sustainability

Article
Removal of Cs-137 from Liquid Alkaline High-Level Radwaste
Simulated Solution by Sorbents of Various Classes
Vitaly Milyutin 1 , Natalya Nekrasova 1 , Pavel Kozlov 2 , Arseni Slobodyuk 3 , Darya Markova 2 ,
Sergey Shaidullin 2 , Kirill Feoktistov 2 , Eduard Tokar 3 , Mikhail Tutov 3 and Andrei Egorin 3, *

1 Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky
Prospect, Moscow 1119071, Russia; [email protected] (V.M.); [email protected] (N.N.)
2 Mayak Production Assosiation, 31 Prospect Lenina, Ozersk 456780, Russia; [email protected] (P.K.);
[email protected] (D.M.); [email protected] (S.S.); [email protected] (K.F.)
3 Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, 159 Prosp. 100-letiya Vladivostoka,
Vladivostok 690022, Russia; [email protected] (A.S.); [email protected] (E.T.); [email protected] (M.T.)
* Correspondence: [email protected]

Abstract: The present work describes the results of the removal of cesium by sorbents of various
classes from highly mineralized alkaline solutions simulating the clarified phase of storage tanks
with high-level radioactive waste (HLW) of the Mayak Production Association. Within the scope of
the performed works, inorganic sorbents of the Clevasol® and Fersal brands, as well as resorcinol-
formaldehyde ion-exchange resins (RFRs: RFR-i, RFR-Ca, and Axionit RCs), were used. The sorbents’
characteristics under both static and dynamic conditions are presented. The Fersal sorbent has
demonstrated the best sorption characteristics in the series of sorbents under study. The disadvantage
of inorganic sorbents is the loss of mechanical strength upon cesium desorption, which complicates
their repeated use. It has been demonstrated that RFRs, despite their lower selectivity towards
cesium and adsorption capacity, can be used many times in repeated sorption-desorption cycles. The
latter makes RFRs more technologically attractive in terms of the total volume of decontaminated
Citation: Milyutin, V.; Nekrasova, N.;
HLW. However, RFRs tend to be oxidized during storage, which results in the formation of carboxyl
Kozlov, P.; Slobodyuk, A.; Markova,
D.; Shaidullin, S.; Feoktistov, K.;
groups and a decrease in sorption characteristics—this must be further taken into account in the real
Tokar, E.; Tutov, M.; Egorin, A. processes of liquid radioactive waste (LRW) management.
Removal of Cs-137 from Liquid
Alkaline High-Level Radwaste Keywords: selective sorbents; resorcinol–formaldehyde resin; adsorption; cesium; liquid
Simulated Solution by Sorbents of radioactive waste
Various Classes. Sustainability 2023,
15, 8734. https://doi.org/10.3390/
su15118734
1. Introduction
Academic Editors: Michael I. Ojovan,
Vladislav A. Petrov and Sergey The necessity to process liquid alkaline high-level wastes (HLW) from storage tanks
V. Yudintsev of the Mayak Production Association and, subsequently, transfer them to a stable matrix
form is an important and urgent task. To process HLW, schemes were suggested involving
Received: 29 April 2023 the sorption removal of Cs-137 as the main dose-forming radionuclide of the waste from
Revised: 20 May 2023
the supernatant. After removal of Cs-137, the decontaminated waste can be solidified
Accepted: 25 May 2023
by cementation, resulting in solid waste in the intermediate-level category (ILW). The
Published: 29 May 2023
ferrocyanide sorbent FS-10 was chosen for the selective removal of Cs-137 from HLW [1].
However, the disadvantage of using the FS-10 sorbent consists in the need for preliminary
neutralization of HLW to pH 6–8 due to the fact that sorbents based on poorly soluble
Copyright: © 2023 by the authors.
transition metal ferrocyanides undergo destruction in alkaline media [2]. For this reason,
Licensee MDPI, Basel, Switzerland. the search continues for sorption materials capable of selectively removing Cs-137 from
This article is an open access article alkaline HLW without prior neutralization.
distributed under the terms and As the above-mentioned sorption materials, one can consider resorcinol-formaldehyde
conditions of the Creative Commons resins (RFR), which at present are actively used to remove cesium from alkaline radioactive
Attribution (CC BY) license (https:// waste streams [3]. The selectivity of RFR towards some single-charge cations changes as fol-
creativecommons.org/licenses/by/ lows: Na+ < K+ < Rb+ < Cs+ < H+ [4]. This property makes it possible to reversibly remove
4.0/). cesium from alkaline LRW with subsequent desorption with suitable acid solutions [5–7].

Sustainability 2023, 15, 8734. https://doi.org/10.3390/su15118734 https://www.mdpi.com/journal/sustainability

Sustainability 2023, 15, 8734 2 of 17

The mechanism of cesium adsorption is related to the occurrence of ion exchange on

deprotonated functional groups [8]. The selectivity of ion-exchange resins towards cesium
can be explained by the predominance of the stage of transfer of alkaline metal cations from
the liquid phase of the polymer to its solid phase over the stage of electrostatic binding with
ion-exchange groups [9,10]. Another model explaining the nature of selectivity suggests
that swelling in alkaline media results in an increase in the osmotic pressure in the resin
and, consequently, a tension in the polymer network. Sorption of low-hydration cesium
and rubidium is preferential in comparison with that of sodium and potassium, as it allows
reducing the polymer network tension [11].
Sphere-granulated RFRs (sRFR) became widely used [12–14] due to their advantage of
reducing hydrodynamic resistance as well as greater mechanical strength as compared to
granular ion-exchangers [14–16]. To solve the problem of RFR oxidation in alkaline media,
samples with improved chemical resistance and selectivity to cesium were prepared [7].
Inorganic sorbents can serve as a cheaper and more effective alternative for selective
ion-exchange resins to solve the problem of treating LRW with complex chemical composi-
tion. The Clevasol® sorbent, commercially manufactured by the French company LEMER
PAX Innovative, can be considered as such an alternative. The sorbent is marketed as an
effective material for the removal of radionuclides from solutions in a broad pH range [17].
The Clevasol® sorbent comprises a polymer structure with high selectivity to a number
of cations, especially cesium, silver, and thallium [18]. Due to its mechanical strength and
large particle size, the sorbent can be used under dynamic conditions as a load for adsorp-
tion columns. It was shown that the Clevasol® sorbent effectively removed Cs+ from nitric
acid solutions at concentrations of 1–8 mol/dm3 (Kd for Cs+ greater than 104 cm3 /g) [19].
Composite sorbents were prepared by embedding the Clevasol® sorbent particles into the
polyvinyl alcohol (PVA) cryogel [20]. According to the authors, this material can be used
as part of anti-migration barriers due to its high distribution coefficients for Cs+ and Sr2+ .
The information on the sorbent composition and a detailed mechanism of the adsorption
process is a commercial secret of the LEMER PAX Innovative company.
The Institute of Physical Chemistry and Electrochemistry RAS, in collaboration with
Komfinservis LLC, has developed a novel inorganic sorbent of the Fersal brand based on
modified nickel ferrocyanide selective to cesium ions. Insoluble ferrocyanides of transition
metals and sorbents on their basis demonstrated good results in the processes of cesium
ion removal. The mechanism of cesium adsorption on ferrocyanides of transition metals
is known in detail and is related to the exchange of potassium and, partially, transition
metals by cesium [21–23]. Despite the fact that the sorption-active phase of a sorbent is
represented by nickel ferrocyanide, earlier performed tests demonstrated the possibility of
cesium removal from alkaline solutions [24].
The above-mentioned materials can be used in the processes of decontamination of
highly mineralized alkaline LRW from cesium. However, to choose the most effective
sorbent in order to optimize the LRW treatment process, it is necessary to compare their
sorption characteristics towards cesium under identical experimental conditions simulating
the real ones to a maximal degree. The earlier published results on cesium removal from
liquid media do not enable one to conduct this comparison since they were obtained under
different experimental conditions using different criteria of efficiency assessment. At the
same time, despite the encouraging prospects of the available sorption materials for HLW
treatment, there is a necessity for a preliminary assessment of the sorption characteristics
and features of the cesium extraction process on the mentioned sorption materials under
practically real-life conditions. The present work was devoted to the study of the physical-
chemical and sorption characteristics of RFRs: RFR-i, RFR-Ca, and Axionit RCs, as well as
inorganic sorbents Clevasol® and Fersal, in order to determine the most promising of them
in terms of the decontamination of alkaline HLW from cesium radionuclides.
Sustainability 2023, 15, 8734 3 of 17

