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international journal of hydrogen energy 35 (2010) 3598–3609

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Generalized model development for a cryo-adsorber and 1-D


results for the isobaric refueling period

V. Senthil Kumar a,*, Sudarshan Kumar b


a
India Science Lab, General Motors Global R & D, Creator Building, International Technology Park, Bangalore 560066, India
b
Chemical Sciences and Material Systems Lab, General Motors Global R & D, Warren Technical Center Campus, 30500 Mound Road, Warren,
MI 48090, USA

article info abstract

Article history: We have developed 3-D model equations for a cryo-adsorption hydrogen storage tank,
Received 1 December 2009 where the energy balance accommodates the temperature and pressure variation of all the
Received in revised form thermodynamic properties. We then reduce the 3-D model to the 1-D isobaric system and
7 January 2010 study the isobaric refueling period, for simplified geometry and charging conditions. The
Accepted 8 January 2010 hydrogen capacity evolution predicted by the 1-D axial bed model is significantly different
Available online 13 February 2010 than that predicted by the lumped-parameter model because of the presence of sharp
temperature gradients during refueling. The 1-D model predicts a higher hydrogen capacity
Keywords: than the lumped-parameter model. This observation can be rationalized by the fact that
Hydrogen storage modeling a bed with temperature gradients on equilibration should desorb gas, whenever the
Cryogenic adsorption adsorbed phase entropy is lower than the gas phase entropy. The 1-D analysis of the
Metal-organic frameworks isobaric refueling period does not show any significant difference in hydrogen capacity
Refueling evolution among the axial, single and multicartridge annular bed designs. Hence, a multi-
cartridge annular design, though giving a slightly lower pressure drop, does not offer any
heat and mass transfer enhancement over the single cartridge design. And, the single
cartridge annular design appears to be optimal.
ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction Consider a fuel-tank with an initial operating condition of


20 bar and about 80 K, and a fuel cell operating at about 4 bar.
On-board storage of hydrogen by adsorption at low tempera- The four processes occurring in a cryo-adsorber fuel-tank are:
tures (around 77 K, liquid nitrogen temperature) and moder-
ately high pressures (less than 60 bar) is considered viable and  Refueling – A depleted fuel-tank at low pressure (say 4 bar or
competitive with other storage technologies including liquid 1.1 bar) and higher temperature (say 120–140 K) is charged with
hydrogen, compressed gas, and metallic or complex hydrides hydrogen. Heat released during adsorption is removed by the
[1]. Nanoporous metal-organic frameworks (MOFs) as adsor- recirculation of cool hydrogen gas entering at 80 K or below.
bents offer good gravimetric capacity and fast and reversible  Discharge – When the vehicle is in motion, the fuel cell stack
kinetics. For example, MOF-5 has a reversible capacity of about demands are met by desorbing hydrogen from the cryo-
6 wt% at 77 K and 50 bar [2]. MOF-5 as an adsorbent material adsorber bed. Desorption is enhanced by the recirculation of
has been studied extensively and we consider it to assess the hot hydrogen gas. The tank pressure may eventually drop to
tank performance in our previous [3] and current works. say 4 bar or 1.1 bar.

* Corresponding author. Tel.: þ91 80 41984567; fax: þ91 80 41158262.


E-mail addresses: senthil.v.kumar@gmail.com, senthil.vadivelu@gm.com (V.S. Kumar).
0360-3199/$ – see front matter ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.01.025
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international journal of hydrogen energy 35 (2010) 3598–3609 3599

Notation mg gas viscosity, Pa s


aPg, kTg isobaric thermal expansion coefficient and
T, P temperature and pressure, K, bar
isothermal compressibility, 1/K, 1/bar
L, R, dp length and radius of the adsorbent bed, pellet
Hg, Hq, Hs specific enthalpy of gas, adsorbate and
diameter, m
adsorbent, J/kg
ms, Vb mass and volume of the adsorbent bed, kg, m3
CPg, CPs specific heat capacity of gas and adsorbent, J/kg/K
U, Q superficial gas velocity and volumetric flow rate
q, q* excess adsorbate concentration and its
through the bed, m/s, m3/s
equilibrium value, kg H2/kg adsorbent
3p, 3b, 3t pellet, bed and total porosities, 3t ¼ 3b þ (1  3b)3p,
qm, b the two Langmuir parameter, kg/kg, 1/bar
m3/m3
DHa heat of adsorption, J/kg H2 adsorbed
rs, rp, rb skeletal, pellet and bed densities, rp ¼ rs(1  3p),
leff effective thermal conductivity of the adsorbent
rb ¼ rp(1  3b), kg/m3
bed, W/m/K
rg, vg gas density and specific volume, vg ¼ 1/rg, kg/m3,
m3/kg

 Dormancy & Venting – While the vehicle is parked, due to non-ideal, and its specific heat capacity varies significantly
continuous heat leak into the fuel-tank, its pressure builds with temperature. Hence, in this work we develop a generic
up to vent pressure, say 25 bar, and gas is vented to the fuel form of the 3-D model, which allows variation in all the
cell (or atmosphere). The process of venting is also called thermodynamic properties. We then reduce the 3-D model to
boil-off, in analogy with liquid hydrogen storage systems. the 1-D isobaric system and study the isobaric refueling
The time period till the start of venting is called dormancy. period, for simplified geometry and charging conditions. We
study only the isobaric period of refueling herein, since the
Interestingly these fuel-tank processes occur over different isobaric period is much longer than the initial adsorption
time scales: refueling over a few minutes, discharge over a few period. We have solved these 1-D equations using finite
hours, dormancy over a few days, and venting over a few element method, using the commercial package COMSOLª.
weeks. In [3] we had shown that even the fastest process, i.e.
refueling, is quasi-static i.e. local equilibrium conditions
prevail. Hence, the slower processes are obviously quasi-
static. When the molecular processes are fast, slow processes
are expected to have negligible internal gradients and are
generally amenable for a lumped-parameter analysis. Hence,
we had developed a quasi-static lumped-parameter model for
the cryo-adsorber fuel-tank in [3]. However, one might antic-
ipate that higher dimensional models might be required,
especially for the fastest process i.e. refueling. The refueling
period could be divided into two periods:

