Asfari 1996

Chapter 26
Cesium Removal from Nuclear Waste Water

by Supported Liquid Membranes Containing
Calix-bis-crown Compounds
1 1 1,3 2 2,3
Z. Asfari , C. Bressot , J. Vicens , C. Hill , J.-F. Dozol ,
2 2 2 2
H. Rouquette , S. Eymard , V. Lamare , and B. Tournois
1
Ecole Européenne des Hautes Etudes des Industries Chimiques de
Strasbourg, Unité de Recherche Associée 405 du Centre National de la
Downloaded by AUBURN UNIV on April 18, 2017 | http://pubs.acs.org
Publication Date: May 5, 1996 | doi: 10.1021/bk-1996-0642.ch026
Recherche Scientifique, 1 rue Blaise Pascal, F-67008 Strasbourg, France

2
S.E.P./S.E.A.T.N., Centre d'Etudes de Cadarache, Commissariat
à l'Energie Atomique, 13108 Saint-Paul-lez-Durance, France
Calix[4]-bis-crowns 1-7 are used as selective cesium-carriers in

supported liquid membranes (SLMs). Application of the Danesi
137
diffusional model allows the transport isotherms of trace level Cs
through SLMs (containing calix[4]-bis-crowns) to be determined as a
function of the ionic concentration of the aqueous feed solutions.
Compound 5 appears to be much more efficient than mixtures of
crown ethers and acidic exchangers, especially in very acidic media.
Decontamination factors greater than 20 are obtained in the treatment
of synthetic acidic radioactive wastes. Permeability coefficient
measurements are conducted for repetitive transport experiments in
order to determine the SMLs stability with time. Very good results
(over 50 days of stability) and high decontamination yields are
observed with 1,3-calix[4]-bis-crowns 5 and 6.
It is well known that 137-cesium is one of the most important radionucleotides present
in the nuclear wastes and its removal can reduce storageriskscaused by its long half-
6
life (2 χ 10 y) (/,2). It has been demonstrated that crown ethers are promising metal
ion extractants and carriers in liquid membranes (3). A new family of crown ether-type
compounds is now emerging: the calixcrowns. These molecules combine calixarene
and crown ether elements in their molecular structure. Since Alfieri et al.(4) reported
the synthesis of the first member of a new class of macropolycyclic crown compounds
with the two opposite OH groups in />-ter/-butylcalix[4]arene bridged by a
pentaethylene glycol chain, the 1,3-capping of calix[4]arenes at the lowerrimhas been
achieved with poly(oxyethylene) chains leading to calixcrown ethers (5), doubly
crowned calixes (5c, 6), and a double-calix-crown (7). Due to the presence of a glycol
chain in their framework, calixcrowns have been used as complexing agents of alkali
and alkaline-earth metal cations. The selectivities of complexation were shown to
3
Corresponding author
0097-6156/96/0642-0376$15.00/0
© 1996 American Chemical Society
Bartsch and Way; Chemical Separations with Liquid Membranes

ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
26. ASFARI ET AL. Cesium RemovalfromNuclear Waste Water 377
depend on the conformation (cone, partial cone, 1,2-alternate and 1,3-alternate)

adopted by therigidifiedcalix[4]arene unit. For example the partial-cone isomer of 1,3-
dimethoxy-/?-/^r/-butylcalrx[4]crown-5 exhibited the highest free energy for
complexation of potassium cation (5b) and was used as a selective carrier of this cation
+
in supported liquid membranes (5c). The K selectivities of three different conformers
of l,3-diethoxy-p-/e/*/-butylcalix[4]crown-5 have been measured for chemically
modified field effect transistors (CHEMFETs) (5k) and membrane ion-selective
+ +
electrodes (ISEs) (5d). The ionophores showed decreasing K /Na selectivities in the
order: partial cone > 1,3-alternate > cone. The l,3-dialkoxycalix[4]crown-6
compounds in the l 3-alternate conformation exhibited binding preference for cesium
t
ion (5e). The X-ray crystal structure of the 1:1 complex of 1,3-
dimethoxycalix[4]crown-6 with cesium picrate indicated the presence of cation/π-
electron interactions (5e). In this contribution, we report the use of l,3-calix[4]-W.s-
crowns 1-7 (Chart I) as selective cesium-carriers in supported liquid membranes

