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A lumped-parameter model for cryo-adsorber
hydrogen storage tank
V. Senthil Kumar
a,
*, K. Raghunathan
a
, Sudarshan Kumar
b
a
India Science Lab, General Motors R & D, Creator Building, International Technology Park, Bangalore 560066, India
b
Chemical and Environmental Sciences Lab, General Motors R & D, 30500 Mound Road, Warren, MI 48090, USA
a r t i c l e i n f o
Article history:
Received 24 March 2009
Received in revised form
30 April 2009
Accepted 1 May 2009
Available online 2 June 2009
Keywords:
Hydrogen storage modeling
Cryogenic adsorption
Metal-organic frameworks
a b s t r a c t
One of the primary requirements for commercialization of hydrogen fuel-cell vehicles is
the on-board storage of hydrogen in sufcient quantities. On-board storage of hydrogen by
adsorption on nano-porous adsorbents at around liquid nitrogen temperatures and
moderate pressures is considered viable and competitive with other storage technologies:
liquid hydrogen, compressed gas, and metallic or complex hydrides. The four cryo-
adsorber fuel tank processes occur over different time scales: refueling over a few minutes,
discharge over a few hours, dormancy over a few days, and venting over a few weeks. The
slower processes i.e. discharge, dormancy and venting are expected to have negligible
temperature gradients within the bed, and hence are amenable to a lumped-parameter
analysis. Here we report a quasi-static lumped-parameter model for the cryo-adsorber fuel
tank, and discuss the results for these slower processes. We also describe an alternative
solution method for dormancy and venting based on the thermodynamic state description.
2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
One of the primary requirements for the commercialization of
hydrogen fuel-cell vehicles is the on-board hydrogen storage
for a range of about 500 km, see Satyapal et al. [1]. On-board
storage of hydrogen by adsorption at low temperatures
(around 77 K, liquid nitrogen temperature) and moderately
high pressures (less than 60 bar) is considered viable and
competitive with other storage technologies: liquid hydrogen,
compressed gas, and metallic or complex hydrides, see Zhou
[2]. Nano-porous metal-organic frameworks (MOFs) as adsor-
bents offer good gravimetric capacity and fast and reversible
kinetics. For example, MOF-5 has a reversible maximum
excess adsorption capacity of about 6 wt% at 77 K, see Zhou
et al. [3]. MOF-5 is the adsorbent considered in this report to
study the fuel tank performance.
In this work we assume that the operating pressure of the
cryo-adsorber fuel tank is 20 bar. We assume that liquid
nitrogen at 77 K is available as a coolant at the fuel station.
Hence, the lowest temperature of the cooled hydrogen feed
gas is about 80 K. The four processes occurring in a cryo-
adsorber fuel tank are:
Refueling A depleted fuel tank at low pressure (say 1.1 bar)
and higher temperature (say 120 K) is charged with
hydrogen. Heat released during adsorption is removed by
the recirculation of cool hydrogen gas entering at 80 K.
Discharge When the vehicle is in motion, the fuel-cell stack
demands are met by desorbing hydrogen from the cryo-
adsorber bed. Desorption is enhanced by the recirculation of
hot hydrogen gas. The tank pressure eventually drops to
1.1 bar.
* Corresponding author. Tel.: 91 80 41984567; fax: 91 80 41158262.
E-mail addresses: senthil.vadivelu@gm.com, senthil.v.kumar@gmail.com (V. Senthil Kumar).
Avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ he
0360-3199/$ see front matter 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.05.025
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Dormancy & Venting While the vehicle is parked, its pres-
sure builds up to vent pressure, say 25 bar, due to contin-
uous heat leak into the fuel tank, and gas is vented to the
fuel cell or atmosphere. The process of venting is also called
boil-off, by analogy with liquid hydrogen storage systems.
The time period until the start of venting is called
dormancy.
These fuel tank processes occur over different time scales:
refueling over a few minutes, discharge over a few hours,
dormancy over a fewdays, andventing over a fewweeks. When
themolecular transport processesarefast, slower processeslike
discharge, dormancy and venting are expected to have negli-
gible internal gradients and are generally amenable to a lum-
ped-parameter analysis. Inthis report wedescribeaquasi-static
lumped-parameter model for the cryo-adsorber fuel tank, and
present the results for these slower processes. The fastest fuel
tank process, refueling, requires higher dimensional models to
describe the temperature gradients occurring within the bed,
and these are being currently developed.
Section2 describes the adsorptiondata for MOF-5. Section3
describes a fuel tank design considered in this study. Section 4
identies the assumptions involvedinthe model development
and Section 5 presents the quasi-static lumped-parameter
model for the cryo-adsorber. The simulation results for
dormancy, venting and discharge are presented in Sections 6
8, respectively. While some of the thermophysical properties
are directlytakenfromexisting databases, some are computed
in this work; these details are given in the appendix.
2. Adsorption data
Zhou et al. [3] have reported the adsorption data for MOF-5
powder over a wide range of temperature and pressure. Over
the range of 60125 Ktemperature and 130 bar pressure, their
excess adsorption data can be tted to a Langmuir isothermof
the following form:
q