1. Initial adsorption period. During which a depleted bed at low


pressure is exposed to the high pressure supply, there are
initial pressure transients due to the hydrodynamic filling
of the bed and a rapid initial adsorption leading to
a temperature spike in the bed. Typically this period lasts
a few seconds.
2. Isobaric adsorption period. During which pressure transients
are negligible and the bed is getting cooled by and adsorbs
further hydrogen from the recirculating cool hydrogen gas.
This period is considered isobaric, since the bed is already
filled hydrodynamically in the former period and the pres-
sure drop across the highly porous beds are generally
negligible. Typically this period extends over a few minutes.

The model equations for adsorption storage or pressure


swing adsorption are widely reported in literature [4,5]. These
models generally involve approximations like ideal gas
behavior, constant specific heat capacities, constant heat of
adsorption etc. However, for example, we know that hydrogen
at high pressures and cryogenic temperatures is quite Fig. 1 – Longitudinal view of an axial packed bed.
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3600 international journal of hydrogen energy 35 (2010) 3598–3609

Section 2 describes the three packed-bed designs consid- Feed


ered in this work: axial, single cartridge annular and the
multicartridge annular beds. Section 3 describes the compu-
tation of steady-state pressure drop across these bed designs.
Section 4 describes the 3-D model development, and in
Section 5 it is reduced to the 1-D isobaric system. Section 6 Distribution tube
describes the 1-D axial bed results, and compares these
results with the lumped-parameter model predictions.
Section 7 describes the results for the annular bed designs and Packed bed
compares the three designs. Section 8 studies the effect of
feed flow rate on refueling time. The Appendix describes the Collection tube
various input data used in the 1-D isobaric refueling period
simulations. And, the support material details the derivation
Insulation
of the basic forms of transient mass and energy balances used
in Section 5.

2. Packed-bed designs
Exit

A fixed mass of adsorbent can be packed within a pressure Fig. 2 – Longitudinal and cross-sectional views of a single
vessel in various ways. The classical style is the axial bed, annular packed bed.
shown in Fig. 1, where the gas flows axially through a cylin-
drical bed. An alternative design, giving lower pressure drop,
is the annular backed bed, shown in Fig. 2, where the gas is in its pores. The gaseous hydrogen stored in the dead-spaces
ideally expected to flow radially. Hence, an annular bed design around the packed bed but within the pressure vessel (for
is often used in industrial adsorption or catalytic systems; see example, space between the cartridges, header and collector
for example the metal hydride beds [6,7], adsorption refrig- spaces etc.) are not considered.
eration systems [8], catalytic reactors [9], chromatographic
columns [10] etc. However, it is well-known, both through
simulations and experiments that annular packed beds are
3. Pressure drops for three packed-bed
more prone to flow maldistribution than axial packed beds
designs
[11,12]. The presence and effect of flow maldistribution can be
systematically studied only in a two-dimensional model. The
We compute the steady-state pressure drop for a non-
CFD studies [13,14] show that having the inlet and outlet ports
adsorbing hydrogen gas flow of 120 g/s through these three
on the same side, such that the inner and outer flows are anti-
beds at 20 bar and 80 K. To compute the pressure drop across
parallel gives low flow maldistribution. Note that this design is
different from that given in Fig. 2. Such design variations will
be considered in our future two-dimensional studies.
Instead of arranging the whole bed as a single annular bed,
one could arrange the adsorbent bed into multiple cartridges,
as in Fig. 3. In this work, we study the relative advantages of
these three different designs, especially in the context of
isobaric refueling period. In particular, we seek to answer the
following questions: for a fixed mass of adsorbent, is there any
process advantage (in heat and mass transfer sense) in
increasing the number of cartridges or is there an optimum
number of cartridges? These questions cannot be addressed
within the premise of a lumped-parameter model, since all
the designs are equivalent at that level, and we need at least
a one dimensional model.
In our earlier work [3] we had considered a MOF of bulk
density 385.05 kg/m3 and a bed of 90.37 kg mass and 0.2347 m3
volume. We consider packed beds of the same mass and
volume in this study. For all the designs we fix the bed length
at 1 m and back calculate the bed diameter from the bed
volume. For single and 7-cartridge annular beds, assuming the
distribution diameter to be 1 cm, the outer bed diameters are
respectively 0.5467 m and 0.2068 m. While comparing
different bed designs, we consider only the hydrogen capacity Fig. 3 – Cross-sectional view of a 7-cartridge annular
in the bed, both adsorbed hydrogen and the gaseous hydrogen packed bed.
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international journal of hydrogen energy 35 (2010) 3598–3609 3601

a bed for an unidirectional axial flow the widely used form of values for bed density and total porosity, we have the general
Ergun equation is [15, p. 191], form of mass balance as:

DP vq vrg / ! 
¼ amg U þ brg U2 ; (1) rb þ 3t þ V $ U rg ¼ 0: (9)
L vt vt
where Expanding the gradient term we have