(SLMs).
Sodium-Cesium Extractions.
Removal of cesiumfrommedium-level radioactive wastes involves extraction of cesium

from aqueous solutions which are 1 M in HN0 and 4 M in NaN0 (8). In a preliminary
3 3
study, extraction experiments with ligands 1-7 were performed by mixing equal
2
volumes (5 to 7 mL) of aqueous and organic solutions (calixarene : ΙΟ· M in 2-
nitrophenyl hexyl ether or 2-NPHE) in sealed polypropylene tubes for one hour at room
temperature (25 ± 1 °C). The aqueous solutions contained either NaN0 or CsN0 3 3
(5.0x10 M) in HN0 (1 M) to assess the selectivity toward cesium in the hypothetical

3
presence of sodium. A measure for the selectivity was assumed to be the ratio of the
distribution coefficients obtained separately for both cations :
D Y \M]
«(«-., - ΐ *"· = 114

where :
2 [A/] denotes the total concentration of the metal cation (complexed and
uncomplexed) in the organic phase at equilibrium,
and ^ [M] denotes its total concentration in the aqueous phase at equilibrium.
Σ [M] and 2 [M] were determined experimentally by analyzing aliquots (2 or 5 mL)

of each phase by gamma spectrometry after centrifugation.
From the data shown in Table I, it is seen that ligands 2, 5 and 6 with six oxygen
atoms in the glycol chain are much more selective for cesium over sodium than 1 and 3
with five or seven oxygen atoms in theirrings,or 4 and 7, in which the polyether chains
are sterically constrained by the presence of phenyl units. We have previously noted that
the glycolic chains containing five oxygens in p-tert-butylcal\x[4]-bis-crovm-5, related
to 1, are suitable for potassium and sodium cations, but are too small for the larger
cesium (6e). In comparison, 2, 5 and 6 show 100-times higher selectivities toward
cesium than do crown ethers w-decyl-benzo-21 -crown-7 (8), and ter/-butyl-benzo-21-
crown-7 (9), which are well known for their abilities to complex and extract large alkali
cations from acidic media (8). One explanation is that the complexes with calixarene

378 CHEMICAL SEPARATIONS WITH LIQUID MEMBRANES
l,3-caIix[4]-ô/5-crown-5 1 l,3-calix[4]-to-o-benzo-crown-6 5
l,3-calk[4]-£/s-crown-6 2 l,3-calbc[4]-o«-naphthyl-crown-6 6
l,3-calix[4]-i/$-crown-7 3 l,3-caUx[4]-6/.s-diphenyl-crown-6 7
l,3-ca!ix[4]-o/.y-/?-benzo-crown-6 4
Chart I : l,3-Calix[4]-ow-crowns 1-7.

26. ASFARI ET Cesium RemovalfromNuclear Waste Water 379
Table I : Liquid-liquid Extraction Experiments : Selectivity Determination :

+
Aqueous feed solution: M (N0 ): 5.0xl(H M in H N 0 : 1 M .
3 3
2
Organic solution: Extracting agent: ΙΟ* M in 2-nitrophenyl hexyl ether.
N° Extracting agents Das α

(θ/ΑΤα)
1 1,3-Calk[4]-o/5-crown-5 2xl0* 3
0.4 -
2 1,3-Calix[4]-A/5-crown-6 1.3χ10· 2
19.5 1500
3 1,3-Calix[4]-ow-crown-7 < ίο- 3

0.3 -
4 1,3-Calix[4]-to-/?-benzo-crown-6 <ιο· 3
2xl0- 2
-
5 1,3-Calix[4]-o/5-o-benzo-crown-6 1.7xl0- 32.5 3
19 000
6 1,3-Calix[4]-W.s-naphthyl-crown-6 <10 3
29.5 > 29 000
7 1,3-Calix[4]-é/5-diphenyl-crown-6 <10' 3
7xl0- 2
-
8 w-Decyl-benzo-21 -crown-7 1.2X10- 0.3 3
250
9 ter/-Butyl-benzo-21 -crown-7 1.2xl0- 0.3 3

250

D,Cs
12,
• 0.01 M
•
• π • D 0.02 M
• •
• •
[NaNO\ (M)
0 1 2 3 '
Aqueous solution : NaN0 : various concentrations (pH = 2).
3
Organic solution : l,3-calix[4]-£/s-crown-6 2 in 2-nitrophenyl octyl ether.