T; P q
m
bP
1 bP
; (1)
b b
0
exp
_
B
T
_
; (2)
q
m

q
m0
f T
; (3)
where we have assumed
f T 1 AT
2
: (4)
For the hydrogen adsorption data in AX-21, Benard and
Chahine [4] use
f T 1 AT: (5)
However, for the MOF-5 data in the considered range of
temperature and pressure, we nd that equation (4) gives
a good t. Fig. 1 shows the Langmuir t for data in the range
130 bar and 60125 K, with the following parameters :
b
0
2.8164 10
3
bar
1
, B 332.0158 K, q
m0
11.7134 10
2
kg H
2
/kg MOF and A131.3231 10
6
K
2
. At 20 bar and 77 K,
these parameters give q* 0.0532 kg H
2
/kg MOF.
For MOF-5 powder Zhou et al. [3] report a skeletal density of
about 1.78 g/cc and 66.2%porosity. Due to the lack of densied
MOF-5 adsorption data, we assume that MOF-5 pellets have
same density as the powder. Hence, solid density
r
s
1780 kg/m
3
, pellet porosity 3
p
0.662, and pellet density
r
p
r
s
_
1 3
p
_
601:64 kg=m
3
: (6)
Assuming a dense random packing of spheres gives a bed
porosity of 3
b
0.36, bed density
r
b
r
p
1 3
b
385:05kg=m
3
(7)
and total porosity
Nomenclature
T, P Temperature and pressure, K, bar
m
s
, V
b
Skeletal mass and volume of the adsorbent bed,
kg, m
3
m
w
Mass of tank wall, typically steel, kg
_ m
f
; _ m Inlet and outlet gas mass ow rates, kg/s
3
p
, 3
b
, 3
t
Pellet, bed and total porosities, 3
t
3
b
(1 3
b
)3
p
,
m
3
/m
3
r
s
, r
p
, r
b
Skeletal, pellet and bed densities, r
p
r
s
(1 3
p
),
r
b
r
p
(1 3
b
), kg/m
3
r
g
, v
g
Gas density and specic volume v
g
1/r
g
, kg/m
3
,
m
3
/kg
m
g
, k
g
, k
s
Gas viscosity, gas thermal conductivity and
adsorbent thermal conductivity, Pa s, W/m/K,
W/m/K
d
p
Pellet diameter, m
U Supercial bed velocity, m/s
h
g
Convective heat transfer coefcient on the surface
of a pellet, W/m
2
/K
Nu, Bi, Re, Pr Nusselt, Biot, Reynolds and Prandtl numbers
v
w
; v
s
Mean specic volumes of the steel and
adsorbent, m
3
/kg
a
Pg
; k
Tg
Isobaric thermal expansion coefcient and
isothermal compressibility, 1/K, 1/bar
H
g
, H
q
, H
s
, H
w
Specic enthalpy of gas, adsorbate, adsorbent
(solid) and steel components (wall), J/kg
C
Pg
, C
Ps
, C
pw
Specic heat capacity of gas, adsorbent and
steel, J/kg/K
_
Q
l
;
_
Q
h
Heat leak rate, heat addition rate into the
tank, W
q, q
*
Excess adsorbate concentration and its
equilibrium value, kg H
2
/kg adsorbent
q
m
, b The two Langmuir adsorption isotherm
parameters, kg/kg, 1/bar
DH
a
Heat of adsorption, J/kg H
2
adsorbed
H
sys
Enthalpy of the inner thermal masses, J
T
N
Ambient temperature, K
R
eff
Effective resistance for heat leak into the
inner thermal masses, K/W
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3
t
3
b
1 3
b
3
p
0:7837: (8)
For MOF-5 Panella et al. [5] report a heat of adsorption of
3.8 0.8 kJ/mol, Dailly et al. [6] report 4.1 kJ/mol, Kaye and
Long [7] report 4.75.2 kJ/mol, and Zhou et al. [3] report an
initial heat of adsorptionof about 4.8 kJ/mol. Here we assume
a constant average heat of adsorption DH
a
4.0 kJ/mol.
3. Fuel tank design
A lumped-parameter model does not distinguish between
different packed bed designs. Hence for illustration we
assume a longitudinal packed bed as shown in Fig. 2. Aheader
distributes the hydrogen feed stream to a packed bed of cryo-
adsorbent pellets. The bed adsorbs hydrogen, the unadsorbed
gas owgets collected and ows out of the tank. Hydrogen gas
owing out of the tank can be cooled and recirculated for
further adsorption.
The adsorbent bed is designed for an assumed 5 kg total
hydrogen capacity at 20 bar and 77 K, with 20% excess bed
mass allowed to provide for operating temperatures higher
than 77 K. Total hydrogen in the fuel tank, at any temperature
and pressure, is the sum of hydrogen in the adsorbed and gas
(in bed voids and pellet pores) phases. Thus,
m
H
2
T; P m
s
q

