WM2012 Conference, February 26- March 1, Phoenix, AZ

In-Situ Chemical Precipitation of Radioactive Liquid Waste-12492

Ahmet Erdal OSMANLIOGLU

Çekmece Nuclear Research and Training Centre, Istanbul, Turkey

ABSTRACT

This paper presented in-situ chemical precipitation for radioactive liquid waste by using chemical

agents. Results are reported on large-scale implementation on the removal of 137Cs, 134Cs

and 60Co from liquid radioactive waste generating from Nuclear Research and Training Centre.

Total amount of liquid radioactive waste was 35 m3 and main radionuclides were Cs-137, Cs-

134 and Co-60. Initial radioactivity concentration of the liquid waste was 2264, 17 and 9 Bq/liter

for Cs-137, Cs-134 and Co-60 respectively. Potassium ferro cyanide was selected as chemical

agent at high pH levels 8-10 according to laboratory tests. After the process, radioactive sludge

precipitated at the bottom of the tank and decontaminated clean liquid was evaluated depending

on discharge limits. By this precipitation method decontamination factors were determined as 60,

9 and 17 for Cs-137, Cs-134 and Co-60 respectively. At the bottom of the tank radioactive

sludge amount was 0.98 m3. It was transferred by sludge pumps to cementation unit for

solidification. By in situ chemical processing 97% of volume reduction was achieved. Using the

optimal concentration of 0.75M potassium ferro cyanide about 98% of the 137Cs can be

removed at pH 8. The Potassium ferro cyanide precipitation method could be used successfully

in large scale applications with nickel and ferrum agents for removal of Cs-137, Cs-134 and Co-

60.

1
WM2012 Conference, February 26- March 1, Phoenix, AZ

INTRODUCTION

Removal of radioactive contaminants from radioactive liquid waste is one of the basic methods

of radioactive waste management. By this method, majority of liquid waste could be reused or

discharged to the environment. One of the removal processes is chemical precipitation and

separation of radionuclide in the liquid waste. This process is used in hydrothermal reprocessing

of liquid radioactive wastes from nuclear power plants [1]. In addition, determination of

radiocesium in environmental water samples by using copper ferro(II)cyanide and sodium

tetraphenylborate ,s other application field of this method [2]. Many organic and inorganic

materials are used for removal of radioactive cesium from liquid waste [3]. Selectivity [4] and [5]

ion exchange mechanisms are determined [6]. By using a calix crown ether removal efficiency

of cesium ions from aqueous solution are investigated [7]. Potassium iron(III)

hexacyanoferrate(II) supported on polymethylmethacrylate [8], adsorption-microfiltration process

with potassium zinc hexacyanoferrate [9] and solution using nano-zirconium vanadate ion

exchanger [10] are other research studies for cesium removal from liquid waste. Large scale

implementations were carried out for radioactive liquid wastes by using oxalic acid and titanium

tungstate ion exchanger [11] and [12]. Removal of radioactive contaminant from the liquid waste

is common problem of all these investigations. In this study new removal technique and different

chemical agents were applied on radioactive liquid waste at Nuclear Research and Training

Centre (NRTC). Underground radioactive liquid waste tanks are used for collection of liquid

wastes. These tanks should be emptied before filling up in a short time for further using.

Otherwise it causes to interrupt related waste generation operations. Radioactivity

concentrations in the liquid waste tank were 2264, 17 and 9 Bq/liter for Cs-137, Cs-134 and Co-

60 respectively.

Instead of transportation of all liquid waste to facility for treatment from the tank, in situ chemical

precipitation was applied to avoid additional cost and radiological risks. By this way,

2
WM2012 Conference, February 26- March 1, Phoenix, AZ

transportation would be limited only bottom sludge. Volume of the sludge is extremely smaller

than total liquid amount by application of in-situ precipitation process. Most of the radioactivity

was precipitated by chemical agents to the bottom sludge and large amount of clean liquid could

be removed. Radioactive homogeneity was important for determination of actual specific

radioactivity of the liquid waste. Homogeneity was maintained by a portable air jet mixing in the

tank. After mixing, liquid waste samples were taken from different parts and levels of the tank.

