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Ion Exchange Separation for Decontamination of Centrifuge Enrichment Plant

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Ion Exchange Separation for Decontamination of

Centrifuge Enrichment Plant
a a a b b
Atsushi IKEDA , Masao AIDA , Yasuhiko FUJII , Shinobu KATAOKA , Sotonori ANNEN
c
& Jun SATO
a
Research Laboratory for Nuclear Reactors , Tokyo Institute of Technology , 2-12-1, O-
okayama, Meguro-ku , Tokyo , 152-8550
b
Ningyo-toge Environmental Engineering Center , Japan Nuclear Cycle Development
Institute , 1550, Kami-saibara-mura, Tomata-gun, Okayama , 708-0698
c
School of Science and Technology , Meiji University , 1-1-1, Higashi-mita, Tama-ku ,
Kawasaki , 214-8571
Published online: 07 Feb 2012.

To cite this article: Atsushi IKEDA , Masao AIDA , Yasuhiko FUJII , Shinobu KATAOKA , Sotonori ANNEN & Jun SATO (2002)
Ion Exchange Separation for Decontamination of Centrifuge Enrichment Plant, Journal of Nuclear Science and Technology,
39:10, 1099-1105, DOI: 10.1080/18811248.2002.9715299

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 Journal of NUCLEAR SCIENCE and TECHNOLOGY, Vol. 39, No. 10, p. 1099–1105 (October 2002)

TECHNICAL REPORT

Ion Exchange Separation for Decontamination of Centrifuge Enrichment Plant

Atsushi IKEDA1, ∗ , Masao AIDA1 , Yasuhiko FUJII1 , Shinobu KATAOKA2 , Sotonori ANNEN2 and Jun SATO3
1
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8550
2
Ningyo-toge Environmental Engineering Center, Japan Nuclear Cycle Development Institute,
1550, Kami-saibara-mura, Tomata-gun, Okayama 708-0698
3
School of Science and Technology, Meiji University, 1-1-1, Higashi-mita, Tama-ku, Kawasaki 214-8571
(Received May 16, 2002 and accepted in revised form August 9, 2002)

Ion exchange separation of uranyl ion (UO2+ 2 ) from metal cations has been carried out by the columnar operation
using ion exchange resins in 0.1 mol/dm3 sulfuric acid medium. Uranyl ion was adsorbed in an anion exchange resin
and the rest metal cations, Fe(III), Al(III), Cr(III), Ni(II) and Cu(II) ions, were adsorbed in a cation exchange resin
in this system. Desorption of uranyl ion and metal cations adsorbed in the resins were tested by 2 mol/dm3 sulfuric
acid solution. Desorbed elements were confirmed to be precipitated by appropriate alkaline solutions. On the basis of
the results obtained, a concept was made on a decontamination system for uranium-contaminated waste solution from
centrifuge enrichment plant.
KEYWORDS: separation, uranyl ion, ion exchange, ion exchange resin, sulfuric acid, decontamination, cen-
trifugation enrichment plants
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I. Introduction tion of uranyl ion in a low sulfuric acid can be represented by

the following equation:
Most of the present commercial nuclear power plants uti-
2 + m(SO4 )
[UO2 (SO4 )m ]
UO2+ .
2− 2− 2−2m
lize low enriched (i.e. 3–5%) uranium. The enriched uranium (1)
has been produced by gaseous diffusion plants and centrifuge
In a higher concentration of sulfuric acid, bisulfate ion
separation plants. In Japan, the centrifuge enrichment process
(HSO−4 ) is dissociated as Eq. (2) and the complexation of
has been employed by Japan Nuclear Cycle Development In-
uranyl ion becomes more complicated as Eq. (3):
stitute (JNC, former PNC) and a commercial plant of Japan
Nuclear Fuel Ltd. is in operation at Rokkasho-mura, Aomori. H2 SO4
H+ + HSO−
4 (2)
The pilot plant of JNC at Ningyo-toge has already ended its − 
2 + n(HSO4 ) + m (SO4 )
UO2+ 2−
operation, and the decontamination program of the plant has