T; P V
b
3
t
r
g
T; P: (9)
At 20 bar and 77 K, r
g
6.4851 kg/m
3
. Using these values in
Equation (9) gives an adsorbent mass of 75.3 kg. Allowing
a 20% excess gives m
s
90.37 kg and V
b
0.2347 m
3
234.7 l.
The bed volume will be signicantly lower for densied
adsorbent pellets.
4. Model assumptions
In the next section we develop a quasi-static lumped-param-
eter model for the cryo-adsorber, and here we justify or list the
assumptions of quasi-static behavior and lumping. Quasi-
static behavior implies local thermal and mass equilibrium at
any time i.e. the transient system passes through a series of
equilibriumstates. The adsorbents typically offer large specic
internal surface area, leading to intimate gassolid contact.
Hence, at any location within the bed, there is negligible
temperature difference between the solid and the gas i.e.
T
s
r
!
; tzT
g
r
!
; thT r
!
; t; (10)
and the adsorbate loading is close to its equilibrium value i.e.
q r
!
; tzq

T r
!
; t; P r
!
; t: (11)
These near-equalities can be easily demonstrated using
heat and mass transfer correlations for packed beds, see for
example Wakao et al. [8] and Wakao and Funazkri [9]. These
quasi-static approximations are implicitly assumed for
example in the work of Mota et al. [10]. The advantages of
quasi-static approximation are the following: when local
thermal equilibrium prevails a single energy balance can be
used to describe both solid and gas phases; when local mass
equilibrium prevails, we can replace dq/dt (usually described
using a linear driving force model) by dq*/dt. When the fuel
tank processes are quasi-static, to design or simulate the fuel
tank, only adsorption isotherms and heat capacity of the
adsorbent need to be measured at different temperatures.
A lumped-parameter model involves intra-pellet lumping
andacross-the-bedlumpingof temperature, pressureandsolid-
phase concentration elds. The intra-pellet lumping of
temperature and concentration can be systematically justied
by a Biot number analysis. For example at 80 K and 20 bar, the
hydrogen gas thermal conductivity is 0.061663 W/m/K, NIST
web book [11]. Then, for a 0.5 mm diameter pellet, in the stag-
nant gas limit from Nu h
g
d
p
/k
g
2 we get the convective heat
transfer coefcient as h
g
246.65 W/m
2
/K. Huang et al. [12]
report an effective thermal conductivity of k
s
z0.32 W/m/K for
MOF-5. Using all these data we compute the Biot number of
a spherical pellet as Bi h
g
d
p
/6k
s
0.0642. Since the computed
Biot number is lower than 0.1, we can safely assume that the
pellets are thermally thin i.e. the intra-pellet temperature
gradients are negligible, see Incropera et al. [13].
Fig. 2 Fuel-tank details: longitudinal (left) and cross-
sectional (right) views.
Fig. 1 Langmuir t (lines) for MOF-5 excess adsorption
data (symbols) of Zhou et al. [3].
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The pressure drop across a bed of highly porous pellets is
often negligible, and it can be easily shown using an Ergun
equation analysis or see for example the results of Sankararao
and Gupta [15], justifying an across-the-bed pressure lumping.
For example at 80 K and 20 bar, the hydrogen gas density and
viscosity are 6.2069 kg/m
3
and 3.7453 10
6
Pa s, NIST web book
[11]. We assume a particle diameter of d
p
0.5 mm and a bed
porosity of 3
b
0.36. For a particular design of 0.5467 m diam-
eter, a 60 g/s ow of 80 K 20 bar gas corresponds to a supercial
velocity of U0.041181 m/s. Using these values in the Ergun
equation DP/L am
g
Ubr
g
U
2
, where a 1501 3
b