150ð1  3b Þ2 rb
vq
þ 3t
vrg ! / / !
þ U $ V rg þ rg ðV $ U Þ ¼ 0: (10)
a¼ (2) vt vt
33b d2p

and Now, we introduce the quasi-static approximations i.e. the


gas and the adsorbate are in local equilibrium. This statement
1:75ð1  3b Þ implies that any change in the property of gas or the adsorbate
b¼ : (3)
33b dp at any location is solely due to the temperature and pressure
As in [3] we assume a bed porosity of 3b ¼ 0.36 and a pellet change at that location. For example, with gas density we have
diameter of dp ¼ 1.0 mm. From the NIST web book [16], we get
rg ð!
r ; tÞ ¼ rg ½Tð!
r ; tÞ; Pð!
r ; tÞ; (11)
hydrogen gas density and viscosity at 80 K and 20 bar as
rg ¼ 6.2070 kg/m3 and mg ¼ 3.7453  106 Pa s. Using these
and then the temporal and spatial derivatives of density could
values, we get a pressure drop of 1417.33 Pa across the axial
be written in terms of those of temperature and pressure
bed.
using the chain rule as:
Ergun equation is generalized for a three dimensional flow
in a differential element as [17, p. 48], vrg vT vP
¼ rg aPg þ rg kTg ; (12)
vt vt vt
/ ! !!
 V P ¼ amg U þ brg j U j U : (4)
and
For a radial flow in a differential element this equation
/ / /
becomes V rg ¼ rg aPg V T þ rg kTg V P: (13)

vP Similarly the adsorbate concentration at any location is


 ¼ amg Ur þ brg U2r ; (5)
vr approximated to the equilibrium adsorbate concentration at
where that location i.e.

Q r ; tÞzq ½Tð!
qð! r ; tÞ; Pð!
r ; tÞ; (14)
Ur ¼ (6)
2prL
and
is the radial superficial velocity. Note that in a radial flow the
superficial velocity varies with radial location. Integrating this vq vq
z : (15)
equation for an annular bed from the inner radius ri to the vt vt
outer radius ro gives The Langmuir adsorption isotherm is
     2  
Q ro Q 1 1 q bP
Po ¼ Pi  amg ln  brg  : (7) ¼ : (16)
2pL ri 2pL ri ro qm 1 þ bP

Using this equation, the pressure drop across a single and Temperature dependence of the two Langmuir parameters are
seven cartridge annular beds are 337.72 Pa and 12.05 Pa, represented as in [3] as
respectively. These calculations show that there is significant  
B
reduction in pressure drop as we move from axial bed design b ¼ b0 exp (17)
T
to single cartridge annular bed design to seven cartridge
annular bed design. and

qm0
qm ¼ ; (18)
f ðTÞ
4. Development of 3-D model equations with

4.1. Transient mass balance f ðTÞ ¼ 1 þ AT2 : (19)

Then, we have
The basic form of the transient mass balance (derivation
   
details are in the supporting material) is vq vq vT vq vP
¼ þ
vt vT P vt vP T vt
v  / ! 
 0   
r q þ 3t rg þ V $ U rg ¼ 0: (8) f ðTÞ B vT q vP
vt b ¼ q þ þ ; (20)
2
f ðTÞ ð1 þ bPÞT vt ð1 þ bPÞP vt
The adsorbate diffusion in and out of the element is generally
negligible compared to the convective component, and hence see [3] for the intermediate steps. Using these expressions in
it is typically neglected in the literature [4]. Assuming constant the mass balance, we have
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3602 international journal of hydrogen energy 35 (2010) 3598–3609

vT vP ! / ! / / ! vHg vHg vHs vq vP ! /


a11 þ a12  rg aPg U $ V T þ rg kTg U $ V P þ rg ðV $ U Þ ¼ 0; (21) 3t rg þ rb q þ rb þ rb DHa  3t þ rg U $ V Hg
vt vt vt vt vt vt vt
 
where
/  / vq vrg / ! 
þ V $ leff V T þ Hg rb þ 3t þ V $ U rg
vt vt
 0  ¼ 0: (29)
f ðTÞ B
a11 ¼ rb q þ  rg aPg 3t (22)
f ðTÞ ð1 þ bPÞT2 Noting that the coefficient of gas enthalpy in the above
equation is identically zero from the mass balance equation
and
(9), we have
   vH
rb q g vHs vq vP ! /
a12 ¼ þ rg kTg 3t : (23) 3t rg þ rb q þ rb þ rb DHa  3t þ rg U $ V Hg
ð1 þ bPÞP vt vt vt vt
/  /
þ V $ leff V T ¼ 0: (30)

In this form, all the enthalpies appear as derivatives. Hence,


the numerical evolution of the above equation is obviously
4.2. Transient energy balance
independent of the reference states assumed for computing
the enthalpies.
The basic form of the transient energy balance (derivation
Now, as in mass balance, let us introduce the quasi-static
details are in the supporting material, see also [15, p. 335]) is
approximations. Assuming local equilibrium we have
v  vP / ! 
vt
3t rg Hg þ rb qHq þ rb Hs  3t þ V $ U rg Hg
vt Hx ð!
r ; tÞ ¼ Hx ½Tð!
r ; tÞ; Pð!
r ; tÞ; (31)
/  /
þ V $ leff V T ¼ 0: (24) and hence, we have