been initiated. It is considered in the program that an acid
[UO2 (HSO−
4 )n (SO4 )m  ]
2− 2−n−2m
. (3)
solution is employed for washing equipments, probably 0.1–
0.2 mol/dm3 of sulfuric acid solution will be adopted for the The reaction between the complex of uranyl ion and a strong
decontamination. anion exchange resin can be expressed schematically by
This washing process is expected to produce an acid waste (|2 − n − 2m  |)R − NH+
4
solution which contains uranium and several metal elements, 
and the direct disposal of this waste solution will produce + [UO2 (HSO−
4 )n (SO4 )m  ]
2− 2−n−2m

large amount of radioactive or uranium-contaminated waste.
To reduce the radioactive waste of the decontamination sys-
tem, the radioactive elements should be separated from other
non-radioactive metal elements.
There is a variety of techniques to remove uranium from the
waste solution containing metal elements. One of the promis-
ing techniques is the ion exchange method. The ion exchange
method has been employed in many separation processes.
The advantages of this method are:
• a columnar (i.e. fixed bed) operation is applicable,
• the ion exchange resin used can be reused by regeneration.
In the nuclear fuel cycle, an anion exchange resin has been
used for uranium recovery from the leaching acid solution of
ores:1, 2) uranium ores are dissolved in sulfuric acid solution
and uranium oxide in the leaching solution is recovered from
other metal elements by an anion exchange resin. Uranium
oxide exists as uranyl ion (UO2+
2 ) in solution, the complexa-
∗
Corresponding author, Tel.&Fax. +81-3-5734-2958,
E-mail: aikeda@nr.titech.ac.jp

(|2 − n − 2m  |)R − NH4 [UO2 (HSO−
4 )n (SO4 )m  ],
2−
(4)
where R is the matrix of ion exchange resin, and the value of
“2−n−2m  ” is postulated to be minus.
The present work was initiated to apply the uranium sepa-
ration process using ion exchange resins to the decontamina-
tion of centrifuge enrichment plant. The aim of this work is to
develop several concepts of the decontamination system, the
several concepts are as follows:
(1) Uranium recovery from the decontamination system
(2) Recycle use of the decontamination solution of sulfuric
acid
(3) To minimize any kind of waste from every process.
To attain the concepts mentioned above, the present process
is considered to consist the following sub processes:
1) Separation of uranium in sulfuric acid by anion exchange
resin
2) Recovery of other metal elements by cation exchange