2
=3
3
b
d
2
p
and
b 1:751 3
b
=3
3
b
d
p
, Bird et al. [14], gives DP/L 0.013 bar/m,
which is negligible compared to the feed pressure of 20 bar.
Across-the-bed lumping of temperature and concentration
elds is intuitively assumed for the slower tank processes:
discharge, dormancy and venting. For a fast process like
refueling, however, we anticipate signicant temperature
gradients within the bed for which higher dimensional
models are being currently developed.
5. Model development
The quasi-static lumped-parameter model contains transient
mass and energy balances, resulting in two equations. For
a given bed and feed ow (when present), there are three
unknowns: the tank temperature, pressure and mass outow
rate. Closure is achieved by specifying one of these three
unknowns:
1. During discharge the mass outow rate is specied by the
fuel-cell demand. Hence, the model is solved for tempera-
ture and pressure.
2. During dormancy the outow is zero by denition. Hence,
the model is solved for temperature and pressure.
3. The vent is typically operated by a pressure controller.
Therefore neglecting valve transients, venting can be
treated as an isobaric process. Hence, the model is solved
for mass outow rate and temperature.
5.1. Transient mass balance
The rate of change of hydrogen content of the tank balances
the net ow into the tank. Hence the transient mass balance
for hydrogen is given by
dm
H
2
dt
_ m
f
_ m: (12)
Using Equation (9) we get
m
s
dq
dt
V
b
3
t
dr
g
dt
_ m
f
_ m: (13)
Now, expressions are developed for the two time deriva-
tives in the above equation. Assuming that the gas phase is in
equilibrium at the corresponding temperature and pressure
gives
r
g
t r
g
Tt; Pt: (14)
Then,
dr
g
dt

_
vr
g
vT
_
P
dT
dt

_
vr
g
vP
_
T
dP
dt
: (15)
The isobaric temperature derivative of density is related to
the isobaric thermal expansion coefcient a
Pg
according to
a
Pg

1
v
g
_
vv
g
vT
_
P

1
r
g
_
vr
g
vT
_
P
(16)
The isothermal pressure derivative of density is related to
the isothermal compressibility factor according to
k
Tg

1
v
g
_
vv
g
vP
_
T

1
r
g
_
vr
g
vP
_
T
; (17)
see Smith et al. [18], page 62. Using these results, the time
derivative of density is given by
dr
g
dt
r
g
a
Pg
dT
dt
r
g
k
Tg
dP
dt
: (18)
The quasi-static approximation for the adsorbate
concentration
qt q

