. Low extraction of the
technetium can relate to the face that nitric acid slowly
oxidizes the reduced forms of technetium, which can be
occluded as oxocations on the silica gel surface. For more
complete oxidizing of Tc(IV) it is required to increase the
holding period (without solution supply) or to use more
kinetically active oxidizing agent, for example, hydrogen
peroxide.
Global 2013, Salt Lake City, Utah, September 29-October 3, 2013
Volume proportion О/A
Regeneration of the column after the experiment 2
was performed by nitric acid of 3 mole/l concentration
with addition of [Н2О2]=0.2 mole/l. Volume of the column
was filled with regenerating solution and held in the
column for 30 minutes at 50 °С. After extraction of the
first volume of the solution, the second volume of
regenerating solution was held for 15 min more and then
also extracted from the column. The silica gel layer in the
column became the same as in initial state, i.e. colorless by
appearance. Analysis results showed that in the
regenerating solution quantity of technetium was about 85
% of its initial contents in the extract. It is possible that for
more complete extraction of technetium longer period of
holding in the column is required.
Regeneration of the column after the third experiment
was performed by the same solution as after the second
experiment at 50 °С. The last portion of the extract was
extracted by the regenerating solution and the regenerating
aqueous solution was held for 30 min. During contracting
of the regenerating solution with the reduced form of Тс in
the column, intensive gas formation and disappearance of
silica gel brown color were observed. After supply of the
second portion of the solution we switched off the pump
again and held the solution for 10 min. Then the reducing
solution was supplied continuously. Total proportion of the
regenerating solutions and purified extract in that case was
О/A=19. Fig. 6 demonstrates the results of Тс extraction
from the column depending on volume of regenerating
solution and regeneration method.
360
 100

% of Тс extraction from the column

90
80 1 3
70
2
60
50
40
30
20
10
0
0 2 4 6 8 10 12
Number of column volumes

Fig. 6. Fullness of Тс extraction depending on volume of regenerating solution. Numbers of curves correspond to
numbers of experiments.

Increase of technetium extraction from the liquid
chromatography column in case of overloading of aqueous
phase on condition of preliminary oxidizing to Tc(VII) has
currently no unambiguous explanation. Supposedly it can
be related to:
- passing of technetium into the anionic form,
avoiding influence of the silica gel as slight cation
exchanger;
- destruction of polymer (high-molecular) oxolated
reduced forms of technetium that change rheology of
aqueous phase removed from porous grains.
Based on performed tests of the process of
chromatographic purification of uranium extract from
technetium, the following conclusions can be drawn:
1. The process of extract cleaning from technetium
effectively passes at temperature over 40 ºС.
2. Improvement of effectiveness of extract
chromatographic purification from technetium is possible
by decrease of load acting on the column section during
extract supply.
3. The more concentration of the reducing agent
(DFH) in the aqueous phase, the more effective this
process.
4. Fullness of column regeneration from technetium
increases, when loading on the column section during
extract supply decreases and either concentrated HNO3 or
H2O2 is used as component of the oxidizing agent.
3. APPARATUS FOR
CHROMATOGRAPHIC PURIFICATION OF
URANIUM EXTRACT FROM
TECHNETIUM
General view of the liquid chromatography column is
given in Fig. 7. The column consists of checker portion 1,
upper and lower phases separation chambers 2,3 with
inlets and outlets of phases 4,5,6,7. The phases separation
chambers are arranged concentric to the casing of the
column, equipped with multi-position detector of phase
boundary position 8,9 and connected to the checker
portion of the column 10 with partitions 11 that are
penetrable for liquid flows and attach the checker in the
column casing. Upper cover of the casing has connector 12
with full-way valve for loading and unloading of checker.
The device operates as follows (variant: cleaned
organic flow, cleaning aqueous flow, supply of flows –
cyclically alternating counterflow).
The column is filled through the loading connector 12
with the required volume of checker supplied as a
suspension in the cleaning flow phase (aqueous phase),
excess of aqueous phase is drained through the valve 13 to
the transient receptacle for cleaning flow. After filling of
the column with checker containing the cleaning phase in
the porous volume of grains, the purification stage begins.
The cleaned flow goes through the valve 14 to the
lower chamber, extracts the aqueous phase from the
chamber, intergrain space of checker part and upper
chamber 2. Then the aqueous phase is dumped through the
open valve 13 to the transient receptacle.
When the phase boundary in the chamber 2 reaches
the position, in which overflow holes in the chamber are in
the organic phase, the valve 13 closes by the signal of the
detector 9 and the valve 15 opens. The organic phase flows
through the valve 15 for further operations.

Global 2013, Salt Lake City, Utah, September 29-October 3, 2013 361

Fig. 7. Liquid chromatography column (general view of
the industrial apparatus)
After the required volume of the cleaned flow passes
through the column, the process passes to the unloading
stage. The valve 15 closes and the valve 13, through which
the aqueous phase is supplied to the column, opens. The
organic phase extracted from the chamber 2, intergrain
space of checker part and chamber 3 returns through the
open valve 14 to its own transient receptacle. When the
phase boundary in the chamber 3 reaches the position, in
which overflow holes in the chamber are in the aqueous
phase, the valve 14 closes and the valve 16, through which
the worked-out cleaning flow goes for further treatment,
opens.
Global 2013, Salt Lake City, Utah, September 29-October 3, 2013
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