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Procedia Chemistry 7 (2012) 575 – 580

ATALANTE 2012
International Conference on Nuclear Chemistry for Sustainable Fuel Cycles

Precipitation of zirconium and molybdenum in simulated high-

level liquid waste concentration and denitration process
Liu Xueganga*, Chen Jina, Zhang Yanchaoa, Wang Jianchena
a
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing, 100084, China

Abstract

This paper focuses on the precipitation behaviors of zirconium and molybdenum during concentration and denitration by
using simulated HLLW. The dependences of precipitates on final acidity of nitric acid, concentration factors and initial mass
ratio of Mo/Zr were investigated. As a result, the presence of zirconium molybdate hydrate (ZMH) is confirmed in all
experiments by the analysis of X-ray diffraction (XRD), but mass ratio of Mo/Zr in ZMH shows large deviations from the
precipitate yield of Mo/Zr in solution. This is considered as a result of the generation of amorphous precipitate of Mo.

©2012
© 2012The
TheAuthors.
Authors.Published
Publishedby
byElsevier
ElsevierB.V.
B.V.Selection and /or peer-review under responsibility of the Chairman of the
Selection and/or
ATALANTA 2012peer-review under responsibility
Program Committee Open accessofunder
the Chairman of thelicense.
CC BY-NC-ND ATALANTE 2012 Program

Keywords: Denitration, formic acid, high-level liquid waste, Zirconium, Molybdenum

1. Introduction

High-Level Liquid Waste (HLLW) is produced from first extraction cycle in spent nuclear fuel reprocessing
by PUREX. It includes the majority of fission products, minor actinides (MAs) and nitric acid presented in
raffinate of first extraction cycle. In current commercial reprocessing plants, the vitrification of HLLW is the
internationally recognized standard to minimize the impact to environment from HLLW conditioning and final
disposal. Prior to vitrification, HLLW is generally concentrated in order to reduce the volume of interim storage
between PUREX process and the vitrification and also to reduce the required evaporation duty of the vitrification
process itself. To prevent the corrosion from strong nitric acid, denitration is implemented during the

* Corresponding author. Tel.: +8610-89796063; fax: +8610-62771740

E-mail address: liu-xg@mail.tsinghua.edu.cn

1876-6196 © 2012 The Authors. Published by Elsevier B.V. Selection and /or peer-review under responsibility of the Chairman of the ATALANTA 2012
Program Committee Open access under CC BY-NC-ND license.
doi:10.1016/j.proche.2012.10.087
576 Liu Xuegang et al. / Procedia Chemistry 7 (2012) 575 – 580

concentration process. So, concentration and denitration are regarded as a significant step for HLLW waste
management in reprocessing plants [1]. In complement of and in parallel with the industrial vitrification process,
several HLLW partitioning processes have been developed worldwide [2]. Most extractants used in partitioning
processes are restricted to low acidity. For instance, in Chinese TRPO process the preferred concentration of
nitric acid for extraction is 0.9 to 1.2 mol/L in feed solution [3]. The reduction of nitric acid concentration is
required before partitioning. The concentration and denitration is considered to be promising as a pretreatment
process for the downstream partitioning process.
It is well known that precipitations arise during HLLW concentration and denitration process. Some reports
have described the formation of precipitates containing Ba, Sr, Zr, Mo and etc [4-6]. Unlike the vitrification
process, in which both solution and suspended solids are converted into glass, only solution will be sent into
extractive partitioning process. So, the chemical compositions of HLLW solution are very important parameters
and solids formations during concentration and denitration process should be closely studied. Zr and Mo are of
most importance in partitioning process. And in our previous research by using simulated HLLW, Zr and Mo are
found to be the majority of precipitations. The present work aimed to clarify the dependences of precipitates on
final acidity of nitric acid, concentration factors and initial mass ratio of Mo and Zr were investigated. The
mechanism of the precipitation of Zr and Mo was discussed.

2. Experimental

2.1. Simulated HLLW solutions

Table 1 Chemical composition and compounds for preparation of s-HLLW

Element Elemental concentration Compounds

/g˜L-1
Zr 0.708 Zr(NO3)4·5H2O
Mo 0.680 (NH4)6Mo7O24·4H2O
Ru 0.464 Ru(NO3)3
Rh 0.077 Rh(NO3)3
Pd 0.318 Pd(NO3)2
Ba 0.359 Ba(NO3)2
Sr 0.151 Sr(NO3)2
Cs 0.474 CsNO3
Pr 0.226 Pr(NO3)3 solution
Nd 0.808 Nd(NO3)3 solution
Sm 0.147 Sm(NO3)3 solution
Ni 0.046 Ni(NO3)2˜6H2O
Fe 0.237 Fe(NO3)3˜9H2O
Cr 0.062 Cr(NO3)3˜9H2O
Na 1.136 NaNO3