All samples were analyzed by using gamma spectrometry system. Potassium ferro cyanide,

nickel nitrate and ferrum nitrate were selected as chemical agents at high pH levels 8-10

according to laboratory tests. Potassium ferrocyanide, also known as yellow prussiate of potash

or potassium hexacyanoferrate(II), is a coordination compound of formula K4[Fe(CN)6]·3H2O.

According to analyze results, chemical precipitation procedure was determined at laboratory

conditions. Experimental studies were used for selection of the best chemical precipitation

conditions. Chemical precipitation in the laboratory was scale up to the liquid waste tank. Initially,

liquid waste properties were arranged to laboratory conditions in the tank. Then in-situ chemical

precipitation procedure was applied.

EXPERIMENTAL METHOD

Initial specific radioactivity of the liquid waste was determined by analyzing of the samples which

were taken from the tank. In this study, a spectrometric analysis system was used to determine

activity concentrations. The system consisted of a coaxial-type high-purity germanium (HPGe)

detector that was linked to a multi-channel buffer (MCB) consisting of an analog-to-digital

converter (ADC). For data acquisition, ACCUSPEC was used as the multi-channel analyzer

software. The energy resolution (FWHM) observed in the measurements was 1.8 keV at the

1.33 MeV 60Co reference transition. Counting times were arranged up to 20,000 s to provide

3
WM2012 Conference, February 26- March 1, Phoenix, AZ

sufficient counting statistics. The detector was surrounded by lead and copper that provide an

efficient suppression of background γ radiation present at the laboratory.

In this study, different chemical agents were used as in radioactive waste management.

Potassium ferro cyanide and ferrum nitrate were selected as chemical agents on chemical

precipitation processes. Potassium ferro cyanide was selected for Cs-137 and Cs-134. Ferrum

sulphate was selected for Co-60 and also nickel nitrate was chosen for supporting of

precipitation process. Temperature was recorded as 21ºC. Chemical agent amounts and pH

levels were selected as main parameters with a constant mixing time and temperature.

Optimum precipitation conditions were determined at the laboratory according to the main

parameters (Fig.1).

Fig 1. Chemical precipitation test for radioactive liquid waste.

Decontamination Factors (DF) for each radionuclide was calculated by the initial and final activity

of the radionuclide. Decontamination factor of each sample versus pH levels were shown in Fig

2. Sample S4 parameters were selected for application of in-situ chemical precipitation process.

4
WM2012 Conference, February 26- March 1, Phoenix, AZ

Fig 2. Decontamination factors at different pH levels.

In-Situ Chemical Precipitation

Chemical agents in the solid phase were taken into liquid phase by mixing with pure water

before adding into the tank. During the mixing operation by air jet, initial pH level was determined

by using portable pH meter. By slightly addition of NaOH solution into the tank pH level was

increased to 8. Then chemical agents were poured into the tank. After 3 hours of mixing, tank

was remained for settling. After 7 days, samples were taken from different levels of the tank.

Radioactivity of the liquid at upper levels was almost zero. Activity levels were increased

regularly at transition level between the liquid and the sludge. Upper decontaminated liquid was

pumped to outside tank for further control of environmental polluters. Liquid from transition zone

was pumped outside to another tank for further settling and the sludge was taken to drums for

solidification process. Clean liquid was evaluated according to EPA limits for discharging to

environment and discharged. Transition zone liquid was remained for two weeks for further

settling and upper clean liquid was taken for analyze and discharge. Sludge was taken to drums

for solidification process. Drums were transported to waste processing facility. Total amounts of

the sludge and liquid was shown in Table I.

5
WM2012 Conference, February 26- March 1, Phoenix, AZ

Table I. In-Situ Chemical Precipitation Process.

