Fusion Engineering and Design 84 (2009) 11081112

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Fusion Engineering and Design
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Molecular-sieving effect of zeolite 3A on adsorption of H
2
, HD and D
2
K. Kotoh

, S. Takashima, Y. Nakamura
Faculty of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan
a r t i c l e i n f o
Article history:
Available online 14 February 2009
Keywords:
Hydrogen-isotope separation
Adsorption
Molecular sieve
Sieving
Connement
Tritium
a b s t r a c t
Synthetic zeolite 3A has the molecular-sieving windows of nominal diameter 0.3nm in its crystal lattice
framework, which obstruct the crystalline adsorption of molecules of diameter larger than 0.3nm, except
water, hydrogen and helium. The windows diameter slightly varies with temperature, however, that is
endorsed in experimental results that hydrogen cannot be adsorbed at the liquid-nitrogen temperature.
Authors measured the range of temperature where zeolite 3A permits hydrogen adsorption, and revealed
the temperature difference of several degrees in appearance of molecular sieving for H
2
and D
2
. This
difference is important because from a H
2
D
2
mixture one isotope could be isolated by adsorption if
operated at a temperature regulated between the molecular-sieving appearance temperatures. We have
reported large values of D
2
/H
2
separation factor obtained from molecular-sieving experiments. In this
study, the effect of sieving for the hybrid-atomic isotope HD is examined using a H
2
HDD
2
mixture. We
here report the experimental HD/H
2
separation factor evaluated between the D
2
/H
2
factor and unity. This
result is signicant because where the effective molecular diameter concerning the sieving mechanism
is suggested. From this knowledge, the isotopic effect of sieving for HT and DT can be predicted.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Synthetic zeolites having the strong power of adsorption
for water are conventionally used in such as tritiated water
safety-connement systems [14]. Since zeolites also exhibit the
adsorptive power for hydrogen under cryogenic condition, zeo-
lite packed-bed columns are applicable to the system of tritium
recovery from DT fusion blanket [58]. In cryogenic adsorption
of hydrogen isotopes onto zeolites, isotope separation is observed
[911]. Authors have claried the isotope separation factors among
six species H
2
, HD, D
2
, HT, DT and T
2
adsorbed onto synthetic zeo-
lites 5A and 13X at the liquid-nitrogen temperature 77.4K, through
volumetric adsorption experiments and theoretic analyses [12].
The separation factors suggest the reality of a hydrogen-isotope
separation system using adsorption columns. Authors and collab-
orators hence have been developing a system of pressure swing
adsorptionor pressure-and-temperatureswingadsorption[1315],
which may have advantages over the cryogenic distillation system
in operational convenience, cost performance and reactant process
inventory.
The isotope effect on adsorption is due to the difference in ther-
modynamic interaction between adsorbent material and adsorbate
molecules. Synthetic zeolites, however, havenot onlytheadsorptive

Corresponding author. Tel: +81 92 802 3507; fax: +81 92 802 3507.
E-mail address: kotoh@nucl.kyushu-u.ac.jp (K. Kotoh).
power and selectivity but also the mechanical function of selec-
tivity for molecular size or/and structure, molecular sieving, as
they are so-called molecular sieves. This sieving phenomenon
is never observed in the adsorption of hydrogen isotopes onto
zeolite-4A, -5A and -13X at least above 77.4K. In a previous
study, however, we have shown the appearance of molecular-
sieving effect on adsorption of H
2
and D
2
onto zeolite-3A, through
pseudo-isobaric adsorption experiments, where the isotopic dif-
ference is observed. And then, we have veried the isotope effect
of molecular sieving with abnormally large values of D
2
/H
2
sepa-
ration factor obtained by a sequential experiment of adsorption,
connement, evacuation and desorption using a H
2
D
2
mixture
[16].
An important interest is leaved in the previous work [16] how
a hybrid-atomic isotope such as HD behaves on the sieves. If the
larger atomic diameter were the sieving determination factor, the
hybrid HD would behave as its larger atomic twin H
2
. Experimen-
tal results shown here demonstrate that the sieving determinant is
not the atomic diameter but the larger molecular-diameter, that is,
the kinetic diameter of a two-atomic molecule inrotational motion.
The rotational motion would be required for hydrogen molecules
to pass through sieve meshes. Since the molecular sieving is of
mechanical manner, this suggests the possibility of isolation of HT
from a H
2
HT mixture or DT from a D
2
DT mixture. If the sieving
is applicable to hydrogen-isotope separation, remarkable progress
would be expectable in development of effective tritium-handling
processes for fusion reactor fuel-cycle system.
