Calixarene based Cs resins

Titre Illarion Dovhyi

Raddec-Triskem International TechnicalWorkshop, 18th April 2024
Sous-titre

MATERIALS
Calix[4]arene-bis(tertoctylbenzocrown-6, C72H92O12(ВOBCalix)

1,3-alt-25,27-Bis(3,7dimethyloctyl-1oxy)calix[4]arene-benzocrown6, C62H82O8(MAXCalix)

Calix[4]arene-bis[4-(2ethylhexyl)benzo-crown-6],
C72H92O12(ВEBHCalix)(1Bil

OUR GOALS
To develop new resins based on different calixarenes and diluents for:► separation of Cs and Rb from weak acid solutions with possibility of elution with strong acid,► separation of Cs and Rb from elevated acid solutions with possibility of elution with water or weakacid.
It is necessary to perform some experiments to achieve these goals:► to prepare prototypes based on the different calixarenes► to study dependence of Dw of different element on prototypes in HNO3 and HCl► to study influence of interferenting ions (like potassium) on Cs separation► to determine breakthrough and full capacities of prototypes► to perform elution tests for Rb and Cs separation

LITERATURE REVIEW
TK300 resin• Calixarene based• High selectivity for Cs andRb over other elements atlow to medium acid
• Interference by K+• Limited capacity• Work on additional resinsCs sorption on 0.05 M BC6B in 1,2-DCE
supported on Amberchrom CG-71 m[Dietz, 2006].

LITERATURE REVIEW• Cs and Rb loaded
from 0.01 – 1M HNO3
• Rinse with 1M HNO3
to remove impurities• Elution at high HNO3
• Cs/Rb separation
possible if needed• Preferably use for low
K samples (e.g.
decommissioningsamples)

COMPOSITION OFPROTOTYPES
Table 1. Compositions of the sorbents.
PrototypeCACapacity

PR1

MAXHigh (>14 mg Cs/g)

PR2

BEBH

High

PR3

BOB

Low (<3 mg Cs/g)

PR4

BOBLow

PR5MAХLow

PR6

BEBH

Low

PR7*

MAXHigh

PR8*

BEBH

Low

PR9*

MAXHigh

PR10*

BEBH

High

PR11*

BEBH

High

PR13

BEBH

High

* – prototypes based on IL.

DW of Cs, Rb and Tl in HNO3

Fig. 1: Acid dependency of Dw for Cs+
on PR1-13 in HNO3
Most of element were not sorbed in HNO3
Dw Cs > Dw Rb
PR7,9-11 > PR1-6,8,13

Fig. 2: Acid dependency of Dw for Rb+
on PR 1-13 in HNO3

Fig. 3: Acid dependency of Dw for Tl+
on PR1-13 in HNO3

Maximum of Dw Cs, Rb in 2-3 M HNO3 for PR1-6
Decrease of Dw Cs, Rb for IL PR7,9-11

DW of elements in HCl

Fig. 4: Acid dependency Dw
for various ions on PR1 in HCl

Fig. 5: Acid dependency Dw
for various ions on PR1 in HCl► PR1 weakly sorb Cs from HCl and only at high concentration► Dependences of Cs and Rb Dw on IL PR7 in HCl are like HNO3
► Elements which form chloride complexes sorb at high concentration of HCl

Fig. 6: Acid dependency Dwfor various ions on PR7 in HCl

KNO3 dependency of Dw for Cs ion

Fig. 7: KNO3 dependency of Dw for Cs ion
on high-capacity PR 1,2,7-11 in 1 M HNO3

Fig. 8: KNO3 dependency of efficiency of sorption on highcapacity PR 1,2,7 in 1 M HNO3
►Efficiency of sorption decreases by 50% in 1 M KNO3

KNO3 dependency of Dw for Cs ion

Fig. 9: KNO3 dependency of efficiency ofsorption on low-capacity PR 4-6 in 1 M HNO3

Fig. 10: KNO3 dependency of efficiency of sorption on lowcapacity PR 4-6 in 1 M HNO3 in the presence of KNO3
► There are no sorption in 1 M KNO3

Capacity of prototypes (column experiment)

Fig. 11: Sorption curves of Rb on high-capacity prototypes Fig. 12: Sorption curves of Cs on high-capacity prototypes
in 3 M HNO3. Initial concentration of Rb is 2,5 mg/mL.
in 3 M HNO3. Initial concentration of Cs is 2,5 mg/mL.

Capacity of prototypes (column experiment)

Fig. 13: Sorption curves of Rb on low-capacity prototypes
in 3 M HNO3. Initial concentration of Rb is 0,25 mg/mL.