Since the gas–solid contact area is very large in porous vHg vT  vP


¼ CPg þ vg 1  aPg T ; (32)
packed beds, local thermal equilibrium could typically be vt vt vt
assumed for physisorption scenarios and hence one single
energy balance could be used, instead of a separate energy / /  /
V Hg ¼ CPg V T þ vg 1  aPg T V P; (33)
balance for the gas and solid phases, further details are
available in [3, Section 4].
vHs vT vP
Assuming constant bed density and total porosity, the ¼ CPs þ vs ; (34)
vt vt vt
above equation is expanded as follows:
see for example Section 2.1 of Ahluwalia and Peng [18].
vHg vrg vHq vq vHs vP ! / Using these results in Eq. (30) and simplifying we have,
3t rg þ 3t Hg þ rb q þ rb Hq þ rb  3t þ rg U $ V Hg
vt vt vt vt vt vt
/ !  /  / vT vP ! /  ! /
þ Hg V $ U rg þ V $ leff V T a21 þ a22 þ rg CPg U $ V T þ 1  aPg T U $ V P
vt vt
/  /
¼ 0: þ V $ leff V T ¼ 0; (35)
(25)
where
In this form we see that the gas and adsorbate enthalpies  0 
  f ðTÞ B
appear as coefficients of derivatives, which at the outset could a21 ¼ 3t rg þ rb q CPg þ rb CPs  q rb DHa þ ;
absurdly mean that the numerical evolution of this equation f ðTÞ ð1 þ bPÞT2
depends on the reference state assumed for the computation (36)
of these enthalpies. We will now demonstrate that it is not so. and
The adsorbate enthalpy is obtained from the definition of heat
  
of adsorption as   q rb DHa
a22 ¼ 3t þ rb vg q 1  aPg T þ ð1  23t Þ þ : (37)
ð1 þ bPÞP
Hq ¼ Hg þ DHa : (26)
We have used
This study assumes a constant average heat of adsorption,
independent of temperature and pressure. Hence,
rb
r b vs ¼ ¼ 1  3t (38)
vHq vHg rs
z : (27) during the above simplifications.
vt vt
Note that this development of transient energy balance
Using these results, we have
does not contain the heat leak into the system. The heat leak
vHg vrg vHg  vq vHs vP term should be considered in the energy balance for the
3t rg þ 3t Hg þ rb q þ rb Hg þ DHa þ rb  3t
vt vt vt vt vt vt structural steel domain and not the adsorbent bed domain,
! / / !  /  /
þ rg U $ V Hg þ Hg V $ U rg þ V $ leff V T with a heat flux continuity boundary condition at the interface
allowing the heat exchange between the two domains. The
¼ 0: (28)
energy balance developed above is only for an element in the
Collecting all the terms having gas enthalpy as their coeffi- adsorbent bed. For the system considered herein, during
cient gives refueling or discharge, the heat effects due to adsorption or
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international journal of hydrogen energy 35 (2010) 3598–3609 3603

desorption are significantly larger than the heat leak into to ! /


U ¼ 2ð V PÞ
the tank. Hence, the heat leak can be neglected. For example, rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi (42)
/
for an adsorbent with 4 kJ/mol heat of adsorption, adsorbing amg þ a2 m2g þ 4brg jV Pj:
5 kg of hydrogen in 5 min, the average rate of heat generation
is about 33.3 kW. While typical heat leaks are of the order of This expression is used in the mass and energy balances Eqs.
a few Watts. Thus, for these two fast processes, i.e. refueling (21) and (35), to eliminate superficial velocity in terms of
and discharge, it is not necessary to draw two separate energy pressure gradient. Then, we solve the coupled mass and
balances for the structural steel and adsorbent bed domains. energy balances for the variables ( T,P).
However, to estimate the impact of heat leak, one could
4.5. Comparison with literature
‘‘numerically’’ add that heat to the feed gas and study the bed
dynamics. For the slow processes, i.e. dormancy and venting,
The mass balance and steady-state momentum equations
the lumped-parameter description uses a single energy
described in Mota et al. [4] are identical to our Eqs. (9) and (4).
balance which contains the heat leak term. In fact in these
The energy balance equation of [4], in our notation is
processes, the heat leak drives the tank dynamics.
4.3. Steady-state momentum balance v h  i vq vP vT /  !
CPg 3t rg þ rb q T þ rb DHa  3t þ rb CPs þ CPg V $ Trg U
vt vt vt vt
/  /
Using Ergun equation (4) i.e. the steady-state momentum  V $ leff V T
equation locally for the pressurization of adsorber gives ¼ 0:
numerical results comparable to that of the unsteady (43)
mechanical energy balance (which is merely a dot product of
the unsteady momentum balance equation and velocity) [19]. We will recover the above equation from Eq. (24) by stating the
Hence, in adsorption literature it is common to use the Ergun assumptions systematically. Using the adsorbate enthalpy
equation locally even when flow and pressure transients exist. definition Eq. (26), assuming a constant average heat of
adsorption Eq. (27), and a constant bed density, Eq. (24)
4.4. General solution procedure simplifies to

4.4.1. Three-variable formulation v   vH


g vq vHs vP
Hg 3t rg þ rb q þ 3t rg þ rb q þ rb DHa þ rb  3t
We solve the mass and energy balances, Eqs. (21) and (35), vt vt vt vt vt
!
coupled with Ergun equation (4) for the variables ð U ; T; PÞ. / !  /  /
þ V $ U rg Hg  V $ leff V T ¼ 0: (44)
Simplistically, it could be stated that the mass balance
describes the flow rate or velocity changes due to adsorption,
the energy balance describes the temperature changes due to Assuming that the effect of pressure on the gas and solid
the heat released on adsorption, and the Ergun equation enthalpies are negligible in the given operating range of
describing the pressure drop due to flow. The coupled effects pressures, and that the specific heat capacities of the gas and
like pressure changes in the gas phase due to adsorption, flow solid are constants i.e. they do not vary with temperature, we
rate or density changes due to temperature gradient etc. are of have,
course built into the model exactly. dHg ¼ CPg dT; (45)