2. Materials and Methods

2.1. Sorbents
The following resorcinol-formaldehyde ion exchange resins were used in the present
work:
- Axionit RCs, the sample was synthesized and provided for experiments by JSC
“Axion—Rare and Noble metals”. Two batches of RFR, synthesized in 2017 (Axionit
RCs 2017) and 2022 (Axionit RCs 2022), respectively, were used in the study.
- RFR-i is an experimental laboratory sample, synthesized and provided for testing
by the Institute of Chemistry of the Far Eastern Branch of the Russian Academy of
Sciences (Vladivostok, Russia).
- RFR-Ca is an experimental laboratory sample with a porous surface morphology,
synthesized and provided for testing by the Institute of Chemistry of the Far Eastern
branch of the Russian Academy of Sciences (Vladivostok, Russia).
The following inorganic sorbents were used in the present work:
- Sorbent of the Fersal brand, an inorganic composite sorbent based on modified nickel
ferrocyanide. According to the X-ray fluorescence analysis data, the sorbent contains
%: N—24.38; O—56.83; Si—9.46; K—0.20; Fe—1.87; Ni—2.86; Cs—3.65. It is supplied
in the K+ —form. The cesium sorption proceeds through the exchange of K+ ions in
the sorbent phase with the Cs+ ions in the solution. The sorbent is manufactured by
the LEMER PAX Innovative company, France. A sample for tests was provided by the
official distributor of this sorbent in Russia—Komfinservis LLC (Russia).
- Sorbent of the Clevasol® brand, a macroporous inorganic polymer. According to the
X-ray fluorescence analysis data, the sorbent contains %: B—83.0; O—6.27; Na—0.46;
S—6.86; Cl—3.44. It is supplied in the H+ —form. The cesium sorption proceeds
through the exchange of H+ ions in the sorbent phase by the Cs+ ions in the solu-
tion. The sorbent is manufactured by the LEMER PAX Innovative company, France.
A sample for testing was provided by the official distributor of this sorbent in
Russia—Komfinservis LLC (Russia).
Figure 1 shows SEM images of the sorbents under study. Resorcinol-formaldehyde
resins comprise monolithic, glasslike structures. The sorbent Axionit RCs 2022 comprises
regular spherical granules with smooth surfaces. The sorbents RFR-i and RFR-Ca are
represented by granules of an irregular shape with surface chips formed during grinding.
A specific feature of the sorbent RFR-Ca is the presence of micropores formed as a result of
the dissolution of a part of CaCO3 preliminarily introduced into the oligomeric phase at
the initial synthesis stage.
The sorbent of the Clevasol® brand is represented by granules of an irregular shape,
containing large fissures and cracks. Granules of the Clevasol® sorbent are formed through
the agglomeration of smaller particles of irregular and spherical shapes. Granules of the
Fersal sorbent are monolithic and do not contain fissures and cracks. As can be seen on
the insert with large magnification, the surface of the Fersal sorbent granules includes
pores with an average diameter of 5–6.5 µm, which probably ensures high accessibility of
adsorption sites.
The resorcinol-formaldehyde resins Axionit RCs, RFR-i, and RFR-Ca were converted
to a working sodium form prior to the experiments and sequentially treated with the
following under static conditions: HNO3 solution with a concentration of 1 mol/dm3 ,
distilled water, and NaOH solution with a concentration of 1.0 mol/dm3 . Then the sorbents
were washed with distilled water and dried in the air at a temperature of 60 ◦ C to a constant
weight. The Clevasol® and Fersal sorbents were preliminary sieved to obtain a fraction of
0.25–0.50 mm and then dried in air at a temperature of 60 ◦ C to a constant weight.
Sustainability 2023, 2023,
Sustainability 15, x 15,
FOR PEER REVIEW
8734 4 of 18
4 of 17

(a) (b) (c)

(d) (e)
Figure 1. SEM
Figure images
1. SEM imagesofofsorbents,
sorbents, (a) Clevsol,(b)
(a) Clevsol, (b)Fersal,
Fersal,(c)(c) RFR-i,
RFR-i, (d) (d) RFR-Ca,
RFR-Ca, (e) Axionit
(e) Axionit RCs 2022.
RCs 2022.

The bulk weight 3

The sorbent of the(dClevasol
bw, g/cm ®) brand
of the sorption materialsby
is represented was calculated
granules by Formula
of an irregular(1): shape,
containing large fissures and cracks. Granulesmofs the Clevasol® sorbent are formed through
the agglomeration of smaller particles of=irregular
dbw , (1)
V(dry) and spherical shapes. Granules of the
Fersal sorbent are monolithic and do not contain fissures and cracks. As can be seen on
insertmwith
thewhere s is the massmagnification,
large of the sorbent (g) and
the V (dry) isofthe
surface thevolume
Fersalofsorbent
dry sorption material
granules includes
3
(cmwith
). Theanarithmetic
pores average mean of theofthree
diameter parallel
5–6.5 definitions
µm, which was taken
probably as thehigh
ensures test result, and
accessibility of
the relative
adsorption sites. discrepancy should not exceed 5%.
The specific volume value (V specvol, cm3 /g) was calculated by Formula (2):
The resorcinol-formaldehyde resins Axionit RCs, RFR-i, and RFR-Ca were converted
to a working sodium form prior to the experiments V(svel) and sequentially treated with the fol-
lowing under static conditions: HNO(specvol V =
3 solution with , 3 (2)
)
ms a concentration of 1 mol/dm , distilled
water, and NaOH solution with a concentration of 1.0 mol/dm . Then the sorbents were 3

washed V (svel)distilled
where with is the volume
waterofandthe swollen
dried insorption
the airmaterial (cm3 ).
at a temperature of 60 °C to a constant
weight.The Thearithmetic
Clevasolmean® andof three sorbents
Fersal parallel definitions was takensieved
were preliminary as the test result, and
to obtain the
a fraction of
relative discrepancy must not exceed 5%
0.25–0.50 mm and then dried in air at a temperature of 60 °C to a constant weight.
Table 1 shows the physical-chemical characteristics of the sorption materials; errors
The bulk weight (dbw, g/cm3) of the sorption materials was calculated by Formula (1):
do not exceed 5%. A characteristic difference between ion-exchange resins and inorganic
sorbents is their significant swelling, which 𝑚
𝑑bwincreases
= 𝑠 ,during the transition from distilled (1)
𝑉(dry)
water to an alkaline model solution and must be taken into account when using this
class of sorption materials. Strong swelling may be accompanied by an increase in the
where ms is the mass of the sorbent (g) and V(dry) is the volume of dry sorption material
hydrodynamic resistance of the stationary sorbent layer, as well as the rupture of the
(cmcolumn;
3). The arithmetic mean of the three parallel definitions was taken as the test result,
therefore, ion-exchange resins were soaked under a layer of distilled water before
andthe
the relative discrepancy should not exceed 5%.
experiment.
The specific volume value (Vspecvol, cm3/g) was calculated by Formula (2):
𝑉(svel)
𝑉(specvol) = , (2)
𝑚𝑠

where V(svel) is the volume of the swollen sorption material (cm3).

The arithmetic mean of three parallel definitions was taken as the test result, and the
relative discrepancy must not exceed 5%
Sustainability 2023, 15, 8734 5 of 17

Table 1. Physical and chemical characteristics of the studied sorption material.

The Value of the Indicator for the Sorbent

Indicator
RFR-Ca RFR-i Axionit RCs Fersal Clevasol
Granule size (mm) 0.25–1.0 0.25–1.0 0.25–0.80 0.25–3.0 0.25–1.0
Bulk weight (g/cm3 ) 0.61 0.68 0.82 0.53 0.52
dbw (cm3 /g) 1.63 1.47 1.22 1.87 1.92
V (specvol) (cm3 /g) 2.73 2.08 3.29 1.87 1.92
V (specvol) in model solution * (cm3 /g) 2.87 2.16 3.40 1.87 1.92
* HLW simulated solution.