13?
Figure 1. Extraction Isotherms for Cs in Sodium Nitrate Solutions by 1,3-
Calix[4]-£/s-crown-6 2 in 2-NPOE.
100 ,
10
J
A A
[HNO ] y (M)
ι ι ι ι 11— ι ι—I I I I
0.001 0.01 0.1 10

Aqueous solution : H N 0 : various concentrations 3 2
Organic solution : l,3-o/s-calix[4]-crown-6 2 (10 M) in 2-nitrophenyl octyl ether.
Figure 2. Extraction Isotherm for Cs in Nitric Acid Solutions by 1,3-Calix[4]-

o/5-crown-6 2(10" M) in 2-NPOE.

26. ASFARI ET AL. Cesium Removal from Nuclear Waste Water 381
derivatives are best formed because they are stabilized by the p-bonding interactions
with the phenyl rings present in the basket-frame of 2, 5 and 6 (5e,9).
Although ligands 1-7 present two potential complexation sites, the complex
stoichiometry was found to be 1:1 (calixarene:cesium cation) (10). This behaviour may
be explained by a negative allosteric effect which has been found in complexing
systems containing two conformationally related crown ether subunits (77). These
systems are only able to complex cations in one of their two subunits at a time because
when one complex is formed, the other subunit has an unsuitable conformation to bind
any species (77).
As shown in Figures 1 and 2 which display cesium extraction isotherms for
compound 2 as a function of aqueous salt concentrations (0 < [NaN0 ] < 4 M, 0 < 3
[HN0 ] < 7 M and cesium at trace level), back-extraction of cesium was usually
3
allowed and favored in deionized water (where D is very small). This remarkable
Cs
property allowed the use of 1-7 as cesium selective carriers in supported liquid
membranes. Since cesium extraction was strongly enhanced in concentrated acidic

media for 1-7, as compared to mixtures of a crown 9 (72) and an acidic exchanger
ligand, it appeared 1-7 might be used to treat medium-level radioactive wastes. The
decrease of D for sodium nitrate concentrations greater than 0.5 M (Figure 1) or for
Cs
nitric acid concentrations greater than 2 M (Figure 2) reveal both the competitive
extraction of HN0 or NaN0 by the tested calixarenes and the decrease of the mean
3 3
activity coefficient of trace-level cesium in a concentrated aqueous media.
Cesium Transport Through Supported Liquid Membranes (SLMs).
Selective alkali cation permeation through liquid membranes has been intensively
studied to mimic natural antibiotics, to transduce chemical information into electronic
signals and to treat radioactive wastes (73). For instance, taking advantage of the
phenolic ionization of the parent calixarenes (p-tert-buty\- and p-tert-
pentylcalix[n]arenes) under basic conditions, Izatt et al (14) achieved quantitative
cesium transport through bulk liquid membranes (25 % v/v CH C1 -CC1 )fromaqueous
2 2 4
feed solutions of CsOH (pH > 12) to water. However, no cesium permeation was
observed in the case of neutral metal nitrate feed solutions during similar experiments
(14). Polyether-bridged calix[4]arenes were first applied to SLMs in order to study
potassium/sodium permeation selectivities as compared to those of valinomycin (13a).
We therefore decided to determine the selective ionophoric properties of calix[4]-£/s-
crowns 1-7 by measuring under similar experimental conditions (stirring rates,
concentration gradients) the permeability coefficients of cesium as described in the
Danesi model of trace level cation permeation through SLMs (75). Although the Danesi
model was applied to ion-pair extraction in apolar solvents, constant permeability
coefficients have also been observed in long term transport experiments (over 10 hours)
using a more polar organic solvent such as 2-nitrophenyl octyl ether (2-NPOE) (16).
The use of 1-7 as carriers in SLMs led to coupled co-transport of cesium and
nitrate ions from aqueous feed solutions of 4 M in NaN0 and 1 M in HN0 -
3 3
simulating concentrated medium-level radioactive wastes - to deionized water ^he

receiving solution) because of the N0 " concentration gradient. The decrease of Cs
3
radioactivity in the feed solutions was flowed by regular measurements with gamma
1 1
spectrometry analysis (1500 kBq.L* < Cs initial aqueous activity < 2500 kBq.L" )

Table Π : "Cs Transport Experiments

Through Flat Sheet Supported Liquid Membranes:
Permeability Determination after Six Hours of Permeation.
Aqueous feed solution: NaN0 (4 M) and HN0 (1 M).