4.4.2. Two-variable formulation integrating it from a reference temperature and enthalpy


Ergun equation expresses pressure gradient in terms of the gives
superficial velocity. It can be inverted to express superficial
velocity in terms of the pressure gradient as follows. Taking Hg ¼ Hg0 þ CPg ðT  T0 Þ: (46)
modulus of Eq. (4) gives Similarly, for the adsorbent enthalpy we have
/ ! !
jV Pj ¼ amg j U j þ brg j U j2 : (39) dHs ¼ CPs dT: (47)
! Using these results in Eq. (44), and simplifying we have
This quadratic equation in j U j is solved to get
  / ! 
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  v v h  i
! /
Hg0 CPg T0 3t rg þrb q þ V $ U rg þCPg 3t rg þrb q T
j U j ¼ amg þ a2 m2g þ 4brg jV Pj vt vt
(40) vq vT vP / ! 
2brg : þrb DHa þrb CPs 3t þCPg V $ U rg T
vt vt vt
Here, we use the positive sign for the square root so that the /  /
 V $ leff V T ¼0: (48)
modulus is non-negative. This expression is substituted in the
vector equation and rearranged to get Note that the above equation is identical to that in [4] except
 for the first term, which is identically zero from the mass
/ ! !! ! !
V P ¼ amg U þ brg j U j U ¼ amg þ brg j U j U balance equation (9). Thus, our model reduces to that of [4]
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi when the effect of pressure on enthalpies is negligible and
0 / 1
amg þ a2 m2g þ 4brg jV Pj ! specific heat capacities and heat of adsorption are constant.
¼@ AU: ð41Þ The model developed herein is quite generic with rigorous
2
accounting of the temperature and pressure dependence of all
Hence, we have the thermodynamic properties.
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3604 international journal of hydrogen energy 35 (2010) 3598–3609

More complicated boundary conditions have been proposed in


5. Reduction of 3-D model to 1-D isobaric the literature; see for example [21,22]. However, we observe that
system the Danckwerts’ boundary condition is used widely in the
adsorption literature, see for example [23,24].
For an isobaric system, we drop the Ergun equation (4) and the
temporal and spatial derivatives of pressure in the mass and
energy balances (21) and (35), and solve the coupled mass and
! 6. Results & discussion for axial bed design
energy balances for ð U ; TÞ i.e. mass balance describes the flow
rate or velocity changes due to adsorption and energy balance
The whole bed is initially at 140 K. As the 80 K feed gas starts
describes the temperature changes due to the heat released
blowing through the bed simultaneous cooling and adsorption
on adsorption. For the isobaric system, mass balance equation
takes place. For example, in the temperature evolution in
(21) reduces to
Fig. 4 at t ¼ 0.5 min, one could see three regions existing within
vT ! / / ! the bed. The region 0–A is the part of the bed which has
a11  rg aPg U $ V T þ rg ðV $ U Þ ¼ 0; (49)
vt already cooled to 80 K and it has got saturated to its capacity at
where a11 is given by Eq. (22). For unidirectional axial flow, it 80 K. The region A–B is the region where simultaneous cooling
reduces to and adsorption are currently taking place. Here, the temper-
atures are between the initial bed temperature and the feed
vT vT vUx gas temperature. As the gas flows through this region it gets
a11  rg aPg Ux þ rg ¼ 0: (50)
vt vx vx heated up. At about point B, the gas gets heated up to 140 K,
For unidirectional radial flow, in cylindrical coordinates, it
reduces to

vT vT 1 v a
a11  rg aPg Ur þ rg ðrUr Þ ¼ 0: (51) 140
vt vr r vr B
t = 0.5 min
Expanding the last term gives
1.0 min
vT vT vUr rg Ur 120
a11  rg aPg Ur þ rg þ ¼ 0: (52)
vt vr vr r
1.5 min
T (K)

The energy balance equation (35), with the additional


assumption of constant effective thermal conductivity, 2.0 min
reduces to 100
2.5 min
vT ! /
a21 þ rg CPg U $ V T  leff V2 T ¼ 0; (53) 3.0 min
vt A
80
where a21 is given by Eq. (36). For unidirectional axial flow it
reduces to 0 0.5 1
x (m)
vT vT v2 T
a21 þ rg CPg Ux  leff 2 ¼ 0: (54)
vt vx vx
b 120
For unidirectional radial flow, in cylindrical coordinates, it A 3.0 min
reduces to
2.5 min
 
mass flow rate (g/s)

vT vT 1 v vT
a21 þ rg CPg Ur  leff r ¼ 0: (55)
vt vr r vr vr 110 2.0 min
Expanding the last term and rearranging we have 1.5 min
 
vT leff vT v2 T
a21 þ rg CPg Ur   leff 2 ¼ 0: (56)
100
1.0 min
vt r vr vr

We solve the coupled mass and energy balance equations in t = 0.5 min
COMSOLª, with the initial conditions: U ¼ 0 and T ¼ T0, all over B
the domain at t ¼ 0, and the boundary conditions U ¼ Uf and T ¼ Tf
90
at the feed side, and vT=vx ¼ 0 or vT=vr ¼ 0 at the exit side. This 0 0.5 1
Neumann-type exit boundary condition for flow systems is x (m)
popularly known as the Danckwerts’ boundary condition [20].
Theoretically, this boundary condition can be applied only for Fig. 4 – (a) Temperature and (b) mass flow rate evolution in an
a steady system. For an unsteady system, this boundary condition axial flow bed. At t [ 0.5 min, the region 0–A is the saturated
is believed to suppress the gradients near the exit or induce region at feed temperature (80 K), the region A–B is the
numerical instability. However, in Section 6, we observe that adsorption zone where the bed is simultaneously cooling
there is no perceptible gradient suppression near exit in our (from 140 K to 80 K) and adsorbing, and the region B–1 is the
results, even when the adsorption front is moving out of the bed. non-adsorbing region at initial bed temperature (140 K).
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international journal of hydrogen energy 35 (2010) 3598–3609 3605