2.2. Compositions of Model Solutions

The sorption characteristics of Cs-137 were evaluated using model solutions of the
following composition:
• NaNO3 solutions of concentrations at 0.5, 1.0, 2.0, and 3.0 mol/dm3 , pH = 13. pH
adjustment was carried out with NaOH solution;
• KNO3 solutions of concentrations at 0.1, 0.25, 0.5, and 1.0 mol/dm3 , pH = 13. pH
adjustment was carried out with NaOH solution;
• NaOH + NaNO3 solutions with constant sums of concentrations of NaOH + NaNO3 =
3.5 mol/dm3 , containing 0.1, 0.25, 0.50, 1.0, 1.5, and 2.0 mol/dm3 of NaOH and 3.4,
3.25, 3.0, 2.5, 2.0, and 1.5 mol/dm3 of NaNO3 ;
• Model solution simulating the clarified phase of HLW storage tanks of the Mayak Pro-
duction Association with the following composition, g/dm3 : NaOH—100, NaNO3 —128,
Al(NO3 )3 × 9H2 O—82.5 (6.0 by Al), K2 CrO4 —7.72, CsNO3 —0.0733 (0.050 by Cs),
density—1.190 g/cm3 [1].
Model solutions were prepared by dissolving the corresponding salts in distilled water.
Sodium hydroxide was introduced as a concentrated solution.
Prior to the sorption experiments, the model solutions were labeled with Cs radionu-
clide in an amount of about 105 Bq/dm3 and then held for more than 3 days to achieve
equilibrium between the active and inactive components of the solution. The specific
activity of Cs-137 was determined by a direct radiometric method on the 661 keV gamma
line using the SCS-50M spectrometric complex (Green Star Technologies, Russia). The
geometry of the measuring sample was a Petri dish, the sample volume was 20 ± 2 cm3 ,
the measurement time was 300 s, and the relative error of measuring activity was no more
than 15%.
The C-13 NMR spectra of the polymers in the solid phase were recorded using a Bruker
Avance AV-300 spectrometer (Rheinstetten, Germany) with a proton resonance frequency
of 300 MHz. To record the spectra, the method of rotating samples at a magic angle (MAS)
was used. Tetramethylsilane was used as a standard for carbon nuclei. The chemical shift
reference (CS) was set in a separate experiment. The determination error for chemical shift
(CS) was 0.3 ppm, while for the intensity of the spectral line it was 5% of its area. The
spectra were recorded at 300 K.

2.3. Evaluation of Sorption Characteristics under Static Conditions

Sorption characteristics under static conditions were evaluated as follows: A sample
weight of air-dry sorption material of 0.10 ± 0.01 g was placed in a polyethylene container,
into which 20 cm3 of the model solution was poured (W/T ratio = 200 cm3 /mg), after
which it was stirred for 24 h. After that, the solid phase was separated from the solution
by filtering through a white ribbon paper filter, and the specific activity of Cs-137 was
determined in the filtrate.
Sustainability 2023, 15, 8734 6 of 17

Based on the results of the analyses, the values of the distribution coefficient (Kd )
Cs-137 were calculated; see Equation (3).

A0 − A(resact) V(solut)
Kd = × , (3)
A(resact) ms

where A0 and A(resact) are the initial specific activity of Cs-137 in the solution and the
residual activity of Cs-137 in the solution after sorption, respectively (Bq/cm3 ), and V (solut)
is the volume of the liquid phase (cm3 ).
The value of static exchange capacity (SEC, mg/cm3 ) in solutions with a macro con-
centration of stable cesium was calculated using Equation (4):

C0 − C(resid) × V(solut)
SEC = , (4)
ms × V(specvol)

where C0 and C(resid) are the initial and residual concentrations of cesium in solution,
respectively (mg/cm3 ).
The measurement error for the confidence probability 0.95 (p < 0.05) was estimated
on the basis of three parallel measurements of the solution gamma-activity using the
one-sample t-criterion.

2.4. Evaluation of Sorption Characteristics under Dynamic Conditions

Sorption characteristics under dynamic conditions were evaluated as follows: First,
3.0 cm3 of the sorption material held under a layer of water for more than 12 h was trans-
ferred to a polypropylene sorption column with an inner diameter of 8.5 mm. Percolation of
the HLW model solution was carried out by a peristaltic pump from Longerpump (China),
model BQ-50J at a speed of 10.0 ± 0.5 cm3 /h. The rate of solution percolation was selected
based on the fact that to establish equilibrium under dynamic conditions, the contact time
must be at least 10t0,5 , where t0,5 is the time of half-exchange. Based on the data of [25],
the time of half-exchange of cesium ions on selective absorbents is about 1–2 min, so the
contact time must be at least 20 min, which corresponds to the specific filtration rate of
3 BV/h.
Filtrates after the column were collected by fractions, and the residual specific activity
of Cs-137 was determined. Based on the results of the filtrate analysis, the output adsorption
curves were constructed in coordinates f (DF) = BV, where BV is the bed volume calculated
as the ratio of the sorbent volume in the column (cm3 ) to the volume of the solution being
passed (cm3 ), and DF is the decontamination factor for dynamic conditions, which was
calculated by the Formula (5):
A0
DF = , (5)
A(filtrate)

where A(filtrate) is the specific residual activity of Cs-137 in the filtrate (Bq/cm3 ).
When using an HLW simulated solution containing stable cesium, the dynamic ex-
change capacity up to reaching a given slip (DEC, mg/cm3 ) was calculated as an integral of
the dependence of the amount of adsorbed cesium on the amount of the fed solution (6).
  
Z n C0 − C(filtrate) V(i)
DEC = f dV(t) , (6)
0 V(svel)

where C(filtrate) is the residual concentration of cesium in the i-th fraction of the eluate
(mg/cm3 ), V (i) is the volume in the i-th fraction of the eluate (cm3 ), m is the mass of the
sorbent (g), an dV (t) is the volume of the fed solution (cm3 ).
Sustainability 2023, 15, 8734 7 of 17

To determine the total dynamic exchange capacity (TDEC, mg/cm3 ) for the output
curves of cesium adsorption in coordinates f (C(filtrate) /C0 ) = t, the Thomas model (7)–(9)
was used as follows:
C(filtrate) 1
= , (7)
C0 1+e a − b × t )
(

KTh × TDEC × m
a= , (8)
Q

b = KTh × C0 , (9)
where KTh is the adsorption rate constant (cm3 /mg × h), m is the mass of the sorbent (g),
Q is the volume rate of the solution (cm3 /h), and t is the duration of the experiment (h).
The experimental data were processed using Veusz software (ver. 3.4) [26].

2.5. Desorption of Cs-137 and Regeneration of Sorbents

After the sorption of Cs-137 from the HLW simulated solution was completed, the
sorbent in the column was washed with distilled water with a volume of 30 cm3 at a
rate of 6–9 cm3 /h to remove the residues of the solution. Then a desorbing solution was
fed through the column with the washed sorbent using a peristaltic pump at a rate of
2.5–3.0 cm3 /h (0.8–1.0 BV/h). The eluates after the column were collected by fractions,
and the residual specific activity of Cs-137 in them was determined. Based on the results
of the filtrate analysis, the output desorption curve was constructed with the coordinates
Des% = f (BV). The degree of desorption of cesium (Des, %) under dynamic conditions was
calculated by the Equation (10):

∑1i V(el) × C(eluate)

!
Des% = × 100, (10)
CDEC

where C(eluate) is the concentration of the cesium in the i-th fraction of the eluate (mg/cm3 ),
V (el) is the volume of the eluate (cm3 ), CDEC is the amount of the adsorbed cesium (mg),
and i is the ordinal number of the eluate fraction.
For the repeated sorption of cesium, the RFR-i and RFR-Ca ion exchange resins were
washed with water to remove acid residues and treated with a 1.0 M NaOH solution to
transform them into sodium form. The volume of a 1.0 M NaOH solution was 30 cm3 , and
the transmission rate of the solution was 2.5 cm3 /h.
Under dynamic conditions, the error with the confidence probability 0.95 (p < 0.05)
for a single measurement of the solution gamma-activity was determined using the
Equation (11). √
n
SD = × 1.96 (11)
t
where n is the quantity of registered impulses and t is the measurement time (min).