Tt; Pt (19)
gives
dq
dt

dq

dt

_
vq

vT
_
P
dT
dt

_
vq

vP
_
T
dP
dt
: (20)
The temperature-dependence of q
*
comes from that of the
two Langmuir parameters: b(T ) and q
m
(T ). Using Equations (2)
and (3), and simplifying give
_
vq

vT
_
P
q

_
f
0
T
f T

B
1 bPT
2
_
: (21)
The pressure dependence of q
*
is only due to the explicit P
terms. Hence, from Equation (1) we get
_
vq

vP
_
T

1 bPP
: (22)
Using Equations (21) and (22) in (20) we get
dq

dt
q

_
f
0
T
f T

B
1 bPT
2
_

dT
dt

_
q

1 bPP
_

dP
dt
: (23)
Using equations (18) and (23) in equation (13) and rear-
ranging, the transient mass balance takes the form
a
11
dT
dt
a
12
dP
dt
b
1
; (24)
with
a
11
m
s
q

_
f
0
T
f T

B
1 bPT
2
_
V
b
3
t
r
g
a
Pg
; (25)
a
12

m
s
q

1 bPP
V
b
3
t
r
g
k
Tg
; (26)
and
b
1
_ m
f
_ m: (27)
Note that the dimensions of a
11
, a
12
and b
1
are mass/
temperature, mass/pressure and mass/time, respectively.
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5.2. Transient energy balance
The thermal masses associated with the fuel tank are the gas
phase, adsorbed phase, adsorbent, pressure vessel including
the bed restrainers and other bed internals, insulation layer,
outer shell and ambient, as shown in Fig. 2. The insulation
layer isolates the inner thermal masses (gas, adsorbed phase,
adsorbent, and pressure vessel) fromthe outer ones (shell and
ambient). When the fuel-tank processes are slow, a single
lumped temperature can be used for the inner thermal
masses. Sircar [16] shows that any adsorption measurement
directly gives only the Gibbsian surface excess adsorption and
not the absolute adsorption, and suggests using mass and
energy balances with excess adsorption to simulate practical
adsorption systems. The transient energy balance for the
inner thermal masses (system) is given by
dH
sys
dt
_ m
f
H
g
_
T
f
; P
f
_
_ mH
g
T; P
_
Q
l
V
b
3
t
dP
dt
: (28)
Computation of H
sys
is elaborated in the appendix. Each
term in the above equation is analyzed below, and the time
derivatives of temperature and pressure are collected
explicitly.
The differential change in the enthalpy of inner thermal
masses is dened as
dH
sys
T; P dm
w
H
w
dm
s
H
s
d
_
m
s
qH
q
_
d
_
V
b
3
t
r
g
H
g
_
: (29)
All the steel components in the inner thermal masses
(distribution tubes, restrainers, holding plates and pressure
vessel) are accounted as a steel wall of mass m
w
. For
a particular design for example we had m
w
z125 kg. Adsor-
bate enthalpy is obtained from the denition of heat of
adsorption as
H
q
H
g
DH
a
: (30)
This study assumes a constant average heat of adsorption,
independent of temperature and pressure. Hence, dH
q
dH
g
,
and
dH
sys
T; P m
w
dH
w
m
s
dH
s

_
m
s
q V
b
3
t
r
g
_
dH
g
m
s
_
H
g
DH
a
_
dq V
b
3
t
H
g
dr
g
: (31)
And its time derivative is
dH
sys
dt
m
w
dH
w
dt
m
s
dH
s
dt

_
m
s
q V
b
3
t
r
g
_
dH
g
dt
m
s
_
H
g
DH
a
_
dq
dt
V
b
3
t
H
g
dr
g
dt
: (32)
Substituting equation (32) in equation (28), and collecting
the terms containing H
g
(T, P) on one side and the remaining
time derivatives on another side gives
m
w
dH
w
dt
m
s
dH
s
dt

_
m
s
q V
b
3
t
r
g
_
dH
g
dt
m
s
DH
a
dq
dt
V
b
3
t
dP
dt
_ m
f
H
g
_
T
f
; P
f
_

_
_ mV
b
3
t
dr
g
dt
m
s
dq
dt
_
H
g
T; P
_
Q
l
:
(33)
From the mass balance equation (13), note that the coef-
cient of H
g
(T, P) in the above equation is _ m
f
. Then,
m
w
dH
w
dt
m
s
dH
s
dt

_
m
s
q V
b
3
t
r
g
_
dH
g
dt
m
s
DH
a
dq
dt
V
b
3
t
dP
dt
_ m
f
_
H
g
_
T
f
; P
f
_
H
g
T; P