3 3
Aqueous strip solution: deionized water.

2
Organic solution: Carrier : ΙΟ- M in 2-nitrophenyl octyl ether.
N° Carriers Pes (cmh-i)
1 1,3-Calix[4]-o/s-crown-5 9χ10· 2
2 1,3 -Calix[4]-o/s-crown-6 1.3
3 1,3-Calix[4]-£/s-crown-7 4xl0- 2
4 1,3-Calix[4]-o/ir-/?-benzo-crown-6 3xl0- 3
5 1,3-Calix[4]-^/5-o-benzo-crown-6 2.8
6 1,3-Calix[4]-o/s-naphthyl-crown-6 2.7
7 1,3-Calix[4]-o/5-diphenyl-crown-6 0.1
8 /i-Decyl-benzo-21 -crown-7 9xl0- 2

1
Permeability coefficients P (cm.h- ) for cesium permeation through the SLMs
M
C
were graphically determined by plotting the logarithm of the ratio — versus time (15).
ln
tJ =
" V P M t 0)
where :
C = concentration of the cation in the feed solution at time t;
C°= initial concentration of the cation in the feed solution;
θ = volumic porosity of the SLM (%);
2
S = membrane surface area (cm ) depending on the device;
3
V = volume of feed and stripping solutions (cm ) depending on the device; and
t = time (h).
The data summarized in Table Π confirm the results obtained previously in

sodium-cesium extraction studies (see Table I) although the organic solvent used in
these experiments (2-nitrophenyl octyl ether) is a slightly more polar and more viscous
diluent than 2-nitrophenyl hexyl ether. Carriers 2, 5 and 6 with six oxygen atoms in the
glycol chain are much more efficient at transporting cesium through SLMs than 1 and 3,
withfiveor seven oxygen atoms in theirrings,or 4 and 7, in which the polyether chains
are sterically constrained.
Certain assumptions of the Danesi model (75) (transport controlled and limited
only by diffusion) allow the permeability coefficients P to be evaluated by the M
following formula :
PM * η* (2)
where :
D = distribution coefficient of the permeating cation;
M
Δ = the ratio of the organic path length (thickness of the membrane χ

β
tortuosity) to the organic diffusion coefficient: (d χ T ) / D . c 0
Equation 2 shows that P is proportional to D which directly depends on the

M M
organic carrier concentration in the SLM. That is why the cesium transport isotherms
shown in Figures 3 and 4 for compound 2 reproduced the same trends as those found
previously in extraction isotherms (Figures 1 and 2):
• An increase of cesium permeability coefficient for [NaN0 ] < 1 M in the feed solution 3
(Figure 3) and for [HN0 ] < 2 M in the feed solution (Figure 4) as D increased with
3 Cs
salt concentration in the feed solution (Figures 1 and 2);

• A maximum of transport kinetics due to the maximum of D ; Cs
• A decrease of P for [NaN0 ] > 1 M or [HN0 ] > 2M, revealing three different
Cs 3 3
phenomena:
• A decrease of D due to sodium nitrate or nitric acid competitive extraction
Cs
and transport of sodium nitrate or nitric acid;

• A decrease of the trace level cesium mean activity coefficient with an
increase in the salt concentration in the aqueous feed solution;

P (crah")
Cj
1.5 η
• compound 2
Ο compound5
i.o
0.5
[NaN0 ] (M) 3
0.0
0 1 2 3 4 5
Aqueous feed solution : NaN0 : various concentrations (pHj = 1.4).
3
Aqueous stripping solution ^deionized water.