Fig. 14: Sorption curves of Cs on low-capacity prototypes in3 M HNO3. Initial concentration of Cs is 0,25 mg/mL.

Capacity of IL prototypes (column experiment)

Fig. 15: Sorption curves of Rb on high-capacity
prototypes in 1 M HNO3.
Initial concentration of Rb is 2,5 mg/mL.

Fig. 16: Sorption curves of Cs on high-capacity prototypes
in 1 M HNO3.
Initial concentration of Cs is 2,5 mg/mL.Capacity of IL prototypes (column experiment)
Table 2. Capacities of prototypes

Table 2. Capacities of prototypes
PR

Ion

DEC,

FDEC,gtheor,C (CA),mg · g-1 mg · g-1 mg · g-1

mol/L

Elution

PR

Ion

DEC,

FDEC,gtheor,

C (CA),

mg · g-1

mg · g-1

mg · g-1

mol/L

Elution3 M HNO33 M HNO3
PR1

Rb

6,012,613,10,5112,0 (H2O)

PR1

Cs

9,321,520,40,5106,3 (H2O)

PR2

Rb

5,817,612,20,5106,9 (H2O)

PR2

Cs

13,230,319,00,587,2 (H2O)

PR4Rb

0,63

1,291,820,169,2 (0,01 M HNO3)

PR4Cs

0,86

1,662,840,187,5 (0,01 M HNO3)

PR6Rb

1,3

1,91,80,173,4 (0,01 M HNO3)

PR6Cs

1,93,12,80,168,2 (0,01 M HNO3)

PR13

Rb

14,126,917,3

1,062,7 (H2O)

PR13

Cs

19,035,126,91,092,7 (H2O)

1 M HNO3

1 M HNO3
PR7Rb

8,912,012,50,596,0 (10 M HNO3)

PR7Cs

12,219,619,50,5106,9 (10 M HNO3)

PR9Rb

6,510,48,10,3104,0 (10 M HNO3)

PR9Cs

9,314,412,60,391,7 (10 M HNO3)

PR10Rb10,317,311,70,596,5 (10 M HNO3)

PR10Cs13,325,218,20,597,4 (10 M HNO3)

PR11Rb

6,915,87,80,394,1 (10 M HNO3)

PR11Cs

10,021,212,10,397,4 (10 M HNO3)

Capacity of PR2 (static experiment)
Table 3. Capacity data of PR2.
Capacity in
Element

Maximum

column

DEC,

TDEC,

maximumtheoreticalexperiment,

mg/g

mg/g

capacity,

capacity,

mg/g

mg/g

mg/gaLangmuir

Rb

16.2*

6.3

18.6

Cs

26.8*

13.2

30.3

12.2

b24.2

19.0

* – sorption from 20 mL of 2,5 mg/mL Rb (Cs) solution, Rb and Cs
quantitatively desorbed by 10 mL of water.

cdFig. 17. Cs sorption isotherms with PR2: qe – C plot (a), linearized in coordinates1/qe – 1 / Cplot (b), lgqe – lgC (c), lnqe – e2 (d).

Capacity of PR2 (static experiment)
Table 4. – Parameters of the sorption isotherms of Cs on PR2
Langmuir isotherm
Resingm, mg/gKL, L·mg1

Freundlich isotherm
r2KF, mg·g-1

nDubinin-Radushkevich isotherm
r2gm, mg g–1

β, mol2
kJ–2

Е, kJ mol–1

r2

0.9

46.9

0.0061

9.1

0.98

Cs
PR2

24.2

0.00420.98

0.76► For the most of prototypes full Cs andRb capacities are close to theoretical.
► For PR2 full Cs and Rb capacities arehigher than theoretical according of threeexperiments and may be related withcomplex formation of 1 molecule of CA
with 2 ions of Cs, because of the second
crown-ether ring.

2.25

Calix[4]arene-bis(tertoctylbenzocrown-6, C72H92O12(ВOBCalix)

fluorinated(1H,1H,7H-Do
1-heptanol), C(FA

1,3-alt-25,27-Bis(3,7dimethyloctyl-1oxy)calix[4]arene-benzocrown6, C62H82O8(MAXCalix)

1-ButymethylimidBis(trifluoromel)imide (BMIC10H15F6N(IL)

Calix[4]arene-bis[4-(2ethylhexyl)benzo-crown-6],
C72H92O12(ВEBHCalix)

2-nonan
C9H18(2-onElution tests with low- (PR8) and high-capacity(PR7) IL prototypes