1099
 1100
resin
3) Precipitation of uranium and metal elements recovered
by alkaline solutions.
In the present work, some experimental works were car-
ried out to obtain fundamental information on the above men-
tioned three sub processes using porous types of anion and
cation exchange resins. The fundamental concept of the
present system is shown in Fig. 1 and the composition of the
tested solution simulated the waste solution of decontamina-
tion is shown in Table 1.
II. Experimental
1. Materials
All chemicals except uranium chloride were reagent grade
and supplied by Wako Pure Chemical Ind., Ltd. Uranium
chloride was converted to uranyl sulfate by cation exchange
resin before use. The ion exchange resin employed in
the recovery of uranium was strong base anion exchange
resin DIAION-PA316 (Mitsubishi Chemical Ind. Co.) of
around 600 µm diameter and strong acid cation exchange
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resin DIAION-PK216 (Mitsubishi Chemical Ind. Co.) of
500–700 µm diameter was employed for the recovery of other
metal elements.
2. Sample Preparation and Experimental Procedure
(1) Uranium Adsorption on Anion Exchange Resin
(a) Batch Operation
To obtain fundamental information on anion exchange
properties of concerned metal ions except uranyl ion shown
in Table 1, distribution coefficients were determined for the
anion exchange resin in different concentrations of sulfuric
acid solution by the following batch type experiments.
Prior to the use, the anion exchange resin was converted to
◦
sulfato form (SO2− 4 ) after pre-treating and dried at 50 C for
Fig. 1 Concept of decontamination system
Table 1 Composition of cations in waste solution
Element Concentration (mg/dm3 )
Fe(III) 900
Al(III) 120
Cr(III) 10
Ni(II) 20
Cu(II) 20
U(VI) 110
A. IKEDA et al.
24 h. Test solutions were prepared by dissolving a weighed
amount of metal sulfate reagents into 0.05 to 1 mol/dm3 of
sulfuric acid solutions. The concentration of the metal ions
was adjusted to 10 mmol/dm3 . A portion of resin, 1.8 g, was
put into a 20 cm3 of the test solution. The solution was stirred
for 6 h at room temperature. The concentrations of the metal
ions in the original test solution (C b ) and in the solution after
stirring (C a ) were determined by ICP-atomic emission spec-
trometer.
(b) Breakthrough Chromatography
Columnar chromatography operation was made to confirm
the adsorption of uranyl ion (UO2+ 2 ) at low concentrations of
sulfuric acid solution.
The anion exchange resin was packed into a Pyrex glass
column (1 cm in diameter and 30 cm in length), the volume of
resin bed was 8 cm3 . The column was surrounded with water
jacket for keeping the column at 20◦ C. Prior to the exper-
iments, the anion exchange resin in the column was condi-
tioned with desired 0.1 or 0.2 mol/dm3 of sulfuric acid solu-
tion after pre-treating with 2 mol/dm3 of sulfuric acid solution
to convert the resin into sulfato form (SO2− 4 ).
The feed solutions of uranyl ion were prepared by adding
a stock solution of uranyl ion (0.725 mol-U/dm3 ) into the
desired concentrations of sulfuric acid solution. The con-
centration of uranium in the feed solution was 110 mg/dm3
(0.46 mmol/dm3 ). The solution was fed into the column at a
constant flow rate of 50 cm3 /h. The effluent was collected for
every 100 cm3 by a fraction collector. The concentration of
uranyl ion was determined colorimetrically by using aqueous
sodium hydroxide, aqueous sodium carbonate and hydrogen
peroxide at the wavelength of 390.0 nm.
(2) Cation Adsorption and Desorption on Cation Exchange
Resin
Experimental apparatus and procedures of the columnar
operation are similar to those for the experiment of the anion
exchange resin. The cation exchange resin was packed into
the column, the volume of resin bed was 15 cm3 . Prior to the
experiments, the resin in the column was conditioned with de-
sired concentrations of sulfuric acid solution after pre-treating
by 2 mol/dm3 sulfuric acid solution to convert the resin into
hydrogen form (H+ ).
Feed solutions containing Fe(III), Al(III), Cr(III), Ni(II)
and Cu(II) ions were prepared by adding stock solutions of
the metal ions into 0.1, 0.25 and 0.5 mol/dm3 of sulfuric acid
solutions. The composition of the metal ions in the feed so-
lution is shown in Table 1. Uranium was not added into the
feed solution. The solutions of metal ions were fed into the
column at a constant flow rate of 50 cm3 /h. The breakthrough
operation was carried out in each chromatography. The efflu-
ent was collected for every 20 cm3 and the concentrations of
the metal ions were analyzed by ICP-atomic emission spec-
trometer.
To examine the effect of temperature on the adsorption
behavior, another chromatographic operations of cation ex-
change resin column were also carried out in the same way
as mentioned above at elevated temperatures of 50, 80 and
100◦ C.
Desorption behavior of the metal ions was tested at room
temperature (20◦ C) using the same column system which was
