Transactions of the Korean Nuclear Society Autumn Meeting

Pyeongchang, Korea, October 30-31, 2014

14
C Removal Technology for the Treatment of Spent Resin from Nuclear Power Plants
: A Review

Young-Ku Choia, Seunggeon Ana, Dae-Hwan Kima, Jun Ho Choa, Hwan Seo Parkb, Hong Joo Ahnb
a
SunKwang Atomic Energy Safety Co., Woojoo B/D, Gwanakro 120, Gwanak-Gu, Seoul, KOREA
b
Korea Atomic Energy Research Institute, Daedeokdaero 989, Yusung-Gu, Daejeon, KOREA
*
Corresponding author: choiyk09@gmail.com

1. Introduction and gasification of HCO3- ion to CO2 using acid

There are four CANDU commercial Nuclear Power
Plants in Wolsong site in Korea. The operation of the
power reactors produces a large quantity of spent resin
waste streams. These resins originate from clean-up
systems and decontamination facilities. The spent
resins generated from the moderator and primary heat
transfer purification systems comprise the largest
fraction of the radioactive resin waste. They are
classified as low and intermediate level waste, largely
because of their C-14 content; the moderator resins, in
particular, contain elevated levels of C-14 [1]. In
general, the spent resins are moved out of the service
columns as a slurry type and then stored in in-station
resin storage tanks [2]. Especially, spent ion-exchange
resins contaminated with C-14 radioisotope which has
long half-life of 5,730 years influences the strategy for
the disposal of spent. It is recommended that disposal
concentration limit of spent rein loaded with C-14 is 8
Ci/m3 according to US 10 CFR 61.8. Therefore, the
removal of 14C from spent resin and its concentration to
solid sorbents become a desirable feature which can be
disposed of as conventional low level waste. Acid
stripping and thermal stripping methods are under
development for the removal of C-14 from spent resins
[3, 4]. This paper describes the results from a program
undertaken to analyze C-14 in the spent resins produced
from the nuclear operations of Wolsong Nuclear Power
Plant. Total 72 resin samples were sampled from the
in-station storage tank at Wolsong Nuclear Power Plant
Unit 1. Resin samples were collected from both man-
hole (68 samples) and test-hole (4 samples). They were
separated into liquid, activated carbon, zeolite, and
spent resins which were oxidized and analyzed for C-14.
The average concentration of C-14 in the mixed
exchange resin (cation and anion exchange resin) was
determined. A comparison of the C-14 concentrations
in mixed and anion exchange resin was obtained.
Fundamental study was focused to analyze the
characteristics of C-14 removal from IRN-150 spent ion
exchange resin using alkaline solutions. In first,
adsorption characteristics of inactive HCO3- ion and
other ions in stripping solution on IRN-150 mixed resin
was evaluated. Based on these results, detailed
experiments for removal of HCO3- ion adsorbed on
IRN-150 by alkaline stripping solution such as Na3PO4
and NaNO3 was carried out. This experiment includes
removal characteristics of HCO3- ion from mixed resin
solution.
2. Methods and Results
In this section some of the techniques used to resin
sampling, 14C analysis, and 14C removal from spent
resin are described.
2.1 Resin Sampling Technique
Commercially available grain samplers were referred
for resin sampling. The sampler (see Fig.1) was
consisted of main control part, finger, and four
extension stainless steel tubes: they were connected and
disconnected with bolts. The largest of the sampler
connected of all is approximately 6 m long. The finger
which was opened or closed by take-up of the inner
wire has a conical tip to facilitate penetration. For
sampling spent resins from the in-station storage tank 2
at Wolsong Nuclear Power Plant Unit 1, an overall
length of approximately 5.5 m was required. The 15 cm
finger was, therefore, equipped with four extensions
each approximately 1.5 m long. Concrete caps of
manhole and test-hole were first removed from the in-
station storage tank structure to sample the spent resin.
The finger was assembled with the extension pieces,
and then, the sampler being lowered through the
manhole or test-hole into the in-station storage tank.
The maximum dose rate, in contact with the resin
sampler, was about 8mR/h and the tritium level in the
room was about 2.9 DAC during sampling. Lead
blankets were used to minimize dose uptake during
sampling.
Fig. 1. Spent Resin Sampler for in-station storage tank within
Wolsong NPP.
2.2 Carbon-14 analysis
 Transactions of the Korean Nuclear Society Autumn Meeting
Pyeongchang, Korea, October 30-31, 2014