3. Results and Discussion

Figure 2 shows the results for the values of the Cs-137 distribution coefficients and the
static cesium capacity for various sorbents during sorption from a model HLW solution
containing a stable cesium isotope in macro concentrations. Based on the results obtained,
the efficiency of the sorption materials in terms of cesium removal from the HLW simulated
solution under static conditions can be put in the following order: Fersal > RFR-i > Axionit
RCs 2022~RFR-Ca > Axionit RCs 2017 > Clevasol® . One should mention that the storage of
Axionit RCs ion exchange resin for 5 years led to a decrease in SEC by 10% and Kd Cs-137
by 25% due to oxidation processes that negatively affected sorption characteristics [27]. In
order to exclude the oxidation of RFR for a long time, the storage must be carried out in an
inert nitrogen atmosphere at a pressure of 0.26 bar [28].
Sustainability 2023, 15, x FOR PEER REVIEW 8 of 18

Kd Cs-137 by 25% due to oxidation processes that negatively affected sorption characteris-
Sustainability 2023, 15, 8734 8 of 17
tics [27]. In order to exclude the oxidation of RFR for a long time, the storage must be
carried out in an inert nitrogen atmosphere at a pressure of 0.26 bar [28].

(a) (b)
Figure
Figure2.2.Sorption-selective
Sorption-selectivecharacteristics
characteristicsofofthe
thesorption
sorptionmaterials
materialsunder
understudy
studyininthe
theHLW
HLWsimu-
simu-
lated
latedsolution:
solution:(a)
(a)SEC,
SEC,(b)
(b)value
valueofofKKd dCs-137.
Cs-137.

The
Thedependencies
dependenciesof ofthe
thevalues
valuesof ofthetheCs-137
Cs-137distribution
distributioncoefficients
coefficientson onthe
thestudied
studied
sorbents
sorbentson onthe
theconcentration
concentrationofof NaNO
NaNO 3, KNO
3 , KNO 3, and NaOH
3 , and NaOH are are
shown
shownin Figure 3. For
in Figure 3. the
For
Axionit RCs 2022
the Axionit RCs ion
2022exchange
ion exchangeresin, curves are not are
resin, curves presented since itssince
not presented sorption charac-
its sorption
characteristics
teristics are similar
are similar to thosetoof those of RFR-Ca.
RFR-Ca. According According to the presented
to the presented results,results,
when when
the con-the
concentration
centration of NaNO
of NaNO 3 and 3 and
KNO KNO
3 increases,
increases,
3 the the
values values
of K d of K
Cs-137
d Cs-137 naturally
naturally decreasedecrease
due
due
to an to an increase
increase in competitive
in competitive adsorption.
adsorption. In NaNOIn NaNO 3 solutions,
3 solutions, the highest
the highest valuesvalues Kd
of KdofCs-
Cs-137
137 werewere obtained
obtained for for
thethe sorbents
sorbents Fersal,
Fersal, RFR-i,
RFR-i, andand RFR-Ca.
RFR-Ca. Onecan
One cannotenotethat,
that,ininthe
the
presenceof
presence Na++ions,
ofNa ions,the valuesofofKKd dCs-137
thevalues Cs-137for fordifferent
differentsorbents
sorbentsare aresimilar
similarexcept
exceptforfor
Clevasol®®and
Clevasol andAxionit
AxionitRCs 2017.KK+ +ions
RCs2017. ionsmanifest
manifestaagreater
greatercompetitive
competitiveeffect effectthan
thanNa Na++, ,
thusreducing
thus reducingthe theKKddCs-137
Cs-137values
valuesby by0.5
0.5orders
ordersof ofmagnitude
magnitudeon onaverage.
average.The Theexception
exception
is the Fersal sorbent, whose efficiency is equally high in both NaNO
is the Fersal sorbent, whose efficiency is equally high in both NaNO33and KNO33solutions and KNO solutions
due to its extremely high selectivity towards Cs + +ions. With an increase in the concentration
due to its extremely high selectivity towards Cs ions. With an increase in the concentra-
of NaOH,
tion of NaOH, Kd K
thethe Cs-137
d Cs-137 value
value for
forthe
theFersal
Fersalsorbent
sorbentgradually
gradually decreases, while for
decreases, while forthe
the
ion-exchangeresins
ion-exchange resinsAxionit
Axionit RCs,
RCs, RFR-I,
RFR-I, and and RFR-Ca,
RFR-Ca, on the
on the contrary,
contrary, the efficiency
the efficiency of Cs-of
Cs-137 extraction increases. This is related to an increase in the
137 extraction increases. This is related to an increase in the degree of deprotonation of degree of deprotonation of
functional hydroxyl groups as the concentration of hydroxide
functional hydroxyl groups as the concentration of hydroxide ions increases [11]. ions increases [11].
Figure 4 shows the output curves of the dependence of the decontamination factor
on the volume of the fed solution (bed volumes). The sorption characteristics of RFR-I
and RFR-Ca ion exchange resins were additionally tested in three consecutive sorption
cycles (Figure 3b). The dependence curves f (DF) = BV were interpolated by the Akima
spline, which was later used to determine the number of bed volumes fed before reaching
a preset cesium breakthrough into the filtrate. For the sorbents Fersal, RFR-I, and RFR-Ca,
50% cesium breakthrough was calculated using the Thomas model (Equation (7)), since the
obtained curves of the efficiency of Cs-137 extraction from the model HLW solution did not
reach the set values.
To understand the processes of oxidation of RFRs during storage in air, NMR spectra
of C-13 (Figure 5) were obtained, as well as those of RFR-I, which was stored in H-form in
plastic containers for 6, 15, and 21 months.
Table 2 shows the values of chemical shifts and the corresponding peak areas. Relative
integral intensities of the spectrum components were determined by fitting a calculated
resonance line to the experimental one using the least squares method by means of inde-
pendently developed software.
 Sustainability 2023, 15, 8734 9 of 17
Sustainability 2023, 15, x FOR PEER REVIEW 9 of 18

(a) (b) (c)

Figure
Figure 3. Dependence of 3.
theDependence of the
distribution distribution
coefficient coefficient
of Cs-137 of Cs-137
on the on the concentration
concentration of (a) NaNO of (a)
, NaNO3,
Sustainability 2023, 15, x FOR PEER REVIEW (b) KNO3, (c) NaOH. 10 of 18 3
(b) KNO3 , (c) NaOH.
Figure 4 shows the output curves of the dependence of the decontamination factor
on the volume of the fed solution (bed volumes). The sorption characteristics of RFR-i and
RFR-Ca ion exchange resins were additionally tested in three consecutive sorption cycles
(Figure 3b). The dependence curves f(DF) = BV were interpolated by the Akima spline,
which was later used to determine the number of bed volumes fed before reaching a preset
cesium breakthrough into the filtrate. For the sorbents Fersal, RFR-i, and RFR-Ca, 50%
cesium breakthrough was calculated using the Thomas model (Equation (7)), since the
obtained curves of the efficiency of Cs-137 extraction from the model HLW solution did
not reach the set values.

(a) (b)
Figure
Figure4.4.Curves
Curvesofofthe
thedependence
dependenceofofthethedecontamination
decontaminationfactor
factorononthe
thevolume
volumeofofthe
thefed
fedmodel
model
solution: (a) sorbents Fersal, Clevasol ,
®® Axionit RCs 2017, Axionit RCs 2022, (b) removal of
solution: (a) sorbents Fersal, Clevasol , Axionit RCs 2017, Axionit RCs 2022, (b) removal of Cs-137Cs-137in
inthree
threerepeated
repeatedsorption
sorptioncycles
cyclesononRFR-I
RFR-iand
andRFR-Ca.
RFR-Ca.

To understand the processes of oxidation of RFRs during storage in air, NMR spectra
of C-13 (Figure 5) were obtained, as well as those of RFR-i, which was stored in H-form in
plastic containers for 6, 15, and 21 months.
 Figure 4. Curves of the dependence of the decontamination factor on the volume of the fed model
solution: (a) sorbents Fersal, Clevasol®, Axionit RCs 2017, Axionit RCs 2022, (b) removal of Cs-137
in three repeated sorption cycles on RFR-i and RFR-Ca.

To understand the processes of oxidation of RFRs during storage in air, NMR spectra
Sustainability 2023, 15, 8734 10 of 17
of C-13 (Figure 5) were obtained, as well as those of RFR-i, which was stored in H-form in
plastic containers for 6, 15, and 21 months.

(a) (b)
Figure
Figure5.5.C-13 NMR
C-13 NMR spectra of RFRs;
spectra (a) RFR-i,
of RFRs; (b) Axionit
(a) RFR-i, RCs,RCs,
(b) Axionit 1—RFR-i stored
1—RFR-i for 6 months,
stored 2—
for 6 months,
RFR-i stored for 15 months, 3—RFR-i stored for 21 months, 4—Axionit RCs 2017, 5—Axionit
2—RFR-i stored for 15 months, 3—RFR-i stored for 21 months, 4—Axionit RCs 2017, 5—Axionit RCs RCs
2022.
2022.Asterisks
Asterisksmark
markthe
thespinning
spinningsidebands.
sidebands.