SLM : compound 2 or 5 (10 M) in 2-nitrophenyl octyl ether.
13?
Figure 3. Transport Isotherms for Cs from Sodium Nitrate Solutions to
Deionized Water by l,3-Calix[4]-6/s-crown-6 2 and by l,3-Calix[4]-6/s-o-benzo-
crown-6 5(10" M)in2-NPOE.
Pes (cm V )
10
• compound 2
Ο
Ο compounds Q M A
0.1
[HN0 ] (M) 3
0.01
0.001 0.01 0.1 1 10
Aqueous feed solution : HN0 : various concentrations.

3
Aqueous stripping solution : deionized water. 2
SLM : compound 2 or 5 (10 M) in 2-nitrophenyl octyl ether.

13?
Figure 4 : Transport Isotherms of Cs from Nitric Acid Solutions to Deionized
Water for l,3-Calix[4]-£/s-crown-6 2 and for l,3-Calix[4]-^/5-o-benzo-crown-6 5
(10" M) in 2-NPOE.

26. ASFARI ET A L Cesium Removal from Nuclear Waste Water 385
•Leaching of the SLMs by the feed and the receiving solutions favored by the
partitioning of the carrier, especially in the case of compound 2 which shows
very poor lipophilicity.
The higher selectivity and efficiency of 5 compared to 2 can easily be noticed by

comparing both transport isotherms shown in Figures 3 and 4.
Time stability of the most efficiently prepared SLMs was estimated by repeating
transport experiments in which both the aqueous feed and stripping solutions were
renewed every day while the SLMs remained the same. Consequently, daily partitioning
of the carrier from the membrane phase to the renewed aqueous solutions caused a
decrease of the carrier concentration in the SLMs, thus a decrease of D and, M
proportionally, of P . The evolution of the permeability coefficients vs the number of

M
runs was therefore a way to evaluate leaching of the membrane by the aqueous
solutions and characterize the SLMs stability with time.

As shown in Figure 5, repeated cesium pansport experiments showed that 2 rapidly

leached out of the SLMs (P < 0.1 cm.h after 15 runs), because of its low partition
Cs
constants between 2-nitrophenyl octyl ether (2-NPOE) and the aqueous solutions. Very
good stability and efficiency were observed with the more lipophilic compounds 5 and
6, for which the cesium permeability coefficients were 5 times higher than those of the
crown ether 8 even when the concentration of the crown ether was 50 times higher in
2-nitrophenyl octyl ether (2-NPOE).
l,3-Calix[4]-£/s-crowns 5 and 6 allowed selective removal of Csfromsodium
containing solutions. Less than 100 mg of the -100 g of sodium initially present in the
feed solution wf£ transported in 24 hours by compound 6, whereas more than 95% of
the trace level Cs was concentrated in the stripping solution. Nitric acid transport,
due to the basicity of both the organic diluent and the calixarene, could not be limited to
less than 5 % (0.05 M) in 24 hours leading to concentration factors (ratio of initial
waste concentration to final waste concentration) greater than 100 for a single step
process.
To summarize, l,3-calix[4]-o/s-crowns containing six oxygen atoms appeared
to be a promising family of carriers for the selective removal of cesium from high
salinity media, such as medium-level radioactive liquid wastes, with SLMs. By choosing
a highly hydrophobic organic diluent, 2-NPOE, and a very lipophilic calix[4]-o/.s-crown
in the 1,3-alternate conformation suitable for cesium complexation over sodium, very
selective and stable SLMs can be obtained (over a period of 50 days).
Transport of Cesium from Simulated Fission Product Solutions.
Application of calix[4]-ow-crowns 2, 5 and 6 to decontaminate medium or high-level

radioactive wastes, such asfissionproduct solutions, was also investigated. Figure 6
+ 2+ 2+ 3+
shows the effect of the presence of six different nitrate salts (NH , Ca , Mg , Fe ,
4
3+ 2+
A l and U 0 ) on cesium permeation from aqueous feed solutions simulating medium
2
active concentrates (4 M in NaN0 and 1 M in HN0 ) to receiving solutions of

3 3
deionized water. Except for ammonium nitrate salts, which usually behave like alkali
cations and drastically hinder cesium separation in classical industrial decontamination
processes (co-precipitation, ion exchange, ...), none of the other five added species
2+ 2+ 3+ 3+ 2+
(Ca , Mg , Fe , A l and U0 ) potentially present in medium active wastes
2
disfavored trace level cesium permeation through the SLMs.