_
Q
l
: 33
Note that the reference state used in computing the gas
phase enthalpy does not determine the system evolution,
since the gas enthalpy appears as a difference between two
states on the right hand side of equation (34). Hence, as
expected, the energy balance and the results deriving from it
are independent of the reference state used in computing the
gas phase enthalpy.
Now, using quasi-static approximations, all the time
derivatives are expressed in terms of the time derivatives of
temperature and pressure. For the time derivatives of r
g
and q
equations (18) and (23) are used. The time derivative of H
g
(T, P)
is expanded as
dH
g
dt

_
vH
g
vT
_
P
dT
dt

_
vH
g
vP
_
T
dP
dt
; (35)
see for example Section 2.1 of Ahluwalia and Peng [17].
Using the thermodynamic identities
_
vH
g
vT
_
P
T
_
vS
g
vT
_
P
C
pg
(36)
and
_
vH
g
vP
_
T
v
g
T
_
vS
g
vP
_
T
v
g
T
_
vv
g
vT
_
P
v
g
_
1 a
Pg
T
_
; (37)
see Smith et al. [18], page 191 we have,
dH
g
dt
C
Pg
dT
dt
v
g
_
1 a
Pg
T
_
dP
dt
: (38)
For the solid phases (pressure vessel and adsorbent),
neglecting the thermal expansion of the material, similar
equations are written as
dH
w
dt
C
Pw
dT
dt
v
w
dP
dt
; (39)
and
dH
s
dt
C
Ps
dT
dt
v
s
dP
dt
; (40)
Using equations (18), (23), (38)(40) in equation (34), and
rearranging the transient energy balance is in the form
a
21
dT
dt
a
22
dP
dt
b
2
; (41)
with
a
21
m
w
C
pw
m
s
C
ps

_
m
s
q

V
b
3
t
r
g
_
C
Pg
m
s
q

DH
a
_
f
0
T
f T

B
1 bPT
2
_
; (42)
a
22
m
w
v
w
m
s
v
s

_
m
s
q

v
g
V
b
3
t
_ _
1 a
Pg
T
_

m
s
q

DH
a
1 bPP
V
b
3
t
; (43)
and
b
2
_ m
f
_
H
g
_
T
f
; P
f
_
H
g
T; P

_
Q
l
: (44)
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Note that the dimensions of a
21
, a
22
and b
2
are energy/
temperature and energy/pressure and energy/time
respectively.
We assume that the heat leak has the form
_
Q
l
T
N
T=R
eff
(45)
We have assumed a typical value of R
eff
74.0K/W, so that
the heat leak into the tank during typical dormancy condi-
tions is about 3 W. Engineering calculations show that with
a 1-inch multi layer vacuum super insulation and good
mechanical design such values of R
eff
are realistic.
5.3. Solution procedures
Solving equations (24) and (41) simultaneously, gives
dT
dt

b
1
a
22
b
2
a
12
a
11
a
22
a
21
a
12
f
1
T; P; (46)
and
dP
dt

b
1
a
21
b
2
a
11
a
11
a
22
a
21
a
12
f
2
T; P: (47)
Among the coefcients appearing in these two equations
only b
1
contains _ m. Suppose _ m is known (as in the case of
discharge from the fuel-cell operation requirement or during
dormancy where it is zero by denition), these two coupled
rst order differential equations are solved with initial condi-
tions T(t 0) T
0
and P(t 0) P
0
, to give the temperature and
pressure evolution T(t) and P(t). For the isobaric processes of
venting, equation (47) gives the isobaric criterion as
b
1
a
21
b
2
a
11
: (48)
Using the expression for b
1
in the isobaric criterion and
rearranging gives the isobaric mass outow as
_ m _ m
f