the initial bed temperature. Hence, beyond point B, the gas Once we have the temperature and pressure evolution of the
just passes through the bed without cooling the bed any bed, integrating this expression over the entire length of the
further. Thus, in the region B–1 the bed is saturated at its bed gives the total hydrogen content of the bed at any time.
initial temperature. As time progresses region A–B, the We define the refueling time as the time at which the total
adsorption zone, moves downstream, leaving the bed hydrogen content of the bed is 5 kg (as mentioned in Section 2,
upstream fully saturated at 80 K. In the flow rate evolution we do not consider the gaseous hydrogen storage in the dead-
within the bed in Fig. 4, the same inferences could be seen. In spaces). For the isobaric axial bed, with a 120 g/s feed at 80 K
the adsorption zone A–B flow rate decreases due to adsorp- and 20 bar, we found the refueling time to be 135.8 s or
tion, and in the saturated zones 0–A and B–1 the flow rate 2.26 min. From Fig. 4, we can see that even by the end of
remains constant. Once the bed is fully saturated, gas merely refueling significant temperature gradients (about 40 K) exist
passes through the bed without change in flow rate. Fig. 5 within the bed. We will return to this observation later in this
shows the gas density and velocity evolution within the bed. section.
Density changes almost by a factor of two within the bed,
showing that the temperature dependence of thermodynamic
properties should be properly accounted. In the adsorption 6.1. Comparison of 1-D axial bed model and 0-D
zone, it is seen that the gas velocity increases steeply due to model results
sharp rise in temperature and consequent fall in density,
occurring within the adsorption zone. Fig. 6 shows the hydrogen capacity evolution predicted by the
Consider a circular slice of the axial bed at x, of elemental 1-D axial bed model and by the lumped-parameter model for
thickness Dx. Its total hydrogen content is obtained by summing the isobaric refueling period. The respective isobaric refueling
up the adsorbed phase and gas phase contributions as: times are 5.86 and 2.26 min. (Note that this 0-D result is
without the steel thermal mass and heat leak into the system,
pR2 Dxrb q ½Tðx; tÞ; Pðx; tÞ þ pR2 Dx3t rg ½Tðx; tÞ; Pðx; tÞ: (57)
so that the 0-D and 1-D results can be compared on a common
basis.) Such a large discrepancy in the hydrogen capacity
evolution and hence the refueling time is due to the significant
temperature gradients existing within the bed during the
isobaric refueling period, as seen in Fig. 4. We expect lesser
disparity between the 0-D and the 1-D models for slower
processes like discharge, dormancy and venting, since the
temperature gradients are expected to be milder.
In order to check this large discrepancy between the 0-D
and 1-D models during the isobaric refueling period, we
implemented a tanks-in-series model (not reported here).
A 0-D model is a single tank model, while the 1-D model is
equivalent to a sufficiently large number of tanks-in-series. In
fact, serially coupled 0-D models lead to a tanks-in-series
model. A tanks-in-series model showed that the two curves
shown in Fig. 6 can be smoothly interpolated as the number of
tanks increases from 1 to about 25.

4
H load (kg)

3
2

2 0−D

1−D Axial bed

1
0 2 4 6
time (mins)

Fig. 6 – Hydrogen capacity evolution predicted by the 0-D


Fig. 5 – (a) Density and (b) superficial gas velocity evolution model and 1-D axial bed model during the isobaric
in an axial bed. refueling period.
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3606 international journal of hydrogen energy 35 (2010) 3598–3609

Interestingly, from Fig. 6, we see that a 0-D model always from the bed and back into the gas phase, resulting in a slight
predicts lower hydrogen capacity than a 1-D model. The basic increase in the gas pressure.
distinction between the 0-D and 1-D models is the presence of Earlier in this section, we noted that even at the end of
temperature gradients in the latter. The presence of tempera- refueling significant temperature gradients, up to 40 K temper-
ture gradient in a 1-D model facilitates higher hydrogen ature difference exists within the bed. If the tank is isolated after
capacity than the 0-D model. This can be demonstrated by the refueling, with the temperature gradient slowly equilibrating, as
heuristic model shown in Fig. 7. Consider a kilogram of MOF at we note in this section, due to desorption back into the gas phase
80 K and another kilogram of MOF at 120 K being brought in there can be a slight overshoot in the tank pressure.
thermal contact. Assuming that their specific heat capacities
do not change significantly, we could say that the equilibrium
temperature of the composite block (neglecting for the 7. Results for annular bed designs and
moment, the energetics of adsorption or desorption) will be comparison of the three bed designs
about 100 K. From the adsorption data in the Appendix, one
could compute the excess adsorbed hydrogen at 20 bar in 1 kg Figs. 8 and 9 show the simulation results for the single cartridge
MOF at 80 K as 49.73 g, 1 kg of MOF at 120 K as 19.15 g and 2 kg of annular bed. Similar result hold seven cartridge annular bed
MOF at 100 K as 61.69 g. This calculation indicates that 7.19 g of (figures not shown), except that one seventh of the total flow is
hydrogen is returned to the gas phase when the temperature apportioned to each cartridge. The phenomenon of simulta-
gradients equilibrate within the composite block. Note that neous cooling and adsorption in annular beds is similar to that
this heuristic model does not capture the ‘‘secondary’’ effects in the axial bed, except for the geometric effects. From Fig. 8, it
which occur in reality, but illustrates the fact that a bed with can be seen that the adsorption zone moves rapidly near the
gradients has more adsorbed hydrogen than a bed at its inner diameter and slowly near the periphery. In Fig. 9, at long
equilibrated temperature, and thus it explains qualitatively the times the superficial gas velocity approaches a rectangular
discrepancy between the lumped-parameter and 1-D models. hyperbola, since for the non-adsorbing case the radial velocity
We can understand the above fact from a thermodynamic at any location is given by Eq. (6).
perspective too. If an adsorbent bed with internal temperature
gradients is isolated from its environment, the second law of
thermodynamics dictates that, on equilibration the system
a
140
entropy should increase. In most cases of gas physisorption,
the entropy of the adsorbed phase is lesser than that of the gas t = 0.5 min
phase. (If the adsorbed molecule dissociates on the surface, it
could favor an increase in entropy. But compared to the gas 120 1.0 min
phase, typically an adsorbed phase has much lower degrees of
T (K)