1
Pes (cmh- ) • compound 2 : 0.01 M
° compound 5 : 0.01 M
• compound 6 : 0.01 M
2 X w-Decyl-Benzo-21C7 : 0.5 M
v
o 0 ο
1
ο ο
<χχχ
χ Χ"Χ
χ
••• • • * number of runs
0
0 15 30 45 60
Aqueous feed solution : NaN0 (4 M) and HN0 (1 M). 3 3
Aqueous stripping solution : dçionized water.

SLM : compound 2, 5 or 6 (10 M) in 2-nitrophenyl octyl ether.
13?
Figure 5 : Repetitive Transport Experiments of Cs from Simulated Medium-
Active Liquid Wastes for l,3-Calix[4]-£/.s-crown-6 2, for l,3-Calig[4]-6/.r-o-
benzo-crown-6 5 and for l,3-Calix[4]-£/j-l,2-naphthyl-crown-6 6 (10 M) in 2-
NPOE.
(cm.h-1)
Compund 14
Compound 13
Compound 10
+ 2+
Aqueous feed solution : NaN0 (4 Μ), HN0 (1 M) and nitrate species (NH or Ca or
3 3 4
2+ 3 3+ 2+
Mg or Fe ^ or A l or U0 : 0.1 M). 2
Aqueous stripping solution : deionized water.

2
SLM : compound 2, 5 or 6 (10- M) in 2-nitrophenyl octyl ether.
13?
Figure 6 : Influence of the Presence of Nitrate Salts on the Permeation of Cs
from Simulated Medium-active Liquid Wastes to Deionized Water by 1,3-
Calix[4]-^/5-crown-6 2, l,3-Calix[4]-^/5-o-benzo-crown-6 5 and 1,3-Calix[4]-Aw-
2
naphthyl-crown-6 6 (10* M) in 2-NPOE.

Table ΙΠ records the transport yields of eleven main elements (out of thirty-four
present in very high-level radioactive liquid wastes, su^ch asfissionproducts solutions)
from nitric acid feed solutions (3 M in HN0 and 10* M in the element) to deionized
3
water. Metal cation concentrations were determined by atomic absorption spectrometry

of aliquots sampled in the receiving solutions after 24 hours of permeation. Except for
rubidium, whose chemical behavior is similar to that of cesium among the other alkali
cations, the high selectivity of the tested l,3-calbc[4]-ow-crowns toward cesium is
maintained in the presence of the other 9 elements.
Conclusion.
Calix[4]-o#5-crowns 1-7 have been used as Cs-carriers in supported liquid membranes.

Application of the Danesi diflusional model allowed the transport isotherms of trace
level Cs through SLMs (containing calix[4]-*w-crowns) to be determined as a

function of the ionic concentration of the aqueous feed solutions. Compound 5

appeared to be much more efficient than a combination of crown ether and an acidic
exchanger, especially in very acidic media. This allowed a one-step treatment of
synthetic acidic radioactive wastes with decontamination factors greater than 100.
Permeability coefficient measurements were also conducted in repetitive transport
experiments in order to evaluate the SML stability with time. Very good results (over
50 days of stability) and high decontamination yields were observed with l,3-calix[4]-
ô/5-crowns 5 and 6. Thus, the l,3-calix[4]-o/j-crowns are shown to be a new family of
selective carriers for cesium removal from radioactive liquid wastes leading to 1:1
stoichiometry complexes (l,3-calix[4]-£/s-crown : Cs).
Experimental Section
Ligands. Calix[4]-£i5-crowns 1-7 have been prepared according to published