In-Situ Chemical Precipitation Process Volume Specific activities (Bq/lt)

(liter) Cs-134 Cs-137 Co-60
Total liquid waste in the tank 35000 17.2 ± 1 2264 ± 113 9 ± 0.5
Decontaminated liquid after the first process 33550 1 ± 0.2 28 ± 1 0 ± 0.1
Transition zone liquid/sludge mix 600 6 ± 0.5 460 ± 50 2 ± 0.2
Sludge after the first process 850 12 ± 1 1780 ± 75 6 ± 0.3
Clean liquid at secondary settling tank 470 1 ± 0.2 10 ± 1 0 ± 0.1
Sludge at secondary settling tank 130 3 ± 0.3 450 ± 56 1 ± 0.1
Total discharged liquid 34020 2 ± 0.2 38 ± 5 1 ± 0.1
Total Sludge 980 15 ± 1 2210 ± 100 8 ± 0.3

Decontamination factor of each radionuclide was shown in Table II. At the end of this process,

97.2% of the liquid waste amount was decontaminated and discharged.

Table II. Decontamination Factors

Radionuclides Initial Specific Final Specific Decontamination Factor

Radioactivity (Bq/lt) Radioactivity (Bq/lt) (DF)
Cs-134 17.2 ± 1 2 ± 0.2 9
Cs-137 2264 ± 113 38 ± 5 60
Co-60 9 ± 0.5 1 ± 0.1 9

Solidification Process

Sludge drums were transferred to waste treatment facility. Liquid/solid ratio was determined as

0.80 lt/kg by using thermo analyzer. Cementation was used for solidification of the sludge.

Cement/water ratio was taken as 0.50. Water amount in the sludge (980 liters) was 784 liters.

300 kg cement with 60 kg sand was used for cementation. Cementation was applied in drums

by using in-drum mixing machine (Fig 3 and Fig 4).

6
WM2012 Conference, February 26- March 1, Phoenix, AZ

Fig 3. Radioactive sludge in drum.

Fig 4. In-drum mixer for cementation process.

After cementation process, 5 cm of each drum was filled with pure cement paste. Solidified

drums and samples were remained for 21 days in the facility for curing. After 21 days, uni-axial

compressive strength tests were applied on the samples. During cementation, samples were

taken from the mixture for mechanical tests. Samples for uniaxial compressive strength tests

were performed by preparation of mixtures and by using 50 mm diameter cylindrical molds with

a height of 120 mm. For uniaxial compressive strength tests, procedures were followed

according to American Society for Testing and Materials (ASTM C39-86) standard [13].

Preliminary testing of grout compressive strength is used as a classical method, which is

7
WM2012 Conference, February 26- March 1, Phoenix, AZ

practiced in civil engineering. NX type of cylindrical shaped grout samples with 50 mm diameter

and 120 mm height were prepared. Manual loading compressive test machine was used.

Uniaxial compressive strength of the samples was calculated as MPa and mechanical test

results were determined as in the range of 15-25 MPa. Mechanical stability level of cemented

waste form has vital importance in long term. In addition, leaching properties is other important

parameter for solidified waste form in radioactive waste management [14]. Surface radiation

rates of drums were measured between 150-250 µR/h. After surface contamination controls of

drums, final parameters were evaluated as convenient for transporting them safely to storage

facility.

RESULTS AND DISCUSSION

Although DF values of laboratory test were much higher than in-situ implementation, liquid

radioactive waste was decontaminated successfully by using potassium ferro cyanide. Majority

of liquid waste were discharged as clean liquid. %97.2 volumetric amount of liquid waste was

cleaned and discharged at the original site. Reduced amount of sludge transportation in drums is

more economical and safer method than liquid transportation. Although DF values could be

different for each of applications related to main specifications of original liquid waste, this study

shows that in-situ treatment of liquid waste by using potassium ferro cyanide is not only a cost

effective method but also reduce radiological risks as well.