0920-3796/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fusengdes.2009.01.052
K. Kotoh et al. / Fusion Engineering and Design 84 (2009) 11081112 1109
Fig. 1. Models of simplied molecular-sieving mechanism for hydrogen isotopes.
2. Theoretical [17,18]
Synthetic zeolite NaA (SZ-NaA) is the initiator of A-type zeo-
lites, which is the crystal of alminosilicate containing sodium
cations, Na
12
Al
12
Si
12
O
48
(dehydrated), formingacubic latticestruc-
ture. In the lattice framework, adsorptive cavities of 1.23nm in
nominal inner diameter are comprised, where adjacent cavities
are connected together in three-dimension with a window of 8-
oxygen-atomic alminosilicate ring having a nominal inner diameter
of 0.4nm (4). Therefore, molecules of diameter larger than 4
are never adsorbed into SZ-NaA. Since synthetic zeolites exhibit
the molecular sieving, these are so-called molecular sieves and
the type NaA is also known as 4A: SZ-4A. The other zeolites of
A-type are originated by exchanging the Na cations for another
species.
Synthetic zeolite KA (SZ-KA) including potassium makes the
8-oxygen rings to be 3 in nominal inner diameter, also known
as SZ-3A, where water, helium and hydrogen of diameter less
than 0.3nm are permitted crystalline adsorption. Hydrogen hav-
ing nominal diameters of 0.24nm0.31nm, however, cannot be
adsorbed at a cryogenic temperature approaching to the liquid-
nitrogentemperature, becausethe8-oxygenringstructuredepends
on temperature, that is, the sieve meshes reduce with decreasing
temperature [17].
In the previous study [16], authors observed the temperature
effective to the crystalline adsorption of H
2
or D
2
, and revealed the
temperature difference of a few degrees in appearance of molec-
ular sieving for H
2
and D
2
. This difference is important; since the
molecular sieving is of a mechanical separation manner, it is ideally
expectablethat thesmaller isotopemolecules canbeisolatedfroma
H
2
D
2
mixtureif operatedbetweenthesievingappearancetemper-
atures. We have veried the sieving isotope separation with values
of D
2
/H
2
separation factor, abnormally large in comparison with
thoseduetothedifferenceinthermodynamic adsorptioncharacter-
istics. A problem is there, however, that the zeolite sieves regulate
which diameter of a twin-atomic molecule, larger or smaller one,
connecting to the distinction of hybrid-atomic molecules from
twin-atomic ones.
Fig. 1 shows schematic diagrams of simplied models of
molecular-sieving mechanismfor hydrogen isotopes. If the smaller
diameter of a two-atomic molecule corresponding to its larger
atomic diameter is the effective geometry, as shown as Case
(a), the hybrid HD would behave together with the twin H
2
larger than D
2
. In this case, the sieves never isolate HD from a
H
2
HD mixture. On the other hand, if the larger molecular diam-
eter is of determination for the sieving effect as illustrated as
Case (b), the hybrid HD could be isolated from a H
2
HD mix-
ture.
3. Experimental
In order to examine the effect of sieving for hybrid-atomic
molecules, using a volumetric adsorption apparatus shown in
Fig. 2, we carried out the following sequential operations in
an adsorptiondesorption experiment with a packed-bed of SZ-
3A:
Fig. 2. Schematic diagram of volumetric adsorption apparatus.
1110 K. Kotoh et al. / Fusion Engineering and Design 84 (2009) 11081112
Fig. 3. Normalized build-up pressure curves of D
2
and H
2
released frommolecular-
sieving connement with respect to temperature.
(1) Preparation: loading a gas mixture of H
2
HDD
2
at a total pres-
sure around 3.610
3
Pa onto the activated packed-bed cooled
at the liquid-nitrogen temperature 77.4K.
(2) Sieving adsorption: increasing temperature upto a point within
a specic range indicated in pseudo-thermostatic desorption
experiments for D
2
and H
2
, where the sieves govern the crys-
talline adsorption.
(3) Connement: re-cooling down to 77.4K, and then, evacuating
the gas holder including the packed-bed until arriving at lower
than 10
5
Pa.
(4) Desorption: recovering the crystalline-adsorbed sample by
heating up to room temperature.
(5) Analysis: measuring fractions of H
2
, HD and D
2
in gas samples
by a mass-spectrometric system.
