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Article history: Nuclear waste management has to be taken into account for fusion machine using tritium as fuel. Soft
Received 23 August 2013 housekeeping waste (e.g. gloves, tissues, protective clothes, etc.) is produced during the whole life as well
Received in revised form 3 December 2013 as during the dismantling of the reactor and is contaminated by tritium under reduced (HT) and oxidized
Accepted 8 January 2014
(HTO) forms.
Available online 3 February 2014
In collaboration with ENEA, a lab-scaled facility has been built at CEA Cadarache for soft housekeeping
waste detritiation and tritium valorization. The previously milled waste is placed in a reactor to be heated
Keywords:
up to a temperature lower than the housekeeping melting point. A carrier gas is then injected in the
Waste
Soft housekeeping
detritiation reactor to remove tritium, thanks to the combined effects of temperature and carrier gas
Detritiation (type and feed ow). The tritiated gas exhausted from the detritiation reactor is then sent through a
Catalytic membrane reactor catalytic PdAg membrane reactor (CMR) where tritium is recovered via isotopic exchange reaction and
permeation phenomenon.
Based on previous studies that have allowed dening the most efcient operating conditions for the
detritiation process, this work presents the results obtained by the coupling of the detritiation facility
with the CMR. Due to safety considerations, restrictions on the nature of the carrier gas were applied,
rejecting air as the carrier gas even though air was the best candidate for the detritiation part of the
process. The performance of the whole system was estimated by means of a parametric study on the
inuence of ow rates in the CMR and transmembrane pressure.
2014 Elsevier B.V. All rights reserved.
0920-3796/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fusengdes.2014.01.009
2104 K. Liger et al. / Fusion Engineering and Design 89 (2014) 21032107
2. Experimental apparatus
mechanism. As represented on the scheme below, this mechanism Dening the permeability of the membrane as
counts up 7 stages:
o o Hm,Q + HS,Q
PeQ = DQ SQ = DQ SQ exp
RT
molecule mass transfer from uid bulk to membrane surface;
dissociative adsorption on PdAg membrane surface;
o EQ
dissolution of atomic species: transition from PdAg surface to = PeQ exp (5)
RT
PdAg bulk;
diffusion of atomic species through the PdAg bulk;
Then the diffusion rate of specie Q can be estimated by a com-
atomic bulk to surface transition;
bination of Eqs. (3)(5):
recombination of atomic species and molecular desorption;
molecule mass transfer from membrane surface to uid bulk (per- EQ 2L
o
NQ = PeQ exp
meate). RT ln(router /rinner )
Due to the Pd-based membranes selectivity, only hydrogen and PQ2,lumen PQ2,shell (6)
its isotopes can permeate through the membrane. Migration direc-
tion depends on chemical potential gradient of the species in the with PQ2,lumen is the partial pressure of specie Q2 in the lumen side
membrane. Neglecting electrons ux due to the electrical current and PQ2,shell the partial pressure of specie Q2 in the shell side.
applied on the membrane, migration driving force becomes con- Eq. (6) quanties the permeation rate of one specie in a dense
centration gradient. For an ideal solution, the specie ux linked to membrane. For multicomponent transfer, a generalization of Eq.
this gradient in steady-state conditions can be represented by the (6) is proposed by [11]. Eq. (6) and its generalization to mul-
rst Ficks law [9]: ticomponent permeation show that the permeation rate can be
enhanced by an increase of temperature and/or an increase of the
JQ = DQ CQ (1) difference of partial pressure of specie Q in the lumen and the shell
side.