A 15-component simulated HLLW (s-HLLW) was prepared according to the calculated composition
estimated on the assumption that the PWR fuel burned up to 50,000 MWd/tU and cooled for ten years was
reprocessed by the PUREX process. The s-HLLW represented the raffinate solution from the first extractive
cycle of PUREX with specific volume of a8500L/tU containing 3 mol/L of nitric acid. Table 1 shows the
 Liu Xuegang et al. / Procedia Chemistry 7 (2012) 575 – 580 577

chemical composition of the s-HLLW. Pr, Nd and Sm were substituted for all rare-earths (RE) and TRU of
trivalent state, such as Am and Cm. U was also omitted because it does not seem to affect solid formation in
HLLW. Chemicals of analytical grade were used without further purification in the s-HLLW.

2.2. concentration & denitration of s-HLLW

Liquid level
controller

s-HLLW ᐕ֌ㄉ

Liquid level Liquid sampling

& thermal
detector
Formi c acid

Concentration &
denitration vessel

Reaction solution

Fig. 1 Concentration and denitration apparatus of s-HLLW

All experiments were conducted in the apparatus shown in Fig.1. An s-HLLW solution of 50ml was poured
into the concentration and denitration vessel and heated to a95 qC. Without refluxing, the given volume of formic
acid was supplied into the vessel to start denitration reaction. The liquid level was measured and transferred to
computer as a signal to control the flows of feed solution. As chemical reactions and water evaporation went on,
s-HLLW and formic acid were continuously supplied in order to keep a stable liquid level in the concentration
and denitration vessel to imitate the operation in industrial plants [7]. The solution was sampled from the vessel
at intervals. When the given concentration factor was reached, cooling water was pumped into condenser to
condense water vapor. Solution in vessel was kept on reaction at a90 qC for additional a120 min under refluxing
to finish chemical reaction on condition of constant concentration factor. After cooling to ambient temperature,
the precipitate was collected on a filter membrane, washed with distilled water and weighed after drying at
110qC for 2 h.

Crystal structure of undissolved materials from the simulated HLLW solution was determined with an X-ray
diffraction spectrometer. For analysis of the concentration of the main ionic species in the solutions, an
inductively coupled plasma emission spectrometer was used.

3. Results and Discussion

3.1. Precipitation during concentration & denitration

The procedure of experiment was divided into two phases: the early concentration/denitration phase and later
refluxing phase. Fig. 2 (a) and Fig. 2 (b) depicted the dependences of concentration of H+ and Zr/Mo on time
respectively. The mole ratio of HCOOH/HNO3 was 1.25 and final concentration factor was 3.2.
578 Liu Xuegang et al. / Procedia Chemistry 7 (2012) 575 – 580

At the beginning of concentration/denitration phase, the entry of formic acid into s-HLLW increased the
acidity, [H+] of the solution and then [H+] decreased rapidly along with the reactions of HCOOH and HNO3. The
concentration of [H+] was stable when reactions came into steady state. In the concentration/denitration phase,
the concentration of Zr shown monotonic increase. Whereas the concentration of Mo firstly increased then
decreased. In the refluxing phase, it changed very alike that the concentrations of H+, Zr and Mo continuously
decreased with refluxing.

6.0 2.0

5.5 concentration refluxing 1.8 concentration refluxing

5.0
1.6
4.5
1.4
-1

4.0

-1
[H ] /mol.L

concentration /g.L
3.5 1.2 Zr
Mo
3.0 1.0
+

2.5 0.8
2.0
0.6
1.5
0.4
1.0

0.5 0.2

0.0 0.0
0 50 100 150 200 250 0 50 100 150 200 250
time /min time /min

Fig. 2. (a) the dependence of [H+] in s-HLLW on time; (b) the dependences of Zr and Mo concentration in s-HLLW on time

3.2. Dependence of precipitation on concentration and denitration conditions

Table 2 showed the dependences of precipitate yields and final concentration of nitric acid on mole ratio of
HCOOH/HNO3. The final concentration factors were 4.8r0.2 in these experiments. The phenomenon that final
[H+] decreased with increase of mole ratio of HCOOH/HNO3 can be well explained by the reactions between
HCOOH and HNO3. The precipitation of Mo increased with decrease of final nitric acid concentration of the s-
HLLW. But no distinct effect of final concentration of nitric acid was observed on precipitation of Zr.