SZ-3A pellets of 2mm spherical (Merck Ltd.) were packed at
about 24g in a test cell set at the end of a nger. The initial sample
of H
2
HDD
2
was prepared from a mixture of 40% H
2
and 60% D
2
at a total pressure of 5.810
3
Pa by operating an electric discharge
tube producing the reaction, H
2
+D
2
2HD. The three-component
mixtures produced were composed of about 25% H
2
, 30% HD and
45% D
2
. In the second step, 130K, 140K or 160K was selected as the
point of temperature.
In advance, preliminary experiments were made for examining
the temperature ranges of appearance of sieving for H
2
and D
2
, as
follows:
(1) Adsorption/connement: loadingavolumeof H
2
or D
2
at apres-
sure of 8.510
3
Pa onto the packed-bed at room temperature
which has been activated beforehand by heating at 573K under
the evacuation arriving at 510
5
Pa, and then, cooling down
to 77.4K.
(2) Isolation: evacuating the gas holder including the packed-bed
until reaching lower than 10
5
Pa, after arrival at the lowest
temperature of 77.4K.
(3) Recovery: releasing a volume of H
2
or D
2
from connement by
slowly heating up to room temperature.
Inthe rst step, the connement wouldtake place fromthe wall-
side to the central part of the packed-bed in the order of arrival at
the critical temperature. In the second step, the volume of sample
gas except the amount conned in crystalline pores was evalu-
ated. In the last step, the heating has to be operated as slow as
possible, because of pseudo-thermostatic experiment for examin-
ing the temperature range of sieving function appearance. So, we
employed a bulking agent of shaved ice as coolant in the cryogenic
vacuum pot, in alternating combination with liquid nitrogen, in
order to moderate a rising rate of temperature in the test section.
The pressure build-up in the volumetric closed system indicates a
temperaturerange where molecules are releasedfromconnement
by sieves.
4. Results and discussion
Fig. 3 shows results from the preliminary experiments, where
each curve indicates the build-up pressure of H
2
or D
2
in the vol-
umetric closed system. The pressure curves are normalized with
saturated pressures of 300Pa and 460Pa respectively for H
2
and D
2
.
The build-up curves demonstrate the behavior of H
2
and D
2
leaving
from sieving connement within crystalline pores, released by the
sieves increasing their meshsize withelevating temperature. These
sequential experiments were begun fromthe step of loading gas on
adsorbent at a pressure of 8.510
3
Pa. The change of curves indi-
cates the connement release starting around 120K for D
2
or 130K
for H
2
and then establishing at about 180K for D
2
or about 190K
for H
2
. In this transient region, the curves exhibit a temperature
difference around several degrees, D
2
indicating the temperature
lower than that of H
2
. Since the experiments are in temperature-
transitional process, the sieving release occurs sequentially in the
Fig. 4. Schematic illustration of molecular-sieving release in temperature transient process.
K. Kotoh et al. / Fusion Engineering and Design 84 (2009) 11081112 1111
Fig. 5. Schematic process of adsorption of hydrogen isotopes isolated/separated by
sieving dependent on temperature.
packed-bed as illustrated in Fig. 4. The range of T
W
from CT to T
C
corresponds to the changing range shown by the curves in Fig. 4.
The temperature ranges of sieving for H
2
and D
2
agree with those
from pseudo-isobars in the previous work [16].
Referring to the result from preliminary examinations, three
series of experiment with a H
2
HDD
2
sample were performed at
130K, 140K and 160K of T
W
selected as the returning point from
sieving adsorption to connement, where we assumed the adsorp-
tion/connement of hydrogen isotopes separated by the sieving in
a manner explained in Fig. 5. In the desorption process after isola-
tion of conned sample, the heating-up operation was regardless
of moderation in a rate of increase in temperature, anticipating that
the release of D
2
and H
2
would begin respectively at net temper-
atures around 115K and 125K. The released sample-gas build-up
pressures were saturated at 20Pa, 41Pa and 140Pa in the experi-
ments under the conditions of 130K, 140K and 160K, respectively.
If the same pseudo-thermostatic operation as in the preliminary
experiments were carried out, each normalized build-up pressure
curve would be observed behaving between D
2
and H
2
curves
shown in Fig. 3.