Table 2. Values of chemical shifts and corresponding peak areas on the C-13 NMR spectra of the RFRs.

RFR-i Stored for RFR-I Stored for RFR-I Stored for

Organic Axionit RCs 2018 Axionit RCs 2022
21 Months 15 Months 6 Months
Group
Area (%) * CS, ppm * Area (%) CS, ppm Area (%) CS, ppm Area (%) CS, ppm Area (%) CS, ppm
-CH2 -(4,60 ) 12.9 19.3 11.1 19.2 13.2 24.3 10.8 19.6 10.6 21
-CH2 -(4,20 ) 10.4 29.1 13.6 28.3 8.2 32.7 7.5 29.1 9.5 30.2
-CH2 -C6 H6 - - - - - - 6.7 40.2 7 42.1
-CH2 OH 8 50.6 6.5 52.2 10 56.2 5.9 51.7 6.8 53.8
hemiformals - - - - - - - - 2.1 91
C 2 , C6 2.7 105 3.9 104.8 6.7 106.6 - - - -
C4 32.3 117.9 22.1 120.8 26.9 120.1 31 117.6 29 119.2
C5 12.2 131.4 15.6 129.9 14.8 129.5 12.9 131.4 10.4 130.7
>C=C< - - - - - - 3.7 141 4.6 140.7
C 1 , C3 17.5 151.8 23.2 151.2 15.4 154.2 16.4 151.2 16.6 151.7
R-COO-,
4.1 160.1 4.1 159.1 4.7 160.9 5.1 160.2 3.3 158.2
>C=O
* Errors for the area fractions and CS values are ±2% and 0.3 ppm, respectively.

The C-13 NMR spectra of RFR-i and Axionit RCs revealed characteristic features
indicating a change in the molecular structure of ion-exchangers during storage. Axionit
RCs are characterized by the presence of an additional peak around 90.6 ppm related to
hemiformals [29], which, however, disappears during storage, probably due to oxidation
processes. In the spectrum of Axionit RCs, there are peaks around 42.1 and 140.9 ppm,
which were not described in the works on RFRs and can be attributed to the benzyl-
methylene radical [30] and alkenes [31], respectively. The presence of these peaks can be
explained by the impurities in the form of organic compounds used as an emulsifier to
produce spherical resin granules.
RFR-i is characterized by the presence of a peak around 106 ppm, which can be related
to the carbon of the aromatic ring of resorcinol both at the C2 position not associated with
the methylene bridge and at the C6 position [32]. The area of this peak gradually decreases
during the storage of ion-exchange resin, which can be explained by the formation of
para-quinone during oxidation with oxygen in the air [33].
Sustainability 2023, 15, 8734 11 of 17

A common feature of both ion exchange resin samples is a peak around 160 ppm,
which appears after 21 months of storage. This peak is presumably determined by the
formation of quinone and carboxylate groups [33,34]. The formation of carboxylates and
quinones during oxidation is probably one of the main reasons for the decrease in the
efficiency of Cs-137 extraction by RFRs.
Therefore, the negative effects of the RFR oxidation process are more pronounced
under dynamic conditions, making it impossible to use resin as a sorption load in columns.
Thus, during the decontamination of alkaline LRW, it is necessary to use fresh batches of
RFR, and the long-term storage must be carried out in an inert atmosphere.
According to the volume of the fed model solution before attaining the 50% cesium
breakthrough into the filtrate (DF 2, Table 3), the order of sorbents changes and looks as
follows: Fersal > RFR-i > RFR-Ca~Axionit RCs 2022 > Clevasol® . This can be explained by
the fact that, at high SEC values (Figure 2a), the efficiency of cesium removal by RFR-i resin
at the initial stage is presumably limited by mass transfer in the grain volume.

Table 3. The number of bed volumes of the solution passed before reaching the preset cesium
breakthrough into the filtrate.

Removal RFR-i RFR-Ca

Axionit Axionit
Efficiency RCs RCs Clevasol® Fersal Adsorption Cycle Adsorption Cycle
% DF 2022 2017 1 2 3 1 2 3
99 100 41 ± 2 0 22 ± 1 127 ± 6 30 ± 1 45 ± 2 89 ± 4 44 ± 2 31 ± 2 29 ± 1
95 20 56 ± 3 9 ± 0.5 27 ± 1 160 ± 8 50 ± 3 65 ± 3 157 ± 8 53 ± 3 40 ± 2 37 ± 2
90 10 63 ± 3 10 ± 0.5 32 ± 2 177 ± 9 63 ± 3 78 ± 4 195 ± 9 57 ± 3 45 ± 2 42 ± 2
50 2 83 ± 4 13 ± 0.5 45 ± 2 237 ± 12 * 117 ± 6 * 153 ± 8 298 ± 15 * 77 ± 4 73 ± 4 59 ± 3
* Values calculated using the Thomas model.

The disadvantage of the Fersal and Clevasol® sorbents is the loss of mechanical
strength during the desorption of cesium, which makes it impossible to reuse them. Gran-
ules of the ion-exchange resins RFR-i and RFR-Ca after desorption remained in their original
form and were used for the resorption of cesium.
Figure 6b shows the output sorption curves of Cs-137 on the ion exchange resins RFR-I
and RFR-Ca during the first, second, and third sorption cycles. During three repeated
sorption-desorption cycles using RFRs, changes in sorption characteristics are observed
(Table 3). For RFR-Ca, there is a decrease in the volume of the solution fed before reaching a
preset cesium breakthrough into the filtrate due to oxidation at low percolation rates of the
model HLW solution. On the contrary, for RFR-I, an increase in the sorption resource was
observed, which was associated with the gradual transition of the ion-exchange resin to the
operating mode. This transition can be associated with a number of reasons, such as the
gradual removal of potassium ions [35], non-reacted reaction products from the polymer
matrix, and an increase in the mass transfer rate in the bulk of the resin grain.
To calculate the theoretical value of TDEC, we used the output curves of the depen-
dence f (C/C0 ) = t (Figure 6), which were approximated by nonlinear regression using the
Thomas equation (Equation (7)). Table 4 shows the calculated parameters of the Thomas
model equation for the sorbents Fersal, RFR-I, and RFR-Ca. The coefficient of determina-
tion exceeds 0.95, which indicates a good agreement of the experimental values with the
Thomas model.
 (Table 3). For RFR-Ca, there is a decrease in the volume of the solution fed before reaching
a preset cesium breakthrough into the filtrate due to oxidation at low percolation rates of
the model HLW solution. On the contrary, for RFR-i, an increase in the sorption resource
was observed, which was associated with the gradual transition of the ion-exchange resin
to the operating mode. This transition can be associated with a number of reasons, such
Sustainability 2023, 15, 8734
as the gradual removal of potassium ions [35], non-reacted reaction products from12the of 17

polymer matrix, and an increase in the mass transfer rate in the bulk of the resin grain.

(a) (b)
Figure
Figure6. 6.
Dependence curves of C/C on time: ® ,RS
0 on (a) sorbents Fersal, Clevasol ®, Axionit 2017, Axionit
Dependence curves of 0C/C time: (a) sorbents Fersal, Clevasol Axionit RS 2017,
RS 2022, (b)
Axionit RS extraction of Cs-137of
2022, (b) extraction inCs-137
three repeated sorption cycles
in three repeated sorptiononcycles
RFR-ionand RFR-Ca;
RFR-I the dotted
and RFR-Ca; the
lines are curves obtained by the nonlinear regression equation of the Thomas model.
dotted lines are curves obtained by the nonlinear regression equation of the Thomas model.

Table 4. Calculated parameters of the Thomas model equation.