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY
 Ion Exchange Separation for Decontamination of Centrifuge Enrichment Plant
initially charged with the concerned cations by feeding the
cations in 0.1 mol/dm3 of sulfuric acid solution. A 1 mol/dm3
and 2 mol/dm3 of sulfuric acid solutions were used to elute
the adsorbed cations in the resin.
(3) Separation of Uranium from Metal Elements
An experimental apparatus was constructed as shown in
Fig. 2. The anion exchange resin was packed into Column-
1 and the cation exchange resin was packed into Column-2.
The volumes of resin bed were 10 cm3 for the anion exchange
resin and 35 cm3 for the cation exchange resin, respectively.
Column-1 was connected to Column-2 in series. Four three-
way valves were placed in the path of the solution. The taps of
these valves were changed according to the steps in the pro-
cedure. The column temperatures of the anion and cation ex-
change resins were set at 20◦ C and 80◦ C, respectively. A feed
solution of 0.1 mol/dm3 sulfuric acid solution was introduced
into the column at a flow rate of 50 cm3 /h. The composition
of the feed solution is given in Table 1.
Experimental procedure is as follows:
1) A 1,000 cm3 of the feed solution was introduced into
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Column-1 and the effluent from the column was intro-
duced into Column-2.
2) A 200 cm3 of 0.1 mol/dm3 sulfuric acid solution was in-
troduced into Column-1 and Column-2 in order to expel
the remaining feed solution in the pump and free space
completely.
3) The effluent from Column-2 was collected by a fraction
collector and the concentrations of the metal ions in ev-
ery 20 cm3 of fractions were determined by ICP-atomic
emission spectrometer. Geiger-Muller counter was used
to detect the uranyl ion in the effluent.
4) A 400 cm3 of 2 mol/dm3 sulfuric acid solution was intro-
duced into Column-1 to desorb the metal ions adsorbed
in the resin. The effluent was collected and the concen-
trations of the metal ions in the effluent were determined.
5) A 400 cm3 of 2 mol/dm3 sulfuric acid solution was intro-
duced into Column-2 to desorb the metal ions adsorbed
in the resin. The effluent was collected and the concen-
trations of the metal ions in the effluent were determined.
Flow Rate:
50 cm 3 /h
Column- 1 Column- 2
Pump
Anion
Exchange 80
Cation
Resin
Exchange
(2 0 )
Resin
2 mol/dm 3 Sample :Three Way Valve
Sulfuric Acid Solution
Fig. 2 Flow sheet of separation experiment
VOL. 39, NO. 10, OCTOBER 2002
1101
(4) Precipitation for Recovery
It is well known that uranyl ion is precipitated by ammo-
nium hydroxide solution as ammonium diuranate (i.e. yellow
cake). The eluent of uranyl ion desorbed by 2 mol/dm3 sulfu-
ric acid solution, i.e. the eluent from Column-1, was precip-
itated with 25 mass% of ammonium hydroxide solution and
the precipitate was filtrated after 5 h later and the concentra-
tion of the uranyl ion in the filtrated solution were determined
by colorimetric analysis and Geiger-Muller counter. The ura-
nium in the supernatant solution was also checked by gamma-
ray analysis. Other metal cations of Fe(III), Al(III), Cr(III),
Ni(II) and Cu(II) in 2 mol/dm3 sulfuric acid eluent, i.e. the
eluent from Column-2, were precipitated at pH=11 by adding
2 mol/dm3 of aqueous sodium hydroxide and 25 mass% of
ammonium hydroxide solution at pH=6 and 13. The precipi-
tation was filtrated and the filtrated solution was subjected to
concentration analysis by ICP-atomic emission spectrometry.
The recovery rates of the precipitation were calculated from
the measured values of the concentration analysis. The de-
tection limit of uranyl ion was less than 10 mg/dm3 , those of
metal cations were less than 0.01 mg/dm3 .
III. Results and Discussion
1. Uranium Adsorption on Anion Exchange Resin
Distribution coefficient (D), which indicates a degree of
adsorption of a given element on ion exchange resin, was cal-
culated from the results of the batch investigations. The dis-
tribution coefficient is defined by
D = [M]resin /[M]solution ,
where [M]resin and [M]solution are the concentrations of a metal
ion in resin and in aqueous solution phase, respectively, and
experimentally determined by the following equation:
D = (C b − C a )Vsolution /C a Vresin ,
where Vsolution and Vresin are the volume of solution and the ef-
fective volume of resin, respectively. The value of Vresin was
calculated from the mass of the resin and the resin density
calculated by Tap method. The distribution coefficients of the
elements, which calculated by using the values of C b and C a
obtained, were shown as a function of the molarity of sulfu-
ric acid. Their values are shown in Fig. 3 along with that of
1.6
1.4 FeIII)
1.2 Cr(III)
1.0 U(VI)
log D
0.8
0.6
0.4
0.2
0.0
0.0 0.2 0.4 0.6 0.8 1.0
3
Concentration of H2SO4 (mol/dm )
Fig. 3 Distribution coefficients of uranyl ion and metal ions for
anion exchange resin in sulfuric acid medium
Al(III), Ni(II) and Cu(II) ions: No adsorption was observed.
 1102 A. IKEDA et al.