M/H 1003
The distribution of C-14 concentration with elevation 1000 T/H

Concentration of C-14 (GBq/m )

3
in the Wolsong NPP’s spent resins sampled from
manhole is shown in Fig. 2.
900 424 228
187
899
167
91 99 203 414
91
51

91
60 Wall 100
Manhole Testhole
70 29

41
182
3.7 0.7
Water 0
0 50 100 150 200 250 300
Level

465

556
Elevation (cm)
366

Fig. 4. Concentration of C-14 in the Wolsong NPP’s spent

283

Spent resins sampled from man-hole and test-hole.

Resin
units : cm
This explains that most of the C-14 is in the anion
Fig. 2. Schematic of Wolsong NPP Units 1 and spent resin resin because cation-to-anion ratio of Wolsong NPP’s
storage tank 2. spent resin is almost 1: 1.
3500
The distribution of C-14 concentration with elevation Mixed
Anion
in the Wolsong NPP’s spent resins sampled from 3000

Concentration of C-14 (GBq/m )

manhole is shown in Fig. 3. The concentration of C-14 3
2500
at the bottom of tank was about 170GBq/m3 for the
2000
cation/anion mixed resin. The C-14 concentration at
the elevated level from 20 to 40cm was 380GBq/m3, 1500

which was the highest. The concentration of C-14 was 1000

generally decreased with elevation.
500

320 0
E000 NE000 C020 SE020 NE020 SE040 NE040 NW040 NW060 I100

280 Sampling

240
Fig. 5. Concentration of C-14 in the Wolsong NPP’s spent
resin; mixed resin and anion bead fraction.
E leva tio n (cm )

200

160
2.3 Removal characteristics of C-14
120

80 One of technologies for management of spent resin is

40
0
0 50 100
Concentration of C-14 (GBq/m )
Fig. 3. Concentration of C-14 in the Wolsong NPP’s spent
resins sampled from manhole.
A comparison of the C-14 concentrations of the
cation/anion mixed resins sampled from manhole and
test-hole is given in Fig. 4. The average concentration
of C-14 was 460GBq/m3 from test-hole and
53.1GBq/m3 from man-hole. The differences in the
acid stripping using HNO3 solution. IRN-150 resin is a
mixture form of a stoichiometric equivalent of the
strongly acidic cation and the strongly basic anion
150 200 250 300 350 400
3 exchange resins. Therefore, adsorption characteristic of
cation on IRN-150 was evaluated as shown in Fig. 6.
These cations include Cs, Co as radionuclide in coolant
and Na+, NH4+. The degree of adsorption capacity or
selectivity on resin showed Co>Cs>Na>NH4. Cobalt
has a favorable adsorption selectivity on IRN-150
compared to Cs ion.
1.8

1.6
Co
results obtained by two sampling suggest some
Ion-exchange capacity, meq/g

1.4
inhomogeneity exists in the resin storage tank. It is 1.2
possible that resins from test-hole were originated in the 1.0
Cs
higher proportion of C-14 in the system. 0.8 Na
NH4
The concentrations of C-14 for the cation/anion mixed 0.6
Co
and anion resins are given in Fig. 5. The average 0.4 Cs

concentration of C-14 was 546GBq/m3 for cation/anion 0.2

Na
NH4

mixed resin and 1,431GBq/m3 for anion resin. The 0.0

0.0E+00 2.5E-03 5.0E-03 7.5E-03 1.0E-02 1.3E-02 1.5E-02 1.8E-02 2.0E-02
concentration of C-14 for the anion resins was higher Ce (mol/L)

than those found for the cation/anion mixed resins; the Fig. 6. Adsorption isotherms of various cations on IRN-150
C-14 concentration in anion resin was approximately 2 at 30oC.
times higher than in the cation/anion mixed resin.
 Transactions of the Korean Nuclear Society Autumn Meeting
Pyeongchang, Korea, October 30-31, 2014