RFR-Ca RFR-i
Parameters of the
Adsorption Cycle Adsorption Cycle Fersal
Thomas Equation
1 2 3 1 2 3
a 7.7 ± 0.5 5.3 ± 0.3 7.8 ± 0.3 5.4 ± 0.2 4.3 ± 0.2 6.3 ± 0.4 9.1 ± 0.3
b 0.43 ± 0.03 0.24 ± 0.01 0.33 ± 0.01 0.15 ± 0.01 0.09 ± 0.01 0.7 ± 0.1 0.13 ± 0.01
R2 0.9961 0.9909 0.9972 0.9891 0.9886 0.9125 0.9943
KTh 3
(cm /mg × g) 8.69 4.79 6.55 3.03 1.84 1.42 2.54

For the Clevasol® and Axionit RCs sorbents, as the volume of the fed solution increases,
the value of the ratio C0 /C begins to exceed one (Figure 6a), which indicates the desorption
process, presumably associated with the chemical destruction of the sorbents. For this
reason, the Thomas model was not used for cesium output curves obtained with Clevasol®
and Axionit RCs sorbents.
The presence of a macro concentration of a stable isotope of cesium in the LRW imposes
high requirements for the sorption materials in regard to the value of the dynamic exchange
capacity. The latter is caused by the fact that, despite the high selectivity of the sorption
materials for cesium, along with a decrease in the value of the dynamic exchange capacity,
the volume of liquid waste decontaminated from cesium will also decrease.
To calculate the total dynamic exchange capacity, the experimental values were ex-
trapolated to the values of total cesium saturation using the Thomas equation with the
parameters given in Table 3. Figure 7 shows the theoretical integral curves obtained for the
saturation of sorbents with cesium under dynamic conditions.
 exchange capacity. The latter is caused by the fact that, despite the high selectivity of the
sorption materials for cesium, along with a decrease in the value of the dynamic exchange
capacity, the volume of liquid waste decontaminated from cesium will also decrease.
To calculate the total dynamic exchange capacity, the experimental values were ex-
trapolated to the values of total cesium saturation using the Thomas equation with the
Sustainability 2023, 15, 8734 13 of 17
parameters given in Table 3. Figure 7 shows the theoretical integral curves obtained for
the saturation of sorbents with cesium under dynamic conditions.

Figure 7.
Figure 7. Integral
Integral curves
curves of
of the
the adsorption
adsorption of
of cesium
cesium from
fromthe
theHLW
HLWsimulated
simulatedsolution.
solution.

Table 55 shows
Table shows the calculated values
values ofof the
the dynamic
dynamicexchange
exchangecapacity
capacitybefore
beforeattaining
attaininga
apreset
presetcesium
cesiumbreakthrough
breakthrough into
into thethe filtrate,
filtrate, as as well
well as as
thethe theoretical
theoretical values
values of the
of the totaltotal
dy-
dynamic capacity. According to the results obtained during the first cycle, the Fersal
namic capacity. According to the results obtained during the first cycle, the Fersal sorbent has sorbent
has the largest
the largest capacity
capacity for cesium
for cesium among among the other
the other investigated
investigated sorptionsorption materials.
materials.

Table 5. Values of the dynamic exchange capacity (mg/cm3 ) before reaching a preset cesium break-
through into the filtrate, and values of the total dynamic exchange capacity calculated using the
Thomas model.

Removal
RFR-Ca RFR-i
Efficiency
Axionit
Adsorption Cycle Adsorption Cycle Clevasol Fersal
RCs 2022
% DF
1 2 3 1 2 3
99 100 2.1 ± 0.1 1.5 ± 0.1 1.4 ± 0.1 1.5 ± 0.1 2.2 ± 0.1 2.2 ± 0.1 2.5 ± 0.1 1.0 ± 0.1 6.2 ± 0.3
95 20 2.6 ± 0.1 1.9 ± 0.1 1.8 ± 0.1 2.4 ± 0.1 3.1 ± 0.2 7.6 ± 0.4 1 2.9 ± 0.1 1.2 ± 0.1 7.8 ± 0.4
90 10 2.8 ± 0.1 2.2 ± 0.1 2.0 ± 0.1 3.0 ± 0.1 3.8 ± 0.2 9.3 ± 0.4 1 3.2 ± 0.2 1.5 ± 0.1 8.6 ± 0.5
50 2 3.4 ± 0.2 3.0 ± 0.2 2.5 ± 0.1 5.0 ± 0.3 1 6.31 ± 0.3 13.1 ± 0.8 1 3.8 ± 0.2 1.9 ± 0.1 10.8 ± 0.5 1
TDEC 3.8 ± 0.2 1 3.5 ± 0.2 1 2.8 ± 0.1 1 5.8 ± 0.3 1 7.61 ± 0.4 14.7 ± 0.8 1 4 ± 0.2 1 2 ± 0.1 2 11.7 ± 0.4 1
1 The value calculated using the Thomas model. 2 Maximum value before desorption.

The RFR-Ca resin is characterized by a decrease in the theoretical value of TDEC,

which is associated with chemical and physical degradation, whereas the accumulation
of ionizing radiation dose can also intensify this process [36]. RFR-I, with the number of
adsorption cycles increasing, is characterized by an increase in the theoretical value of
TDEC, which, at the third adsorption cycle, is comparable to the value obtained for the
Fersal sorbent. This indicates the high chemical stability of the RFR-I ion exchange resin
and its gradual transition to operating mode. The increase in the total dynamic exchange
capacity can also be explained by an increase in the number of exchange groups due to the
oxidation of methyl groups to carboxyl groups [37].
Solutions of HNO3 were used for the desorption of Cs-137. One should mention
that, at room temperature, 2.0–3.0 M solutions of HNO3 lead to changes in RFR after
24 h due to its nitration [38]. Nitration of RFRs with 0.5–1.0 M HNO3 solutions occurs
when heated to 55 ◦ C or after prolonged exposure for 70 days [38,39]. Nitration of RFRs is
accompanied by the destruction of the polymer matrix as well as a decrease in the sorption
capacity [40]. Therefore, in terms of the volume of the desorbing solution consumed, the
time of desorption, and the destruction of the polymer matrix, the optimal concentration
of the HNO3 solution is 1.0 mol/dm3 [6]. The solution of HNO3 at a concentration of
7.5 mol/dm3 was used as a desorbing solution for the sorbents Fersal and Clevasol® .
The rate of feeding of the desorbing solution was 2.3 cm3 /h (0.77 BV/h). The curves of
desorption of Cs-137 from various sorbents are shown in Figure 8.
Sustainability
Sustainability2023,
2023,15,
15,x 8734
FOR PEER REVIEW 15 14
of of1817

(a) (b)
Figure
Figure8.8.Cs-137
Cs-137desorption:
desorption:(a)(a)
integral
integraldesorption
desorptioncurves,
curves,(b)
(b)output
outputdesorption
desorptioncurves.
curves.Desorbing
Desorbing
solutions: 7.5 mol/dm 3 HNO3 used for Fersal and Clevasol® sorbents, 1.0 mol/dm3 HNO3 used for
solutions: 7.5 mol/dm3 HNO3 used for Fersal and Clevasol® sorbents, 1.0 mol/dm3 HNO3 used for
RFRs sorbents.
RFRs sorbents.