uranyl ion reported.3) 2. Cation Adsorption and Desorption on Cation Ex-

No adsorption was observed for Al(III), Ni(II) and Cu(II)
ions. Although slight adsorption was observed for Fe(III) and
Cr(III) ions in 0.05–0.1 mol/dm3 sulfuric acid, the distribu-
tion coefficient of uranyl ion is six times as large as those
of Fe(III) and Cr(III) ions in 0.1 mol/dm3 sulfuric acid solu-
tion, indicating that the uranyl ion can be separated from the
metal ions in such low concentration of sulfuric acid. The
curve of the distribution coefficients for uranyl ion seems to
be strange as compared with that in hydrochloric acid solu-
tion or nitric acid solution, where the maximum values of
the distribution coefficients are at higher acid concentration
of around ∼10 mol/dm3 in hydrochloric acid medium4) and
around ∼8 mol/dm3 in nitric acid medium.5)
It should be pointed out that bisulfate ion, HSO− 4 , be-
comes predominant in the higher concentration region of
sulfuric acid, and it is well-known that the large oxoacid
anion, i.e. bisulfate ion, perchloric acid and so on, is
strongly adsorbed in an anion exchange resin. Simultane-
ously at the higher concentration of sulfuric acid, uranyl sul-
changes into [UO2 (HSO−
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change Resin
Breakthrough chromatography was carried out to consider
the adsorption of Fe(III), Al(III), Cr(III), Ni(II) and Cu(II)
ions in cation exchange resin. The results obtained at room
temperature (20◦ C) are presented in Fig. 5. Fe(III), Al(III),
Ni(II) and Cu(II) ions in 0.1 mol/dm3 sulfuric acid were com-
pletely adsorbed with sharp breakthrough boundaries. At
higher concentrations of sulfuric acid, the adsorption capac-
ities of the cation exchange resin seem to be decreased; the
breakthrough point for 0.5 mol/dm3 sulfuric acid is 200 cm3
which is almost a half value of that of 0.1 mol/dm3 sulfuric
acid. The important fact observed in Fig. 5 is the ion ex-
change property of Cr(III). Chromium is dissolving as a triva-
lent cation and conceived to be easily adsorbed in cation ex-
change resin. However, the results in Fig. 5 indicated that
Cr(III) was not practically adsorbed in the resin. To facilitate
the adsorption of Cr(III) in the cation exchange resin, the col-

fate anion [UO2 (SO2− 4 )2 ]

2−
4 )2 ] ,
0
3
− 2− − 0.1 mol/dm H2SO4
[UO2 (HSO4 )(SO4 )] , and so on. Therefore, as the concen- 2.00 Fe
tration of sulfuric acid increases, the selectivity of uranyl ion 1.75 Al
for an anion exchange resin is reduced due to the reduction of Cr
1.50
Ni
the negative charged complexes. 1.25
Cu
Figure 4 shows the adsorption behavior of uranyl ion in 1.00
0.1 and 0.2 mol/dm3 sulfuric acid solution: the adsorption 0.75
capacity of uranyl ion at 0.1 mol/dm3 sulfuric acid solution 0.50
is almost twice of that at 0.2 mol/dm3 . On the other hand, 0.25
there are no large differences in the distribution coefficients 0.00
0 200 400 600 800 1000
at 0.1 mol/dm3 and at 0.2 mol/dm3 in Fig. 3. It is consid-
ered that the result of columnar experiment reflects the ion 3
0.25M mol/dm H2SO4
exchange capacity and the kinetics of adsorption-desorption, 2.00
although such information cannot be obtained by batch-type 1.75
experiment. Therefore we give a lot of weight to the informa- 1.50
C/C0