procedures (6b, 17).
Starting Materials for Extraction and SLMs transports. The inorganic salts used to
prepare the synthetic aqueous feed solutions for extraction and transport experiments
(NaN0 , C ^ ï 0 , ...) were analytical grade products from Prolabo and Aldrich.
3 3 13<
1
Radioactive Na and Cs used to spike the aqueous solutions (1500 kBq.L* < initial
1
aquegys activity < 2500 kBq.L' ) were provided by the Amersham Company. The Na
and Cs gamma spectra were obtained on a detection chain from Interchnique : an
EGSP-2000-20R gamma spectrometer equipped with germanium detectors. The
counting was always sufficiently long to insure a relative error in activity measurement
of less than 5 %. The organic diluents, 2-nitrophenyl hexyl ether (2-NPHE) and 2-
nitrophenyl octyl ether (2-NPOE) used to dissolve 1-7 were synthesized by Chimie Plus
and used without further purification.
Transport Measurements. The same Flat-Sheet Supported Liquid Membrane (SLMs)

device described by T. Stolwijk et al. (18) and shown in Figure 7 was used for the
transport experiments. The volume of both aqueous solutions (feed and stripping)
ranged from 45 to 55 mL depending on the glass devices manufactured by Prodilab and
2
Verre & Science Companies. The circular membranes were about 15 to 16 cm in area
and made of polypropylene Celgard® 2500 microporous support (of 25 mm thickness

Table m : Transport Yields (after 24 hours) of Sr, Rb, Y, Zr, Ru, Rh, Cs, Ba, La, Ce and Eu
Permeation from Simulated High-active Wastes to Deionized Water by l,3-Calix[4]-o/s-
crown-6 2, by 1,3-calix[4]-Z>/5-o-benzo-crown-6 6 and by l,3-calix[4]-£/s-naphthyl-crown-6 5
(10"M)in 2-NPOE.
3
Aqueous feed solution : HN0 : 3 M and Element : 10 M.

3
Aqueous stripping solution : deionized water.

SLM: compound 2, 5 or 6 (10 M) in 2-nitrophenyl octyl ether.
1,3- calix[4]-o/s-crown
2 5 6
Element Initial concentration in the Metal concentration in the receiving solution

feed solution (mg L *) after 24 hours (mg L*)
Sr 87.6 2
< 5.10- < 5.10-2 < 5.10-2
Rb 85.5 34 63 47
3 3 3
Y 88.9 < 5.10- <5.10- <5.10-
2
Zr 91.2 < 5.10- < 5.10-2 < 5.10-2
3 3 3
Ru 101.0 < 5.10- <5.10- <5.10-
3 3 3
Rh 102.9 <5.10- <5.10- < 5.10-
Cs 132.9 92 125 105
2
Ba 137.3 < 5.10- < 5.10-2 < 5.10-2
3 3
La 138.5 <5.10- <5.10- < 5.10-3
3 3 3
Ce 140.1 <5.10- <5.10- <5.10-
3 3 3
Eu 151.9 <5.10- <5.10- <5.10-

26. A S F A R I E T A L . Cesium Removal from Nuclear Waste Water 389
-2
and 45 % internal volumic porosity) soaked with a ΙΟ M solution of 1-7 in 2-NPOE.
The measurements were performed at a constant temperature of 25° C.
|: Polymeric support
H : Organic phase
3 : Screw
Ε9'· Screw support
Q : Internal magnet
151: External magnet
7 : Theimostaledjacket
Figure 7 : Flat-sheet supported liquid membrane device for transport experiments.
References
1. Cecille, L. In Radioactive Waste Management and Disposal, Elsevier Applied

Science; New York; 1991.
2. Dozol, J. F. In Future Industrial Prospects of Membrane Processes, Cecille, L.;
Toussaint, J. C. Eds; Elsevier Applied Science; New York; 1989.
3. Shehata, F. A. J.Radioanal.Nucl.Chem. 1994, 185, 411.
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Commun. 1983, 1075.
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E.; Ugozzoli, F. Ungaro, R.; Harkema, S.; El-Fadl, Α. Α.; Reinhoudt, D. N. J. Amer.
Chem. Soc. 1990, 112, 6979. (c) Nijenhuis, W. F.; Buitenhuis, E. G., De Jong, F.;
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Ungaro, R. J. Chem. Soc Perkin Trans. 2 1993, 369. (i) Cacciapaglia, R.; Mandolini,
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Chapter 26