4. Conclusions
Ion-exchange resins have an advantage over inorganic sorbents in requiring solutions
withThe sorption
lower characteristics
concentrations of resorcinol-formaldehyde
of HNO 3 , which is important for resins Axionitthe
reducing Cs,corrosion
RFR-i, andof
RFR-Ca as well
equipment. Theascurves
inorganic sorbents
obtained of Clevasol® and
for ion-exchange Fersal
resins RFR-I brands towards
and RFR-Ca cesiumaions
indicate wide
indesorption front. This
model-simulated featureof
solutions could be associated
high-level alkalinewith a low
waste mass from
streams transfertherate
Mayakinside the
Pro-
resin grain
duction or a significant
Association have beendecrease of the The
evaluated. resinstudied
volumesorbents
due to a canlargebedifference
arrangedbetweenin the
bulk weight
following orderandinspecific
terms of volume value, which
their sorption leads to sorbent
characteristics in the compaction
HLW simulated in thesolution
column,
thus preventing
under the normal
static conditions: flow
Fersal of the desorbing
> RFR-i > Axionit solution. Despite some
RCs 2022~RFR-Ca differences,
Axionit RCs 2017 the
results presented
Clevasol. The Fersal insorbent
Figure 8isshow that, withbythe
characterized theexception of the Fersal
highest selectivity sorbent,
towards when
cesium
10 bed
ions. volumes
Along withofthetheincrease
HNO3 solution
in NaOH areconcentration
fed, the desorption efficiency
in solution, theexceeds 99%,ofwhich
efficiency the
is consistent with the known published data [3].
Fersal sorbent decreases, whereas that of resorcinol-formaldehyde resins increases. It has
been demonstrated that, under dynamic conditions, the resource of the Fersal sorbent un-
4. Conclusions
til the 1% cesium breakthrough is a minimum 2.5-fold larger in comparison with other
Thematerials.
sorption sorption Thecharacteristics
disadvantage of resorcinol-formaldehyde
of inorganic sorbents consists resinsofAxionit Cs,
a loss of RFR-i, and
mechanical
RFR-Ca as well as inorganic sorbents of Clevasol ® and Fersal brands towards cesium
strength upon cesium desorption by a 7.5 M solution of HNO3. Using RFRs, cesium can
beions in model-simulated
desorbed by a 1 V solution solutions
of HNOof high-level alkaline waste streams from the Mayak
3 without a loss of the granule’s mechanical strength.
Production Association have been evaluated.
Within three repeated sorption-desorption cycles, The studied
RFR-i has sorbents
the best canvalues
be arranged in the
of resource
following order in terms of their sorption characteristics in
and full dynamic exchange capacity, as compared with the porous RFR-Ca. A commonthe HLW simulated solution
under static of
disadvantage conditions: Fersal > RFR-i
RFRs is worsening > Axionit
of sorption RCs 2022~RFR-Ca
characteristics as a resultAxionit RCs 2017
of oxidation ac-
Clevasol. The Fersal sorbent is characterized by the highest selectivity
companied by the formation of quinone and carboxylate groups. Based on the obtained towards cesium ions.
Along one
results, withcantheconclude
increase that
in NaOH
in the concentration
decontamination in solution, the efficiency
of high-level wastes in of thethe Fersal
storage
sorbent decreases, whereas that of resorcinol-formaldehyde resins
tanks of the Mayak Production Association, the sorbent of the Fersal brand and the resor- increases. It has been
demonstrated that, under dynamic conditions, the resource of the
cinol-formaldehyde resin RFR-I can be used. However, taking into account repeated use Fersal sorbent until the
1% cesium breakthrough is a minimum 2.5-fold larger in comparison with other sorption
in sorption-desorption cycles and the total amount of the decontaminated HLW, resor-
materials. The disadvantage of inorganic sorbents consists of a loss of mechanical strength
cinol-formaldehyde resins can turn out to be more preferential.
upon cesium desorption by a 7.5 M solution of HNO3 . Using RFRs, cesium can be desorbed
by a 1 V solution of HNO3 without a loss of the granule’s mechanical strength. Within three
Sustainability 2023, 15, 8734 15 of 17

repeated sorption-desorption cycles, RFR-i has the best values of resource and full dynamic
exchange capacity, as compared with the porous RFR-Ca. A common disadvantage of
RFRs is worsening of sorption characteristics as a result of oxidation accompanied by the
formation of quinone and carboxylate groups. Based on the obtained results, one can
conclude that in the decontamination of high-level wastes in the storage tanks of the Mayak
Production Association, the sorbent of the Fersal brand and the resorcinol-formaldehyde
resin RFR-I can be used. However, taking into account repeated use in sorption-desorption
cycles and the total amount of the decontaminated HLW, resorcinol-formaldehyde resins
can turn out to be more preferential.

Author Contributions: Conceptualization, V.M., P.K. and A.E.; methodology, V.M., N.N. and P.K.;
formal analysis, V.M., P.K. and A.E.; investigation, V.M., N.N., A.S., D.M., S.S., K.F., E.T. and M.T.;
writing—original draft preparation, V.M. and A.E.; writing—review and editing, V.M., P.K., A.E. and
E.T.; funding acquisition, P.K. and A.E. All authors have read and agreed to the published version of
the manuscript.
Funding: Cs-137 adsorption studies were carried out within the framework of the agreement No.
N.4d.241.20.22.1057 dated 04.04.2022, for the implementation of the state contract “Development
and justification of options for processing highly active wastes of complex chemical composition,
including experimental design work and experimental industrial testing of equipment”. Synthesis
of the samples of RFR-i and RFC-Ca ion-exchangers, obtaining NMR spectra of C-13 RFRs, as
well as theoretical calculations were carried out within the framework of the State Order of the
Institute of Chemistry of the Far Eastern Branch of the Russian Academy of Sciences, project No.
FWFN(0205)-2022-0002.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: Equipment of the CUC, “Far Eastern Center of Structural Investigations”, was
used in this work.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Kozlov, P.V.; Kazadaev, A.A.; Makarovskii, R.A.; Remizov, M.B.; Verbitskii, K.V.; Logunov, M.V. Development of a Process for
Cesium Recovery from the Clarified Phase of High-Level Waste Storage Tanks of the Mayak Production Association with a
Ferrocyanide Sorbent. Radiochemistry 2016, 58, 295–301. [CrossRef]
2. Milyutin, V.V.; Mikheev, S.V.; Gelis, V.M.; Kozlitin, E.A. Sorption of Cesium on Ferrocyanide Sorbents from Highly Saline
Solutions. Radiochemistry 2009, 51, 298–300. [CrossRef]
3. Fiskum, S.K.; Pease, L.F.; Peterson, R.A. Review of Ion Exchange Technologies for Cesium Removal from Caustic Tank Waste.
Solvent Extr. Ion Exch. 2020, 38, 573–611. [CrossRef]
4. Aleman, S.; Hamm, L.; Smith, F. Ion Exchange Modeling Of Cesium Removal From Hanford Waste Using Spherical Resorcinol-
Formaldehyde Resin; Technical Report WSRC-STI-2007-00030; Washington Savannah River Site (SRS): Aiken, SC, USA, 2007.
5. Fiskum, S.K.; Blanchard, D.L.; Arm, S.T.; Peterson, R.A. Cesium Removal from Simulated and Actual Hanford Tank Waste Using
Ion Exchange. Sep. Sci. Technol. 2005, 40, 51–67. [CrossRef]
6. Milyutin, V.V.; Zelenin, P.G.; Kozlov, P.V.; Remizov, M.B.; Kondrutskii, D.A. Sorption of Cesium from Alkaline Solutions onto
Resorcinol-Formaldehyde Sorbents. Radiochemistry 2019, 61, 714–718. [CrossRef]
7. Tokar, E.; Tutov, M.; Kozlov, P.; Slobodyuk, A.; Egorin, A. Effect of the Resorcinol/Formaldehyde Ratio and the Temperature of
the Resorcinol–Formaldehyde Gel Solidification on the Chemical Stability and Sorption Characteristics of Ion-Exchange Resins.
Gels 2021, 7, 239. [CrossRef]
8. Miller, H.S.; Kline, G.E. Reactions of Cesium in Trace Amounts with Ion-Exchange Resins. J. Am. Chem. Soc. 1951, 73, 2741–2743.
[CrossRef]
9. Kargov, S.I.; Shelkovnikova, L.A.; Ivanov, V.A. The Nature of Ion Exchange Selectivity of Phenol-Formaldehyde Sorbents with
Respect to Cesium and Rubidium Ions. Russ. J. Phys. Chem. A 2012, 86, 860–866. [CrossRef]
10. Samanta, S.K.; Misra, B.M. Ion Exchange Selectivity of a Resorcinol-Fqrmaldehyde Polycondensate Resin for Cesium in Relation
to Other Alkali Metal Ions. Solvent Extr. Ion Exch. 1995, 13, 575–589. [CrossRef]
Sustainability 2023, 15, 8734 16 of 17