with JQ the molar ux of specie Q (mol m2 s1 ), CQ the molar
The approach above assumes that the mass transfer resistance in
concentration of specie Q in the membrane (mol m3 ) and DQ the
the lms at the surface of the membrane can be neglected. The mass
concentration-independent diffusion coefcient of specie Q in the
transfer resistance can be estimated from semi-empirical correla-
membrane (m2 s1 ). Due to the fact that permeation is an activated
tion involving the Sherwood (Sh), Reynolds (Re) and Schmidt (Sc)
process, the temperature dependency of DQ follows a Vant Hoff
numbers [9]:
type of law:
kG,Q2 L
Hm,Q ShQ2 = = Re Sc (7)
o DG,Q2
DQ = DQ exp (2)
RT
with DG,Q2 is the diffusion coefcient of specie Q2 in the gas
With T is the temperature, R the ideal gas constant (8.314 J/mol/K), (m2 s1 ), kG,Q2 the mass transfer coefcient of specie Q2 (m s1 ) and
o a pre-exponential factor (m2 s1 ) and H
DQ ,, the Sherwood number parameters. The Reynolds and Schmidt
m,Q the mobility
enthalpy of specie Q (J/mol). numbers are dened by
Considering a constant temperature along the membrane and Q2 u L
bulk diffusion as an unidirectional radial phenomenon, the trans- Re =
Q2
membrane diffusion rate through a L length membrane is obtained Q2
by integration of the above relation between 0 and ( is the thick- Sc =
Q2 DG,Q2
ness of the membrane):
with Q2 the density of specie Q2 (kg m3 ), Q2 the viscosity of
2L
NQ = DQ (CQ,lumen CQ,shell ) (3) specie Q2 (Pa s) and u the supercial velocity of the gas (m s1 ).
ln(router /rinner )
Eq. (7) shows that mass transfer coefcient depends on the pres-
with NQ the diffusion rate of specie Q (mol s1 ), CQ,lumen the molar sure, the temperature (through the species physical properties) and
concentration of specie Q at the surface in the lumen side (mol m3 ), also on the uid ow rate. As a consequence, increasing the uid
CQ,shell the molar concentration of specie Q at the surface in the shell ow rate should reduce the mass transfer resistance and increase
side (mol m3 ), rinner the membrane inner radius (m) and router the the permeation ux up to a certain limit.
membrane outer radius (m). One last phenomenon that can limit the performance of the cat-
As demonstrated by Caravella et al. [10] for membrane thick- alytic membrane reactor is the isotopic exchange between Q2 O and
ness higher than 10 m, adsorption and dissolution phenomena H2 kinetics, which is assumed to be fast enough compared to the
are widely faster than diffusion leading to an equilibrium between permeation phenomena.
specie in the membrane bulk and specie in the gas:
4. Results and discussion
Q2 gas2Q(membrane bulk)
Former experiments performed on the thermal treatment unit
This equilibrium is represented by Sieverts law in which Siev- have allowed determining the best operating conditions for soft
erts constant SQ follows a Vant Hoff type of law: housekeeping waste detritiation [1]. The best detritiation yield was
obtained using air as a carrier gas with a ow rate of 400 Nml/min
CQ HS,Q
SQ = = o
SQ exp (4) and an oven temperature just below the melting point of the
PQ2 RT soft housekeeping waste (150 C). Nevertheless, considering the
fact that the catalytic membrane reactor will use hydrogen as a
o a pre-exponential
With PQ2 is the partial pressure of specie Q2 , SQ swamping gas and will operate at around 400 C, explosive haz-
factor (m2 s1 ) and HS,Q the dissolution enthalpy of specie Q ard was studied and has lead to retain Ar + 2% O2 as carrier gas,
(J/mol). which is the most efcient carrier gas among those compatible
2106 K. Liger et al. / Fusion Engineering and Design 89 (2014) 21032107
Table 1 Table 3
Operating conditions of the tests. Experimental efciency.
Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Test 7 Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Test 7
with safe operation [1]. In that case, the ternary mixture nitro- by the fact that the membrane requires an activation phase before
gen/oxygen/hydrogen remains below ammability limits even at being well efcient [12]. Furthermore, the small difference of pres-
400 C. Furthermore, the use of air instead of Ar + 2% O2 in the same sure between the shell and the lumen side is not in favour of a
operating conditions did not increase the efciency of the ther- high transmembrane diffusion rate, as demonstrated by modelling
mal treatment. Under these conditions (temperature 150 C, carrier approach [13].