translational freedom. Hence, even with dissociative adsorp- 1.5 min


tion, more often the adsorbed phase entropy is lower than
that of the gas phase, leading to the commonly observed 100
2.0 min
exothermic adsorption. However, in special cases of disso-
ciative adsorption, if the entropy of the adsorbed phase is 2.5 min
higher than the fluid phase, there can be an endothermic
80
adsorption, see [25] for example.) Hence, on equilibration of 3.0 min
the temperature gradient some quantity of gas gets desorbed 0.05 0.1 0.15 0.2 0.25
r (m)

b
49.73 g H2 19.15 g H2 3.0 min
120
1 kg MOF 1 kg MOF
2.5 min
+
mass flow rate (g/s)

at 80 K & at 120 K &


20 bar 20 bar 2.0 min
110
1.5 min

1.0 min
100
2 kg MOF Returned
at 100 K & to
t = 0.5 min
20 bar gas phase

61.69 g H2 7.19 g H2 90
0.05 0.1 0.15 0.2 0.25
r (m)
Fig. 7 – Heuristic model to demonstrate that a bed with
temperature gradients contains more adsorbed hydrogen Fig. 8 – (a) Temperature and (b) mass flow rate evolution in
than the bed at its average temperature. a single cartridge annular bed.
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international journal of hydrogen energy 35 (2010) 3598–3609 3607

a
3.0 min
5
6
2.5 min

2.0 min 4

H load (kg)
(kg/m )
3

5
1.5 min 3

2
g

Axial
1.0 min Annular−1
4 2
Annular−7
t = 0.5 min
1
3 0 1 2 3
0.05 0.1 0.15 0.2 0.25 time (mins)
r (m)
Fig. 10 – Hydrogen capacity evolution among the different
packed-bed designs.
b 0.6
0.035
t = 0.5 min
0.03
flow maldistribution. The material cost increases with the
0.025 number of cartridges due to an increase in the mass of
0.4 1.0 min structural steel (increased diameter of pressure vessel and
U (m/s)

0.02 headers, additional distribution tubes, bed restrainers etc.).


1.5 min Since flow is routed parallel in a multicartridge design, a flow
0.015 2.0 min
short circuit to the outer header in a cartridge will lead to
0.2 2.5 min
3.0 min significant flow maldistribution. As the number of cartridges
0.01
0.1 0.15 0.2 0.25 increases, the radial thickness of the bed in a cartridge
decreases and the chances of short circuiting or flow maldis-
tribution increase. Thus, a single cartridge annular bed offers
0 the advantages of radial flow system, without increasing the
0.05 0.1 0.15 0.2 0.25
material cost, fabrication complexity and flow maldistribution
r (m)
as in a multicartridge annular bed design.
Fig. 9 – (a) Density and (b) superficial gas velocity evolution
in a single cartridge annular bed.

8. Refueling times at various feed flow rates

Fig. 10 compares the hydrogen capacity among the three The results presented in above sections are for a constant feed
different packed-bed designs under consideration. Surpris- flow rate of 120 g/s. Now we present the refueling time at
ingly, there is negligible difference between the three designs different feed flow rates, for the three designs under consid-
in terms of hydrogen capacity evolution. This observation eration, in Table 1. Especially, in the axial bed results, we see
may be explained as follows: since the internal surface area that doubling the feed flow rate approximately halves the
within the pellets is very high, the adsorbent is already in refueling time. This scaling can be reasoned as follows: in this
intimate contact with the gas. Hence, rearranging the bed isobaric model, effective thermal conductivity of the bed is the
geometry does not make much difference in the rate at which only transport property which contains the dimension of
adsorption happens.
The primary motivation of this study was to answer the
following questions: for a fixed mass of adsorbent, is there any
process advantage in increasing the number of cartridges in Table 1 – Refueling time for the three bed designs at
an annular bed design and is there an optimum number of various feed flow rates.
cartridges during the isobaric refueling period? Since we do Feed flow Refueling time (s)
not find significant difference in the hydrogen capacity rate (g/s)
evolution, we infer that there is no significant heat and mass Axial bed Single cartridge Seven cartridge
annular bed annular bed
transfer advantage in moving from axial bed to single
cartridge annular bed or to seven cartridge annular bed 240 68.0 68.2 69.5
designs. Hence, the only difference in these design enhance- 120 136.1 136.9 141.8
ments is the decrease in pressure drop, as we noted in Section 60 272.4 275.7 294.0
30 545.6 557.8 625.0
3. Increase in the number of cartridges in an annular design
15 1093.6 1140.1 1380.5
results in higher material cost, fabrication complexity and
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3608 international journal of hydrogen energy 35 (2010) 3598–3609