REFERENCES

1. Avramenko, V.A.a , Voit, A.V.a , Golub, A.V.a , Dobrzhanskii, V.G.a , Egorin, A.S.a , Maiorov,

V.S.a , Sergienko, V.I.a , Shmatko, S.I.a , Korchagin, Yu.P.b. (2008). Hydrothermal reprocessing

of liquid radwastes from nuclear power plants. Atomic Energy,105, 150-154.

8
WM2012 Conference, February 26- March 1, Phoenix, AZ

2. Popov, L.a , Kuleff, I.b , Djingova, R.b. (2006). Determination of radiocesium in environmental

water samples using copper ferro(II)cyanide and sodium tetraphenylborate. Journal of

Radioanalytical and Nuclear Chemistry, 269, 203-207.

3. Mollah, A.S.a , Begum, A.a , Rahman, M.M.b. (1998). Removal of radionuclides from low level

radioactive liquid waste by precipitation. Journal of Radioanalytical and Nuclear Chemistry,

229, 187-189.

4. Lee, E.-H. , Lim, J.-G., Chung, D.-Y., Yang, H.-B., Kim, K.-W. (2010). Selective removal of Cs

and Re by precipitation in a Na2CO 3-H2O2 solution. Journal of Radioanalytical and Nuclear

Chemistry, 284, 387-395.

5. Mertz, J.L.a , Manos, E.J.a , Kanatzidis, M.G.a b. (2010). Selective radionuclide (Cs+, Sr2+,

and Ni 2+) ion-exchange by K2xMgxSn 3-xS6 (x=0.5-0.95) (KMS-2). Materials Research Society

Symposium Proceedings, 1265, 53-58.

6. Ibrahim G. M. (2010). Removal of Co-60 and Cs-134 radionuclides from aqueous solution

using titanium tungstate ion exchanger. Desalination and Water Treatment,13, 418-426.

7. Xu, C., Yuan, L., Shen, X. , Zhai, M., (2010). Efficient removal of caesium ions from aqueous

solution using a calix crown ether in ionic liquids. Mechanism and radiation effect. Dalton

Transactions,39, 3897-3902.

8. Taj, S., Muhammad, D., Chaudhry, M.A., Mazhar, M. (2011). Lithium, rubidium

and cesium ion removal using potassium iron(III) hexacyanoferrate(II) supported on

polymethylmethacrylate, Journal of Radioanalytical and Nuclear Chemistry,

288, 79-88.

9
WM2012 Conference, February 26- March 1, Phoenix, AZ

9. Zhang, C.-P.a , Gu, P.a , Zhao, J.b , Zhang, D.b , Deng, Y.b. (2009). Research on the

treatment of liquid waste containing cesium by an adsorption-microfiltration process with

potassium zinc hexacyanoferrate. Journal of Hazardous Materials,167,1057-1062.

10. Abd El-Latif, M.M. , Elkady, M.F. (2011). Kinetics study and thermodynamic behavior for

removing cesium, cobalt and nickel ions from aqueous solution using nano-zirconium vanadate

ion exchanger. Desalination, 271, 41-54.

11. Poirier, M.R.a , Hay, M.S.a , Herman, D.T.a , Crapse, K.P.a , Thaxton, G.D.b , Fink,

S.D. (2010). Removal of sludge heels in Savannah river site waste tanks with oxalic acid.

Separation Science and Technology, 451, 858-1875.

12. Duignan, M.R. , Nash, C.A. (2010). Removal of cesium from Savannah river site waste with

spherical resorcinol formaldehyde ion exchange resin: Experimental tests. Separation Science

and Technology, 451, 828-1840.

13. ASTM. (1986) Standard test method for compressive strength of cylindrical concrete

specimens. The American Society for Testing and Materials, ASTM C39-86.

14. Ojovan, M. I., Galina A. Varlackovab, Z. I., Golubevab, Burlakab, O. N.(2011).

Long-term field and laboratory leaching tests of cemented radioactive wastes. Journal of

Hazardous Materials, 187, 296-302.

10