After removal of H14CO3- ion into stripping solution, both man-hole (68 samples) and test-hole (4 samples).
C-14 ion in this solution should be treated by proper The maximum dose rate, in contact with the resin
technology which produces minimum secondary waste. sampler, was about 8mR/h and the tritium level in the
One of possible technology is gasification of HCO3- in room was about 2.9 DAC. Each resin sample was
stripping solution to CO2 gas after separation of only oxidized with sample oxidizer (Perkin Elmer, M307).
stripping solution from spent resin. Fig. 7 shows The average concentration of C-14 in the cation/anion
gasification characteristic of HCO3- in two kinds of mixed resin was 460 GBq/m3 from test-hole and 53.1
stripping solutions to CO2 gas by addition of HNO3 GBq/m3 from man-hole. The C-14 concentration in
solution under nitrogen gas purging condition. As anion resin was approximately 2 times higher than in
similar to acidic stripping method, CO2 gas sharply the cation/anion mixed resin. The C-14 concentration
increased at early stripping stage. Very low was generally decreased with elevation. In the result,
concentration of HCO3- in residual solution after we must separate them into anion and cation resins and
gasification was confirmed. then eliminate the C-14 from the anion resins for legal
disposal of spent resins.
50,000
Na3PO4
Maximum adsorption amount of HCO3- ion on raw
45,000
NaNO3
NaNO3 resin was about 11mg-C/g-resin. This value agrees with
40,000 theoretical adsorption amount calculated by physical
35,000 property data. It was confirmed that alkaline solutions
C O 2 C on c.(p pm )

30,000 such as Na3PO4 and NaNO3 will be applicable for

25,000 effective removal of C-14 from spent resin. The
20,000
Na3PO4
minimum concentration of alkaline solution for
15,000 effective removal of C-14 over 99% should be three
10,000 times higher as a basis of equivalent compared to initial
5,000 loading amount of C-14 on spent resin. It was identified
0 that Na3PO4 and NaNO3 alkaline solutions showed over
0 20 40 60 80 100 120 140 160 180
<Addition of HNO3 1ml > Time(min)
99% of removal efficiency of C-14 from spent resin
under optimal conditions. However, on using Na3PO4
solution, inert atmosphere should be provided for
Fig. 7. Variation of CO2 gas concentration from NaNO3, preventing CO2 absorption from surrounding air gas
Na3PO4 stripping solution with purging time.

Fig. 8 shows Removal rate of 14C radionuclide from REFERENCES

real spent resin stored in Wolsong NPP by using
NH4H2PO4 and H3PO4.
[1] D. L. Moir, K. J. Ross, J. D. Chen, A. W. Tarr, E. L.
Bialas, W. A. Boivin, D. C. Doern, D. L. Hoffman, and J. P.
2.0
1.9 : 1단-H3PO4
M. Ross, “Determination of 14C in Spent Moderator Ion-
: 2단-H3PO4
1.8 : 1단-NH4H2PO4 Exchange Resin from Bruce Nuclear Generating Station A”, J.
1.7 : 2단-NH4H2PO4
Cumulative total C-14 amount (mCi x 10-2)

1.6 Radioanal. & Nucl. Chem.,Vol. 185, p. 69, 1994.

1.5 [2] C. F. Wong and S. Vijayan, “Pre-Disposal Management of
1.4
1.3 14C-Bearing Organic-Resin Wastes", Waste Management '04,
1.2
1.1
Proc. of the Symposium on Waste Management, Tucson,
1.0 Arizona, USA, Feb. 29-Mar. 4, 1-10, 2004.
0.9
0.8
[3] IAEA Technical Report, "Application of Ion Exchange
0.7 Processes for the Treatment of radioactive Waste and
0.6
0.5 Management of Spent Ion Exchangers", IAEA Tech. Report
0.4
0.3
No. 408, IAEA, Vienna, 2002.
0.2 [4] IAEA Technical Report, "Management of Waste
0.1
0.0
Containing Tritium and Carbon-14", IAEA Tech. Report No.
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 421, IAEA, Vienna, 2004.
Time(min)

Fig. 8. Removal rate of 14C radionuclide from real spent

resin stored in Wolsong NPP by using NH4H2PO4 and H3PO4.

3. Conclusions

Spent resins were sampled from in-station resin

storage tank 2 at Wolsong Nuclear Power Plant Unit 1.
Commercially available grain samplers were referred
for resin sampling. Resin samples were collected from