time, and all the remaining properties are thermodynamic or For all the bed designs, we find that the product of refueling
material properties which do not contain the dimension of time and feed flow rate is approximately constant for a given
time. When the effective thermal conductivity is low, as in feed temperature and pressure, i.e. doubling the feed flow rate
MOF, it does not significantly contribute to the thermal halves the refueling time. This scaling, though approximate,
diffusion of the adsorption front through the bed, leaving helps us in estimating the refueling time at arbitrary flow rates
superficial gas velocity or flow rate as the main variable given the refueling time at a flow rate.
scaling the refueling time. This scaling, though approximate,
helps us in estimating the refueling time at arbitrary feed flow
rates given the refueling time at a flow rate, since the product
Acknowledgments
of refueling time and feed flow rate is approximately
a constant, for a given feed temperature and pressure.
The authors would like to thank Raghunathan K, Michael
Compared to the axial bed, the single cartridge annular bed
Herrmann, Scott Jorgensen, Ulrich Eberle, Dieter Hasenauer,
design has a lower flow path length. As the number of
Rainer Immel, Gregory Meisner, Anne Dailly and Eric Poirier
cartridges increases, the radial thickness of the bed and hence
for technical data and/or valuable suggestions during the
the flow path length decreases. As flow path length decreases,
course of model development. Senthil Kumar would like to
the effect of thermal conductivity of the adsorbent on the
acknowledge constructive comments from his group
thermal diffusion of the adsorption front increases. Hence, we
members at India Science Lab during his presentations while
can see that the above scaling is less accurate as we move
the model development was in progress.
from the axial bed to single cartridge annular bed to seven
cartridge annular bed designs.
Appendix A. Simulation input data

A.1. Gas data


9. Conclusions
We have employed the isobaric thermodynamic properties of
hydrogen gas at 20 bar from the NIST web book [16], in the
We have developed generalized 3-D model equations for the
temperature range 60–300 K, and fitted the expressions shown
cryo-adsorber, accommodating the temperature and pressure
below.
variation of all the thermodynamic properties. We have shown
that in the limiting case of negligible temperature and pressure vg ¼ vg0 þ vg1 T þ vg2 T2 þ vg3 T3 þ vg4 T4 (A.1)
dependence of the thermodynamic properties and a constant
heat of adsorption the derived energy balance equation reduces
vg0 ¼ 0:042693; vg1 ¼ 0:0028869; vg2 ¼ 5:5122e  6; vg3
to that reported in the literature. We then reduce the 3-D model
¼ 1:6913e  8; vg4 ¼ 1:9513e  11;
to the 1-D isobaric system and study the isobaric refueling
period, for simplified geometry and charging conditions. We where vg is the specific volume in m3/kg and T in K. We get the
have considered three packed-bed designs: an axial bed, single isobaric thermal expansion coefficient as
cartridge annular bed and a seven cartridge annular bed design.  
The hydrogen capacity evolution predicted by the 1-D axial 1 vvg vg1 þ 2vg2 T þ 3vg3 T2 þ 4vg4 T3
aPg ¼ ¼ ; (A.2)
bed model is significantly different from that predicted by the vg vT P vg
lumped-parameter model, since sharp temperature gradients
 
exist within the bed during refueling. We observe that the lum-  2 exp fT2  
f2 T
ped-parameter model predicts a lower hydrogen capacity than CPg ¼ f1  h   i2 þ f3 þ f4
T 100
the 1-D model. This observation can be explained by the fact that exp fT2  1
due to the second law of thermodynamics, on equilibration an  2    2
T 100 100
isolated bed with temperature gradients should desorb gas þ f5 þf6 þ f7 ; (A.3)
100 T T
whenever the adsorbed phase entropy is lower than the gas phase
entropy. We expect lesser disparity for the slower processes, since f1 ¼ 4:788937e þ 03; f2 ¼ 5:229983e þ 02;
the temperature gradients are expected to be milder. f3 ¼ 1:496674e þ 04; f4 ¼ 1:204579e þ 03;
During the isobaric refueling period, we did not find any f5 ¼ 8:489895e þ 01; f6 ¼ 5:356621e þ 03;
significant difference in hydrogen capacity evolution among
f7 ¼ 2:625154e þ 03:
the axial bed, single cartridge annular bed and multicartridge
annular bed designs. From this observation we conclude the where CPg is the isobaric specific heat capacity in J kg1 K1
following: annular bed design gives a lower pressure drop and T in K.
than an axial bed design but it does not enhance the heat and
mass transfer processes. A multicartridge annular bed design A.2. Adsorption/adsorbent data
gives a lower pressure than a single cartridge annular bed
design but again increase in the number of cartridges does not For the Langmuir adsorption model, Eqs. (16)–(19), the parame-
enhance the heat and mass transfer processes. Hence a single ters used are: b0 ¼ 2.8164  108 Pa1, B ¼ 332.0158 K,
cartridge annular bed design offers the advantages of the qm0 ¼ 11.7134  10 kg H2/kg MOF and A ¼ 131.3231  106 K2.
2

annular bed design without increasing the material cost, As in [3], the remaining adsorbent parameters are
fabrication complexity and flow maldistribution. DHa ¼ 4:0 kJ=mol ¼ 2  106 J=kg, leff ¼ 0:32 W=m=K, and
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international journal of hydrogen energy 35 (2010) 3598–3609 3609

X
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