tion obtained by the columnar experiments. The ion exchange 1.25

capacity in 0.1 mol/dm3 sulfuric acid calculated from the re- 1.00
sult was 11.9 mg-U/cm3 -resin. The uranyl ion adsorbed in 0.75
the resin was desorbed with 2 mol/dm3 sulfuric acid solution 0.50
at 20◦ C. 0.25
0.00
0 200 400 600 800 1000
1.0
3
0.5 mol/dm H2SO4
0.8 2.00
1.75
0.6
C/C0

1.50
0.4 1.25
1.00
0.2 0.75
0.50
0.0
0 400 800 1200 1600 2000 0.25
3
Effluent Volume (cm ) 0.00
0 200 400 600 800 1000

Fig. 4 Results of columnar experiments for uranyl ion adsorption Effluent Volume (cm 3)
in anion exchange resin at 20◦ C
C0 : Concentration in original feed solution Fig. 5 Results of columnar experiments for metal cations adsorp-
C: Concentration in eluent tion in cation exchange resin in different concentrations of sulfuric
: 0.2 mol/dm3 H2 SO4 , ●: 0.1 mol/dm3 H2 SO4 acid at 20◦ C

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

 Ion Exchange Separation for Decontamination of Centrifuge Enrichment Plant 1103
2.00 18
1.75 at 50 C 16 Fe
1.50 14 Al
1.25 12 Cr
10

C/C0
1.00 Ni
0.75 8 Cu
0.50 6
0.25 4
0.00
2
0 200 400 600 800 1000 0
2.00 0 200 400 600 800
Fe at 80 C
3
1.75 Effluent Volume (cm )
1.50
Al
Cr Fig. 7 Desorption behavior of metal cations by 1 mol/dm3 sulfuric
1.25
C/C0

Ni acid at 20◦ C
1.00
Cu
0.75
0.50 30
0.25
25
0.00
0 200 400 600 800 1000
20
Downloaded by [223.86.104.56] at 01:33 22 March 2014