a
11
a
21
b
2
: (49)
Equation (46) is solved with the above isobaric ow rate to
get T(t). This formulation allows an elegant implementation
of isobaric or isothermal processes, by setting f
1
or f
2
to zero
respectively, although for an arbitrary process neither of
them is zero. For an isobaric process, instead of deriving an
expression for the time derivative of pressure and then
setting it to zero, one could directly get an expression for _ m
by setting the pressure derivative to zero during the deriva-
tion. Such a procedure is mathematically identical to the
above method. We prefer the model described by equations
(46) and (47) since it gives a unied formalism for all the fuel
tank processes.
6. Dormancy
In a parked vehicle, continuous heat leak into the fuel tank
causes the hydrogen pressure to build up and gas is vented to
the fuel cell. The time period until the start of venting is called
dormancy. Let T
0
and P
0
respectively be the temperature and
pressure of the tank at the beginning. Let the vent pressure be
P
vent
25 bar. During dormancy, there is no ow into or out of
the tank i.e. _ m
f
_ m 0. Hence, the model equations reduce to
b
1
0, b
2

_
Q
l
. Therefore,
dT
dt


_
Q
l
a
12
a
11
a
22
a
21
a
12
(50)
and
dP
dt

_
Q
l
a
11
a
11
a
22
a
21
a
12
: (51)
Note that both dT/dt, and dP/dt are proportional to
_
Q
l
. The
temperature and pressure evolution equations are solved
simultaneously with the initial conditions T
0
, P
0
and the time
taken for the tank to reach the vent pressure gives the
dormancy. Figs. 3 and 4 show that a full tank (5 kg load),
starting at T
0
85.6 K and P
0
20 bar (for a given pressure and
hydrogen load the corresponding equilibrium temperature
can be got from equation (9)) reaches the vent pressure in 3.5
days, and the temperature at that time is 90.4 K.
An alternate, quick but approximate, method to estimate
dormancy is as follows: The hydrogen content of the tank at
the beginning of the dormant phase is m
H2
T
0
; P
0
. Let the
temperature of the tank at the end of the dormant phase be
T
vent
. By denition, hydrogen is not lost from the tank during
dormancy. Hence, T
vent
is computed by solving the equation
m
H
2
T
0
; P
0
m
H
2
T
vent
; P
vent
: (52)
Neglecting the temperature variation of R
eff
, the arithmetic
average heat leak during dormancy is
C
_
Q
l
D T
N
T
0
T
vent
=2=R
eff
: (53)
For dormancy, setting _ m
f
_ m 0 in the transient energy
balance equation (28), and integrating over the dormant
period gives
H
sys
T
vent
; P
vent
H
sys
T
0
; P
0
C
_
Q
l
DDt
dorm
V
b
3
t
P
vent
P
0
: (54)
The appendix details the computation of H
sys
(T, P). Since
T
vent
is already known, this equation is solved for Dt
dorm
. Note
that this equation is exact with a time-averaged heat leak. But
Fig. 3 Pressure evolution during full load dormancy, with
a 1-inch multi layer vacuum super insulation. The point
marks the end of dormancy.
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with an arithmetic average heat leak as dened above, this
equation is approximate. However, typically the temperature
range (T
0
, T
vent
) is small. Hence, the dormancy estimates from
this equation are generally accurate.
Now we discuss the partial tank dormancy. We note that
a given partial load can correspond to different sets of T
0
and
P
0
, depending on discharge and heat leak histories. For the
same load a lower tank pressure requires a lower tank
temperature with more hydrogen in the adsorbed phase. Fig. 5
shows dormancy as a function of initial tank pressure at
different loads. Figs. 5 and 6 show that decreasing the initial
pressure obviously increases dormancy since there is a larger
pressure rise required to reach the vent pressure. A half-full
tank (2.5 kg H
2
) initially at 99.25 K and 10 bar, with the same
insulation, has a dormancy of 17.3 days. Fig. 5 shows that in
the pressure range of interest, dormancy decreases mono-
tonically with initial pressure. Hence to achieve high
dormancy, the discharge strategy should keep the tank pres-
sure as low as possible at any partial load.
7. Isobaric venting
When the tank pressure reaches the vent pressure, hydrogen
is vented to the fuel-cell stack even though there is no fuel
demand. In an optimal venting strategy, gas is vented only to
the extent that the tank pressure does not rise above the vent
pressure. Hence, optimal venting is necessarily an isobaric
process occurring at the vent pressure. In practice, the vent
valve is operated by a pressure controller. If we neglect valve
transients, the real venting process can be idealized as an
isobaric process. Let T
vent
and P
vent
be respectively the
temperature and pressure of the tank at beginning of venting
phase. During venting, there is no inow i.e. _ m
f
0. Hence,
the equations (27) and (44) reduce to, b
1
_ m and b
2