Table 2 Effects of formic acid on final precipitate yields of Zr and Mo and final concentration of HNO3

Mole ratio of Precipitate Precipitate

[H+]/ mol/L-1
HCOOH/HNO3 yield of Zr /% yield of Mo /%
0.80 35.10 81.56 4.65
1.00 36.92 88.10 3.13
1.10 37.36 90.31 2.76
1.25 38.96 93.62 2.26
1.40 36.34 94.62 1.81

Table 3 showed effects of concentration factors on final concentration of nitric acid, Zr and Mo and precipitate
yields of Zr and Mo corresponding to the same mole ratio of HCOOH/HNO3 as 1.25. The final concentration of
nitric acid increased with increase of concentration factor. The phenomenon suggests that more HCOOH is
required with the higher concentration factor to acquire the same final concentration of nitric acid in concentrated
s-HLLW. The final concentrations of Zr and Mo increased with increase of concentration factor. But their
precipitate yields firstly increased then decreased with the increasing of concentration factor. The maximum
precipitate yields occurred when concentration factor was 5.0.
 Liu Xuegang et al. / Procedia Chemistry 7 (2012) 575 – 580 579

Table 3 Effects of concentration factor on final precipitate yields of Zr and Mo and final concentration of HNO3

Concentration CZr /g˜L-1 CMo /g˜L-1 Precipitate Precipitate

[H+]/ mol/L-1
factor yield of Zr /% yield of Mo /%
3.0 1.43 0.20 31.60 90.95 1.83
3.8 1.82 0.32 31.12 88.50 2.02
5.0 2.16 0.24 38.96 93.62 2.26
7.3 3.42 0.44 33.64 91.92 2.46
13.0 6.32 1.58 30.54 83.63 3.86

3.3. Dependence of precipitation on Mo/Zr ratios

Table 4 showed effects of various mass ratios of Mo/Zr on the precipitations of Zr and Mo. All experiments
were conducted corresponding to 3.1r0.2 of concentration factor, 1.4 of HCOOH/HNO3 mole ratios. The fact
that final concentrations of nitric acid in all experiments were well controlled as 1.6r0.15 implied that
concentration of Mo had little impact on final HNO3 concentration. It is shown that the precipitate yield of Zr
increased greatly with higher Mo/Zr mass ratio. The precipitate yield of Mo also slightly increased with increase
of Mo/Zr ratio.

Table 4 Effects of Mo/Zr mass ratio on precipitations of Zr and Mo

Mo/Zr mass Precipitate Precipitate

CZr /g˜L-1 CMo /g˜L-1
ratio yield of Zr /% yield of Mo /%
0.47 2.06 0.26 3.79 74.61
1.13 1.33 0.16 39.42 93.67
1.62 0.93 0.25 57.99 93.01
2.14 0.55 0.27 75.12 94.29
2.72 0.13 0.24 93.71 95.67

HCOOH/HNO3 ratio Concentration Factor Mo/Zr mass ratio

1.25 3.2 1.0
0.80 5.0 1.0
1.25 4.7 1.0
1.25 7.3 1.0
1.40 3.1 1.6

Fig. 3. X-ray diffraction spectra for the undissolved solids obtained from the concentrated s-HLLW
580 Liu Xuegang et al. / Procedia Chemistry 7 (2012) 575 – 580

3.4. Precipitate analysis

In this study, precipitates in concentrated s-HLLW were collected with a filter membrane, washed with distilled
water and weighed after drying at 110qC for 2 h. The dried precipitates were analyzed with an X-ray diffraction
spectrometer. Fig. 3 showed the X-ray diffraction spectra for the undissolved solids obtained from the
concentrated s-HLLW on different experimental conditions. The spectra were in fair agreement with that for
zirconium molybdate (ZMH, ZrMo2O7(OH)2˜2H2O), in which the mole ratio of Mo/Zr was 2.0. And no crystal
structure was found in XRD spectra. This result was inconsistent with the precipitate yields of Zr and Mo in s-
HLLW solution. This is probably due to the formation of amorphous precipitate containing Mo, which is unable
to be detected by XRD analysis.

4. Conclusion

The present study revealed that during concentration and denitration process Zr and Mo in s-HLLW had
different precipitation behaviors. The concentration of Zr in solution was observed to steady increase whereas Mo
firstly increased and then decreased. The amount of formic acid introduced into the s-HLLW system had obvious
impact on final concentration of nitric acid and Mo. But precipitate ratio of Zr seemed independent with the
variation of formic acid added. The increase of concentration factor increased the final concentration of nitric acid,
Mo and Zr respectively. The precipitate ratios for both Zr and Mo were affected by the increase of concentration
factor as firstly increase and then decrease. Higher Mo/Zr ratio caused the increase of precipitate ratio of Zr.
Though a large variety of precipitate ratios of Zr and Mo were obtained from the deduction of Zr and Mo in
solution, XRD results shown similar spectra for all precipitations collected on different experimental conditions.
This is probably due to the formation of amorphous precipitate of Mo.

Acknowledgements

This work is sponsored by the national natural science foundation committee of china under contract No.
21001067 and 863 High-tech Projects (No. 2009AA050701 and No. 2009 AA050703).

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