When the sieving critical temperature CT for every hydro-
gen isotope is within the temperature distribution formed in the
packed-bed, conned at T
W
the crystalline gas is D
2
-enriched
because D
2
diametrically smaller than H
2
is isolated locally in the
packed-bed. Problem is the behavior of HD. As shown in Fig. 5, if
the critical temperature for HD is between those for H
2
and D
2
, the
hybrid HD would be also enriched in conned samples because of
formationof theintermediateregioncontainingisolatedHDandD
2
,
but reduced relatively to D
2
, of course. This behavior of HDmatches
with the model of sieving for two-atomic molecules assumed as
Case (b) in Fig. 1. On the other hand, if according to the model
assumed as Case (a) of dependence on the molecular larger atomic
diameter, the behavior would be same as that of H
2
because of the
same sieving critical temperature.
Table 1
Experimental separation factors of HD/H
2
and D
2
/H
2
in molecular-sieving adsorp-
tion of SZ-3A.
TW
HD/H
2

D
2
/H
2
130K 3.19 3.71 (4.33)
a
140K 2.60 3.14 (3.04)
a
160K 2.20 2.24 (2.32)
a
a
Obtained in the previous study [16].
Experimental results are listed in Table 1, where the separation
factor
HD/H
2
or
D
2
/H
2
is dened as

i/j
=
(y
i
/y
j
)
conned
(x
i
/x
j
)
loaded
(1)
Here, x and y are the mole fractions of a component in the loaded
gas-phase and the conned crystalline-adsorbed phase, respec-
tively. The subscript i denotes a subjective HDor D
2
, andj represents
H
2
as reference. The experimental
HD/H
2
values 3.71, 3.14 and
2.24 respectively at 130K, 140K and 160K are consistent with ones
previously obtained from similar experiments using H
2
D
2
. How-
ever, these values from sieving experiments are abnormally large
compared with those predictable in physical adsorption charac-
teristics of hydrogen isotopes at these temperatures, referring to
such as a study of multi-component behavior of hydrogen isotopes
onto SZ-5A or -13X at 77.4K [12]. In consideration on a variation
of the experimental values, a rising trend in
D
2
/H
2
with decreas-
ing temperature can be interpreted with the sieving model, due to
reduction of the region of H
2
D
2
or H
2
HDD
2
with reducing the
returning-point temperature.
The values of
HD/H
2
clearly larger than unity suggest that the
molecular sieving occurs in the mechanism considered in Case (b).
And also, the values reduced relatively to
D
2
/H
2
reect the diamet-
ric order of hydrogen isotopes in the sieving model of Case (b). The
enrichment of HD in the SZ-3A packed-bed results from the isola-
tion of HD-D
2
in the intermediate region. Accordingly, the trend of
an increase in
HD/H
2
with decreasing temperature meets with that
in
D
2
/H
2
, due to reduction of the H
2
HDD
2
region.
The sieving behavior of SZ-3A adsorbing the hybrid-atomic
molecules hence suggests the possibility not only of a newmethod
for production of deuterium from natural hydrogen, but also
of a convenient but remarkably effective technique for isolating
removal or recovery of HT diluted in hydrogen. In diametric com-
parisonamonghydrogenisotopes, however, the difference between
D
2
and HT is sensitive. When the effective diameter of a hydrogen-
isotope molecule passing through sieves is assumed corresponding
to its rotational diameter, hybrid-atomic molecules exhibit large
effective diameters relatively to twinones. Reasonis that the hybrid
molecules are rotating with wobbling motion because the center
of mass differs from that of the quantum-mechanical wave func-
tion [12,19]. Thus, the sieving takes place in the order of H
2
, HD,
HT, D
2
, DT and T
2
. Therefore, we would be able to develop various
processes of isolating hydrogen-isotope separation, if temperature
can be controlled preciously between the molecular-sieving critical
temperatures.
5. Conclusions
The molecular sieving of SZ-3Afor HDcontained in a H
2
HDD
2
mixture was examined by the sequential experiments of sieving
adsorption, connement and recovery. The separation factor of
HD/H
2
obtained from the sieving operation was larger than unity
but reduced relatively to that of D
2
/H
2
. This result endorses the
mechanism of sieving for hydrogen isotopes in which the dynamic
diameter of a molecule in rotation is determinant. The sieving is
possible to separate between H
2
, HD, HT, D
2
, DT and T
2
. Moreover,
drastic separation is expectable, since the sieving is of utilizing the
geometric difference. The molecular sieving of SZ-3A would make
it possible to develop a convenient but remarkably effective system
for tritium separation, removal or recovery.
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