Cesium Removal from Nuclear Waste Water

Recherche Scientifique, 1 rue Blaise Pascal, F-67008 Strasbourg, France

Calix[4]-bis-crowns 1-7 are used as selective cesium-carriers in

Bartsch and Way; Chemical Separations with Liquid Membranes

depend on the conformation (cone, partial cone, 1,2-alternate and 1,3-alternate)

crowns 1-7 (Chart I) as selective cesium-carriers in supported liquid membranes

Removal of cesiumfrommedium-level radioactive wastes involves extraction of cesium

(5.0x10 M) in HN0 (1 M) to assess the selectivity toward cesium in the hypothetical

«(«-., - ΐ *"· = 114

Σ [M] and 2 [M] were determined experimentally by analyzing aliquots (2 or 5 mL)

Bartsch and Way; Chemical Separations with Liquid Membranes

Chart I : l,3-Calix[4]-ow-crowns 1-7.

Bartsch and Way; Chemical Separations with Liquid Membranes

Table I : Liquid-liquid Extraction Experiments : Selectivity Determination :

N° Extracting agents Das α

3 1,3-Calix[4]-ow-crown-7 < ίο- 3

9 ter/-Butyl-benzo-21 -crown-7 1.2xl0- 0.3 3

Bartsch and Way; Chemical Separations with Liquid Membranes

Organic solution : l,3-calix[4]-£/s-crown-6 2 in 2-nitrophenyl octyl ether.

0.001 0.01 0.1 10

Organic solution : l,3-o/s-calix[4]-crown-6 2 (10 M) in 2-nitrophenyl octyl ether.

Figure 2. Extraction Isotherm for Cs in Nitric Acid Solutions by 1,3-Calix[4]-

Bartsch and Way; Chemical Separations with Liquid Membranes

membranes. Since cesium extraction was strongly enhanced in concentrated acidic

activity coefficient of trace-level cesium in a concentrated aqueous media.

Cesium Transport Through Supported Liquid Membranes (SLMs).

simulating concentrated medium-level radioactive wastes - to deionized water ^he

Bartsch and Way; Chemical Separations with Liquid Membranes

Table Π : "Cs Transport Experiments

Aqueous feed solution: NaN0 (4 M) and HN0 (1 M).

Aqueous strip solution: deionized water.

N° Carriers Pes (cmh-i)

2 1,3 -Calix[4]-o/s-crown-6 1.3

8 /i-Decyl-benzo-21 -crown-7 9xl0- 2

Bartsch and Way; Chemical Separations with Liquid Membranes

The data summarized in Table Π confirm the results obtained previously in

Δ = the ratio of the organic path length (thickness of the membrane χ

tortuosity) to the organic diffusion coefficient: (d χ T ) / D . c 0

Equation 2 shows that P is proportional to D which directly depends on the

salt concentration in the feed solution (Figures 1 and 2);

and transport of sodium nitrate or nitric acid;

Bartsch and Way; Chemical Separations with Liquid Membranes

Aqueous stripping solution ^deionized water.

Aqueous feed solution : HN0 : various concentrations.

Aqueous stripping solution : deionized water. 2

SLM : compound 2 or 5 (10 M) in 2-nitrophenyl octyl ether.

Bartsch and Way; Chemical Separations with Liquid Membranes

The higher selectivity and efficiency of 5 compared to 2 can easily be noticed by

proportionally, of P . The evolution of the permeability coefficients vs the number of

solutions and characterize the SLMs stability with time.

As shown in Figure 5, repeated cesium pansport experiments showed that 2 rapidly

Transport of Cesium from Simulated Fission Product Solutions.

Application of calix[4]-ow-crowns 2, 5 and 6 to decontaminate medium or high-level

active concentrates (4 M in NaN0 and 1 M in HN0 ) to receiving solutions of

disfavored trace level cesium permeation through the SLMs.

Bartsch and Way; Chemical Separations with Liquid Membranes

Aqueous stripping solution : dçionized water.

Aqueous stripping solution : deionized water.

naphthyl-crown-6 6 (10* M) in 2-NPOE.

Bartsch and Way; Chemical Separations with Liquid Membranes

water. Metal cation concentrations were determined by atomic absorption spectrometry

Calix[4]-o#5-crowns 1-7 have been used as Cs-carriers in supported liquid membranes.