11. Hubler, T.L.; Franz, J.A.; Shaw, W.J.; Bryan, S.A.; Hallen, R.T.; Brown, G.N.; Bray, L.A.; Linehan, J.C. Synthesis, Structural
Characterization, and Performance Evaluation of Resorcinol-Formaldehyde (R-F) Ion-Exchange Resin; Technical Report PNL-10744;
Pacific Northwest Laboratory: Richland, WA, USA, 1995.
12. Duignan, M.R.; Nash, C.A. Removal of Cesium from Savannah River Site Waste with Spherical Resorcinol Formaldehyde Ion
Exchange Resin: Experimental Tests. Sep. Sci. Technol. 2010, 45, 1828–1840. [CrossRef]
13. Adamson, D.J. Pilot-Scale Hydraulic Testing of Resorcinol Formaldehyde Ion Exchange Resin. In Proceedings of the Fluids
Engineering Division Summer Meeting, Vail, CO, USA, 2–6 August 2009; Volume 43727, pp. 545–553. [CrossRef]
14. Duignan, M.R.; Nash, C.A.; Punch, T.M. High Aspect Ratio Ion Exchange Resin Bed—Hydraulic Results for Spherical Resin
Beads. Sep. Sci. Technol. 2008, 43, 2943–2979. [CrossRef]
15. Brooks, K.P.; Augspurger, B.S.; Blanchard, D.L.; Cuta, J.M.; Fiskum, S.K.; Thorson, M.R. Hydraulic Testing of Ion Exchange Resins
for Cesium Removal from Hanford Tank Waste. Sep. Sci. Technol. 2006, 41, 2391–2408. [CrossRef]
16. Fiskum, S.K.; Augspurger, B.S.; Brooks, K.P.; Buchmiller, W.C.; Russell, R.L.; Schweiger, M.J.; Snow, L.A.; Steele, M.J.;
Thomas, K.K.; Wallace, D.E.; et al. Comparison Testing of Multiple Resorcinol-Formaldehyde Resins for the River Protection
Project—Waste Treatment Plant; Technical Report PNWD-3387 WTP-RPT-103, Rev 0; Savannah River Technology Center,
Department of Energy 1000 Independence Ave.: Washington, DC, USA, 2004; p. 2978.
17. Clevasol® —A Novel Cation Exchange Resin for Isotope Capture. Available online: https://www.lemerpax.com/en/products/
clevasol-en/ (accessed on 25 April 2023).
18. Yakushev, A.; Turler, A.; Dvorakova, Z.; Bremen, K. CLEVASOL, a Novel Radiation Hard Cation Exchanger Suitable for
Treatment of Liquid Radioactive Waste with High Salinity. In Proceedings of the APSORC’13—5th Asia-Pacific Symposium on
Radiochemistry Kanazawa, Kanazawa, Japan, 22–27 September 2013; p. 133.
19. Lin, M.; Kajan, I.; Schumann, D.; Türler, A.; Fankhauser, A. Selective Cs-Removal from Highly Acidic Spent Nuclear Fuel
Solutions. Radiochim. Acta 2020, 108, 615–626. [CrossRef]
20. Chaplin, J.D.; Berillo, D.; Purkis, J.M.; Byrne, M.L.; Tribolet, A.D.C.C.M.; Warwick, P.E.; Cundy, A.B. Effective 137 Cs+ and 90 Sr2+
Immobilisation from Groundwater by Inorganic Polymer Resin Clevasol® Embedded within a Macroporous Cryogel Host Matrix.
Mater. Today Sustain. 2022, 19, 100190. [CrossRef]
21. Haas, P.A. A Review of Information on Ferrocyanide Solids for Removal of Cesium from Solutions. Sep. Sci. Technol. 1993, 28,
2479–2506. [CrossRef]
22. Loos-Neskovic, C.; Fedoroff, M. Fixation Mechanisms of Cesium on Nickel and Zinc Ferrocyanides. Solvent Extr. Ion Exch. 1989, 7,
131–158. [CrossRef]
23. Lee, E.F.T.; Streat, M. Sorption of Caesium by Complex Hexacyanoferrates. v. a Comparison of Some Cyanoferrates. J. Chem. Tech.
Biotechnol. 1983, 33, 333–338. [CrossRef]
24. Milyutin, V.V.; Nekrasova, N.A.; Kozlov, P.V.; Markova, D.V.; Feoktistov, K.A. Extraction of cesium from model solutions of
highly active alkaline wastes on an inorganic ferrocyanide sorbent of the brand Fersal. Vopr. Radiatsionnoy Bezop. 2022, 3, 22–27.
(In Russian)
25. Milyutin, V.V.; Gelis, V.M.; Leonov, N.B. Study of the Sorption Kinetics of Cesium and Strontium Radionuclides by Sorbents of
Different Classes. Radiochemistry 1998, 40, 418–420. (In Russian)
26. Sanders, J. Veusz—A Scientific Plotting Package. Available online: https://veusz.github.io/ (accessed on 25 April 2023).
27. Hubler, T.L.; Shaw, W.J.; Brown, G.N.; Linehan, J.C.; Franz, J.A.; Hart, T.R.; Hogan, M.O. Chemical Derivation to Enhance the
Chemical/Oxidative Stability of Resorcinol-Formaldehyde (R-F); Resin Technical Report No. PNNL–11327; Pacific Northwest National
Laboratory: Richland, WA, USA, 1996.
28. Russell, R.L.; Fiskum, S.K.; Smoot, M.R.; Rinehart, D.E. Cesium Isotherm Testing with Spherical Resorcinol-Formaldehyde Resin at High
Sodium Concentrations; Technical Report PNNL-25277; Pacific Northwest National Laboratory (PNNL): Richland, WA, USA, 2016.
29. Kim, M.G.; Wu, Y.; Amos, L.W. Polymer Structure of Cured Alkaline Phenol–Formaldehyde Resol Resins with Respect to Resin
Synthesis Mole Ratio and Oxidative Side Reactions. J. Polym. Sci. Part A Polym. Chem. 1997, 35, 3275–3285. [CrossRef]
30. Christiansen, A.W. Resorcinol-Formaldehyde Reactions in Dilute Solution Observed by Carbon-13 NMR Spectroscopy. J. Appl.
Polym. Sci. 2000, 75, 1760–1768. [CrossRef]
31. Pretsch, E.; Clerc, T.; Seibl, J.; Simon, W. Tables of Spectral Data for Structure Determination of Organic Compounds; Springer Science &
Business Media: Berlin/Heidelberg, Germany, 2013; ISBN 978-3-662-10207-7.
32. Werstler, D.D. Quantitative 13 C n.m.r, Characterization of Aqueous Formaldehyde Resins: 2. Resorcinol- Formaldehyde Resins.
Polymer 1986, 27, 757–764. [CrossRef]
33. Hubler, T.L.; Franz, J.A.; Shaw, W.J.; Hogan, M.O.; Hallen, R.T.; Brown, G.N.; Linehan, J.C. Structure/Function Studies of Resorcinol-
Formaldehyde (R-F) and Phenol-Formaldehyde (P-F) Copolymer Ion-Exchange Resins; Technical Report PNNL-11347 Richland; Pacific
Northwest National Laboratory: Washington, WA, USA, 1996.
34. Pratt, L.M.; Szostak, R.; Khan, I.M. Alkaline degradation of resorcinol- formaldehyde resins: Solid-State nmr, thermal adsorption
and desorption analysis, and molecular modeling. J. Macromol. Sci. Part A Pure Appl. Chem. 1997, 34, 281–289. [CrossRef]
35. Arm, S.T.; Blanchard, D.L. Pre-Conditioning and Regeneration Requirements of Ground Gel Resorcinol Formaldehyde Ion Exchange Resin;
Technical Report WTP-RPT-104, PNWD-3390; Battelle–Pacific Northwest Division, Richland: Washington, DC, USA, 2004.
Sustainability 2023, 15, 8734 17 of 17

36. Fiskum, S.K.; Colburn, H.A.; Rovira, A.M.; Allred, J.R.; Smoot, M.R.; Peterson, R.A.; Landon, M.R.; Colosi, K.A. Cesium Removal
from AP-105 Hanford Tank Waste Using Spherical Resorcinol Formaldehyde Resin. Sep. Sci. Technol. 2019, 54, 1932–1941.
[CrossRef]
37. Shelkovnikova, L.A.; Gavlina, O.T.; Ivanov, V.A. Stability of Phenol-Formaldehyde Ion-Exchange Sorbents in Aqueous Solutions.
Russ. J. Phys. Chem. A 2011, 85, 1652–1659. [CrossRef]
38. King, W.D.; Fondeur, F.F.; Wilmarth, W.R.; Pettis, M.E.; McCollum, S.W. Reactivity of Resorcinol Formaldehyde Resin with Nitric
Acid. Sep. Sci. Technol. 2006, 41, 2475–2486. [CrossRef]
39. Russell, R.L.; Rinehart, D.E.; Brown, G.N.; Schonewill, P.P.; Peterson, R.A. Ion Exchange Kinetics Testing with SRF Resin; Technical
Report PNNL-21109; Pacific Northwest National Laboratory: Richland, WA, USA, 2012.
40. Arm, S.T.; Blanchard, D.L.; Fiskum, S.K.; Weier, D.R. Chemical Degradation of SuperLig® 644 Ion Exchange Resin; Technical Report
PNWD-3315; Battelle-Pacific Northwest Division: Richland, WA, USA, 2003.

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.