gas Ar + 2% O2 ), the maximum efciency (tritium activity extracted Test 2 was an intermediate test for which 2 parameters were
over initial tritium activity in the waste) obtained for the thermal modied: the transmembrane pressure and the ow rate in the
detritiation device is 56.1%. lumen side were increased. The yield and the conversion of Q2 O
Concerning the CMR, ENEA has developed a model analysis into Q2 were slightly improved even though the residence time in
based on a nite element method in order to simulate the behaviour the lumen was reduced. This is probably due to the transmembrane
of the reactor: effect of the main operating parameters such as tem- pressure which is in favour of Q2 removal.
perature and feed ow rates have been studied [8]. As a main result, Test 3 was similar to test 1 with a large increase of the differ-
the temperature effect in the range 300400 C has been found very ence of pressure between the lumen and the shell sides. Due to
negligible while much more relevant is the inuence of the protium the mechanical resistance of the thermal treatment unit, the trans-
feed ow rate in the shell (at 10 Nml/min the detritiation capability membrane pressure chosen corresponds to the limit of the system.
becomes insignicant. 100 Nml/min was found to be a reasonable As expected according to Eq. (6), the yield was improved signi-
value). For the feed ow rate in the lumen, values between 100 and cantly and test 3 is considered as a reference for the parametric
300 Nml/min can be handled. study.
As a consequence, the operating conditions for the present study Maintaining the same difference of pressure between lumen and
consider a temperature of 400 C for the CMR and a carrier gas in shell sides, an increase of ow rate in the shell side (test 4) or in the
the lumen side composed of Ar and 2% of O2 . The parametric study lumen side (test 5) was performed in order to check whether the
performed on the coupling device concerns mainly the inuence of mass transfer resistance in the lms was a limiting factor.
(see Table 1.): Test 4 can be directly compared to test 3 and it comes that an
increase of the ow rate in the shell does not have a signicant effect
the transmembrane pressure; on the performance of the CMR (i.e. the partial pressure of Q2 in the
the ow rates in the shell and lumen sides. shell side is sufciently low so that there is no effect of dilution on
the permeation rate). It is then not necessary to maintain high ow
First a series of tests is performed using approximately similar rate of hydrogen in the shell as it contributes to the dilution of
ow rates in the shell and lumen sides. The difference of pressure the gas exhausting the shell and which will have to be treated in a
between shell and lumen is then increased. Note that for mechan- further step for tritiated hydrogen form recovery.
ical strength reasons, the pressure in the lumen must be always Test 5 has also to be compared to test 3 and shows that an
higher than the one in the shell. Then, a second series of tests was increase of the ow rate in the lumen reduces the performance
performed to assess the effect of the variation of the ow rate in the of the CMR. That proves that mass transfer resistance in the lm is
shell and the lumen. The last test performed has the goal to conrm not the limiting factor and that the residence time of the gas is too
the best result obtained. low to obtain the steady state of permeation phenomenon. This can
Table 2 presents the tritium activity measured by liquid scintil- be deduced from the observation of the speciation measurements
lation at the outputs of the CMR. From these measurements, it is (see Table 2) which show a high amount of Q2 leaving the lumen
then possible to calculate the CMR efciency by means of the yield side.
and the detritiation factor as well as the maximum overall process Test 6 is similar to test 3 but both ow rates in the lumen and the
efciency considering the maximum thermal treatment efciency shell side were increased in order to get closer to the ow rate of
of 56.1% (see Table 3). the thermal unit. The reduction of the residence time in the lumen
For test 1, the yield of the CMR is particularly low even though lowers the conversion yield which is logically between the yield
Q2 O is largely converted into Q2 , which remains in the lumen side obtained in test 5 (ow rate in the lumen side: 284 Nml/min) and
stream (see Table 2). This low permeation rate can be explained test 3 (ow rate in the lumen side: 113 Nml/min). It seems that the
increase of ow rate in the shell side has no effect on the permeation
Table 2 rate of Q2 .
Experimental results. Test 7 is similar to test 3 and was performed to test reproducibil-
ity of the system. Similar yield, DF and ratio Q2 over Q2 O were
Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Test 7
obtained for both experiments.
Output tritium activity (Lumen side) (Bq) In conclusion, the best operating conditions for the designed
Q2 995 707 92 92 313 425 154
Q2 O 50 83 217 226 550 1683 281
CMR are:
Q2 /Q2 O 20 8.5 0.4 0.4 0.6 0.2 0.6