2.00

1.75 at 100 C
1.50
1.25
1.00
0.75
0.50
0.25
0.00
0 200 400 600 800 1000
3 tions of sulfuric acid at 20◦ C
Effluent Volume (cm )
Fig. 6 Results of columnar experiments for metal cations adsorp-
tion in cation exchange resin at different temperatures
Medium: 0.1 mol/dm3 sulfuric acid
umn temperature was elevated. The adsorption of the tested
cations at higher temperatures of 50, 80 and 100◦ C are pre-
sented in Fig. 6. It is noted that Cr(III) can be adsorbed in the
resin at higher temperatures.
Although Fe(III), Ni(II) and Cu(II) ions adsorbed in the
resin were desorbed by 1 mol/dm3 sulfuric acid solution, the
elution curves of Al(III) and Cr(III) ion were not sharp as
shown in Fig. 7. It would need a great deal of eluent to desorb
them completely. The result of Cr(III) elution by 2 mol/dm3
sulfuric acid solution are plotted in Fig. 8 along with the
result obtained by using 1 mol/dm3 sulfuric acid. It seems
that the elution curve of Cr(III) become pretty sharp by us-
ing 2 mol/dm3 sulfuric acid solution. The similar behavior
was observed concerning the elution of Al(III) ion. Therefore
2 mol/dm3 sulfuric acid solution is concluded to be an appro-
priate eluent for cations.
The cause of the peculiar adsorption-desorption behaviors
of Al(III) and Cr(III) ions observed is considered as the ef-
fect of the slow ligand exchange rates. It is well-known
that the exchange of inner-sphere ligand of Al(III) or Cr(III)
ions is far slower than those of other metal elements. For
C/C0
3
15 2 mol/dm H2SO4
10
5
0
0 200 400 600 800 1000 1200 1400
3
Effluent Volume (cm )
Fig. 8 Desorption behavior of Cr(III) ion by different concentra-
◆: 2 mol/dm3 H2 SO4 , ♦: 1 mol/dm3 H2 SO4
example, the ligand exchange rates of inner-sphere water
molecule are 1.6×10−1 s−1 for Al(III) ion6) and 4.3×10−7 s−1
for Cr(III) ion,7) respectively at 25◦ C although that of Fe(III)
is 8.2×103 s−1 .8) Therefore once the neutral or anion complex
of Al(III) or Cr(III) sulfate (e.g. [AlIII (SO4 )2 ]− ) is formed, it
is difficult to be transformed into cation complex and cannot
be adsorbed in the cation exchange resin. The elevation of
column temperature allows faster ligand exchange, the rate of
cation complex in solution increases and the metal ions begin
to adsorb in the cation exchange resin. The similar theory can
be applied to the explanation for the desorption behavior.
3. Separation and Recovery
The experimental results for separation of uranium and
other metals are shown in Fig. 9. It was observed that the
uranyl ion in the solution was adsorbed in the anion exchange
resin in Column-1 and the metal cations were in the cation
exchange resin in Column-2. Until the finish of feeding
the simulated decontamination solution and the rinse solu-
tion of 0.1 mol/dm3 sulfuric acid solution, i.e. until 1,200 cm3
of effluent volume, no uranium was detected at the bottom
of Column-1 and no other metal elements were detected in
the effluent from Column-2. The uranyl ion and the metal
ions adsorbed in the resins were desorbed by 400 cm3 of

VOL. 39, NO. 10, OCTOBER 2002

 1104 A. IKEDA et al.
3
0.1 mol/dm H2SO4
3
2 mol/dm H2SO4
droxide (MII (OH)2 ) in alkaline solution and their hydroxides
Feed Solution precipitate in aqueous sodium hydroxide while they dissolve
in the presence of surplus NH+
1500
3 ion. It is also well-known
1200
on Anion Resin that Al(III) ion forms its hydroxide (Al(OH)3 ) precipitation in
the solution whose pH value is nearly 6. However, at higher
Concentration
(mg-UO2 /dm )
3

900 pH values, over pH=10, the hydroxide changes into alumi-

nate ion ([Al(OH)4 ]− ) and dissolves in water. Therefore, two-
2+

600 U stage precipitation process should be considered: Al(III) ion

precipitates at pH=6 and other ions precipitate at pH=13 by
300
aqueous sodium hydroxide.
0
20 4. Concept of Decontamination System
On the basis of the experimental results obtained, a con-
on Cation Resin cept of an actual decontamination system using ion exchange
15
resins is proposed as shown in Fig. 10. The equipment in the
Fe centrifuge enrichment plant is washed by 0.1 mol/dm3 sulfu-
C/C0

10 Al
ric acid solution to remove uranium on the surface. The waste
Cr
Ni solution from the plant is filtrated to remove sludge and is in-
5
Cu troduced into the columns of the ion exchange resins. The
uranyl ion is adsorbed in the anion exchange resin at room
0
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0 300 600 900 1200 1500 temperature and the metal ions passed through the anion ex-
Effluent Volume (cm )
3 change rein are adsorbed in the cation exchange resin at 80◦ C.
The effluent from the column of the cation exchange resin is
Fig. 9 Adsorption-desorption of simulated waste solution in ion reused for washing the equipments. The uranyl ion adsorbed
exchange resins in the anion exchange resin is desorbed by 2 mol/dm3 sulfu-
ric acid and is recovered by ammonium hydroxide solution as
ammonium diuranate (ADU). To ensure the removal of ura-
Table 2 Precipitation rate nium, the supernatant solution is introduced into the column
of amidoxime type chelating resin,9) which adsorbs uranyl ion
Precipitant
NH4 OH NaOH
Element
pH=11 pH=13 pH=6
Precipitation rate (%)
U(VI) >99.9
Fe(III) >99.9 99.9 >99.9
Al(III) 96 47.2 99.9
Cr(III) 99.9 99.8 99.9
Ni(II) 17.9 99.7 32.6
Cu(II) 15.3 98.9 87.3