Fig. 18: Separation of Rb and Cs on PR8(loading in 0,01 M HNO3)

Fig 19: Separation of Rb and Cs on PR8(loading in 1 M HNO3 solution)

Elution tests with low- (PR8) and high-capacity(PR7) IL prototypes

Fig. 20: Separation of Rb and Cs on PR7(loading in 0,01 M HNO3)

Fig. 21: Separation of Rb and Cs on PR7(loading in 1 M HNO3 solution)

Elution tests with high-capacity
prototype (PR2)

Fig. 22: Separation of 1 µg Rb and Cs on PR2

Fig. 23: Separation of 100 µg Rb and Cs on PR2

Fig. 24: Separation of 1000 µg Rb and Cs on PR2► There is no elution of µg amounts of Rb and Cs from thePR1, PR2 and PR4 with water or weak acid. This
contradicts the capacity and Dw ME experimental data.
► ppb concentrations of Cs on PR1,2, 4-6 cannot be eluted
with water or 0,01 M HNO3.
► It is possible to separate “high” amounts (100 µg, 1000µg) of Rb and Cs with PR1 and PR2. Elution of Rb ispossible with 1 M HNO3, elution of Cs is possible with H2O(with “tail” of Rb in Cs fraction).

Elution tests with high-capacity
prototype PR1Fig. 25: Separation of 1 µg Rb and Cs onPR1

Fig. 26: Separation of 1 µg Rb and Cs onPR1

Elution tests with high-capacity
prototype PR1

Direct sorption of Rb and Cs from seawateron 2 mL cartridges IL prototypes

Fig. 27. Sorption curves of Cs and Rb

Fig. 28. Sorption curves of Cs and Rb

on PR7 from seawater (pH 2).
on PR7 from seawater (pH 7,9).
Flow rate is 1
BV/minDirect sorption of Rb and Cs from seawateron 2 mL cartridges IL prototypes

Fig. 29. Sorption curves of Cs and Rb
on PR9 from seawater (pH 2).

Flow rate is 1
BV/minFig. 30. Sorption curves of Cs and Rbon PR9 from seawater (pH 7,9).

More than 100 BV for Cs breakthrough on the most effective PT9

No difference between seawater with (pH 2) and without (pH 7,9) acidification

The PT10 and PT11 are less effective

Nature of maximum in the beginning retention of Cs and after substitution of Cs with Na, K etc

Cs capture on PT8– 1 mg of Cs and Ba were load with 1 L of 0.01
M HCl on 20 mL cartridges of PT8 (9.9 g);– 50 mL of 0.01 M HCl were used forprecondition of resin– 50 mL of 0.01 M HCl were used for rinsing ofresin– 2*50 mL of 0.5 M (NH4)2CO3 were used forelution of Cs

With loading of 1 mg of Cs:- there is no breakthrough of Cs.
- elution of Cs is full.

– fractions were diluted 10 times– flow rate is 10 mL/min.

CONCLUSIONS► Calixarene based prototypes show high selectivity for Rb and Cs in wide range of HNO3
concentrations.

► The breakthrough capacities up to 19 mg/g resin were achieved. For the most of prototypes fullcapacities are close to theoretical, but for PR9 and BEBH-based PR2, 10,11 they are higher.
► Four ionic liquids-based prototypes with high (PR 7, 9) and low capacity (10-11) were developed forseparation of Rb and Cs from HNO3 solutions in wide range of concentration (0,01 – 1 M). It is possible toeluted Rb and Cs with 10 M HNO3.
► Three high-capacity prototypes (PR 1, 2, 13) were developed for separation of Rb and Cs from 3 M

HNO3. But elution of Cs with water are strongly dependent on initial concentration of metals. It is nopossible to elute them with water after sorption from 1 µg/L solutions.
► The efficiencies of sorption for Cs on PR 1, 2, 7, 9-11 are near 50% even in 1 M KNO3.

POSSIBLE APPLICATION► separation of Cs and Rb isotopes from low (PRRADIOANALYSIS of Cs isotopes
e.g. Cs-135

7,9- 11) and elevated (PR 1, 2, 13) HNO3 solutions

for analysis of the environmental anddecommissioning samples

CS/BA SEPARATION
for nuclear medicine► Cs-131 production (low-capacity PT8)

Application of prototypes

WASTE TREATMENT► direct separation of Cs isotopes from seawaterbased waste (high-capacity PR 9).

RADIOCHEMICALTECHNOLOGIES► direct separation of Cs isotopes from 3 M HNO3
solutions of spent nuclear fuel processing (PR 1, 2,13)

Thank you for your attention!