2 mol/dm3 sulfuric acid solution. The amount of uranyl ion

desorbed was equivalent to that in the original solution. The
amount of metal ions desorbed was also equivalent to that in
the original solution and the uranyl ion was not detected in
the eluent from Column-2. Therefore, it is concluded that the
uranyl ion can be separated effectively from the metal ions.
Table 2 gives the precipitation rates of the uranyl ion
and the metal ions. The uranyl ion was precipitated com-
pletely by the addition of ammonium hydroxide solution at
pH=11. Although Fe(III), Al(III) and Cr(III) ions in the so-
lution were precipitated almost completely, the precipitation
rates of Ni(II) and Cu(II) ions were very low, 18% of Ni(II)
ion and 15% of Cu(II) ion. All the metal ions except Al(III)
ion were precipitated effectively by aqueous NaOH at pH=13
and Al(III) ion was precipitated by aqueous NaOH at pH=6.
It is well-known that Ni(II) and Cu(II) ions form their hy- Fig. 10 Flow sheet of decontamination system

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

 Ion Exchange Separation for Decontamination of Centrifuge Enrichment Plant
efficiently, implemented as a safety countermeasure. The ef-
fluent from the chelate resin column is non-radioactive and
contained ammonium sulfate which could be used as a fertil-
izer. The metal ions adsorbed in the cation exchange resin are
also desorbed by 2 mol/dm3 sulfuric acid and recovered by
aqueous sodium hydroxide as their hydroxide precipitations
at suitable values of pH. The rest solution is introduced into
an electrolytic cell and electrolyzed into sodium hydroxide
and sulfuric acid. These sodium hydroxide and sulfuric acid
are reused as the reagents for precipitation and elution again.
The precipitations may be used as a raw material of ferrite.
The ion exchange resins are regenerated by 0.1 mol/dm3 sul-
furic acid after metal desorption by 2 mol/dm3 sulfuric acid,
are reused for the adsorption process.
The ion exchange capacities of the tested ion exchange
resins are 0.05 mol-UO2+ 3
2 /dm -resin for the anion exchange
n+ 3 radiation-resistant anion exchange resin to liquid radioactive
resin and 0.612 mol-M /dm -resin for the cation exchange
resin, respectively. A 40 dm3 of the cation exchange resin and
10 dm3 of the anion exchange resin are required for recycle
use of 1 m3 of the waste solution.
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IV. Conclusions
The separation of uranyl ion from Fe(III), Al(III), Cr(III),
Ni(II) and Cu(II) ions in 0.1 mol/dm3 sulfuric acid medium
was successfully carried out by using ion exchange resins.
The adsorbed uranyl ion and the metal ions were desorbed
by 2 mol/dm3 sulfuric acid solution. The uranyl ion in the
VOL. 39, NO. 10, OCTOBER 2002
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1105
eluent was recovered as ammonium diuranate by ammonium
hydroxide solution. The metal ions except Al(III) ion were
recovered by aqueous sodium hydroxide as their hydroxide at
pH=13 and Al(III) ion was also recovered at pH=6.
From the experimental results obtained, it is concluded that
the uranium recovery system using ion exchange resins would
bid fair to be applicable for the decontamination of centrifuge
enrichment plant although more practical investigations and
considerations are needed for the application to actual decon-
tamination process.
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