_
Q
l
.
The outow is obtained from the isobaric criterion, equation
(49) as
_ m
_
Q
l
_
a
11
a
21
_
: (55)
The differential equation dT/dt is solved with the initial
condition T(t 0) T
vent
to get the temperature evolution T(t)
and the tank loading at any time is computed as m
H
2
Tt; P
vent
.
The same results can be obtained by employing the ther-
modynamic state method. The temperature at any particular
loading is obtained by solving
Fig. 4 Temperature evolution during full load dormancy,
with a 1-inch multi layer vacuum super insulation. The
point marks the end of dormancy.
Fig. 5 Dormancy as a function of initial pressure at
different loads.
Fig. 6 Initial temperature as a function of initial pressure
at different loads.
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m
H
2
m
H
2
T; P
vent
: (56)
On simplication the differential equation becomes
dT
dt

_
Q
l
a
21

T
N
T
R
eff
a
21
: (57)
Rearranging and integrating over the period required to
reach that load gives
R
eff
_
T
Tvent
a
21
dT
T
N
T

_
Dtvent
0
dt Dt
vent
: (58)
Figs. 7 and 8 give the temperature and hydrogen load
evolution for the full load venting. Initial temperature for the
full load venting is 90.40 Kwhich is the temperature at the end
of full load dormancy calculated in the previous section. A full
load tank (5 kg H
2
), after 100 days of isobaric venting at 25 bar
has 1.10 kg of hydrogen for a 78%venting loss. Fig. 9 shows the
hydrogen load evolution during the isobaric venting at
different initial loads, at 25 bar vent pressure. A half load tank
(2.5 kg H
2
), after 100 days of isobaric venting at 25 bar has
0.85 kg of hydrogenfor a 66%venting loss. Note that the rate of
hydrogen loss by venting decreases as initial load decreases.
8. Discharge
Recirculating hot hydrogen gas through the bed enhances
hydrogen desorption. This mode of heat transfer is preferred
(as compared to an electrical heater surrounding or embedded
inthe bed) due to the highinterfacial area betweenthe gas and
the adsorbent. Let _ m be the total outow from the bed at
temperature T. The outowfromthe tank is split (at point Ain
Fig. 10) into _ m
o
the output sent to the fuel cell, and the rest
_ m
f
_ m _ m
o
is recirculated as the feed, after it is heated up to
a temperature T
f
in an heat exchanger. Let us specify total
heat added to the recirculation systemincluding heat leak, the
pump work and heat added through the heat exchanger as
_
Q
h
and use it as a design variable. The enthalpy balance across
the pump and heat exchanger, assuming negligible pressure
drop (P zP
f
), is
_ m
f
H
g
_
T
f
; P
f
_
_ m
f
H
g
T; P
_
Q
h
: (59)
Using equation (59), equations (27) and (44) reduce to
b
2

_
Q
h

_
Q
l
and b
1
_ m
f
_ m _ m
o
. The differential equa-
tions for T and P can be solved to compute temperature and
pressure proles during discharge. Since
_
Q
h
and _ m
o
are
explicitly specied, T
f
is not required in the solution proce-
dure. Interestingly,
_
Q
h
and
_
Q
l
are treated identically in b
2
.
Hence, when
_
Q
h
is explicitly specied, in a lumped-parameter
description the recirculation loop could be absorbed into the
bed and
_
Q
h
could also represent a mode of heat transfer where
heat is directly added to the bed as in an electrical heater
surrounding or embedded within the bed. The mathematical
equivalence of discharge by hot gas recirculation (when
_
Q
h
is
specied) and the direct heat addition to the bed without
recirculation allows a component level simulation of the
former mode. Hence, the following results are quite generic,
Fig. 7 Temperature evolution during isobaric venting of
a full load tank (5 kg, 25 bar). The point marks the end of
100 days of isobaric venting.
Fig. 8 Load evolution during isobaric venting of a full load
tank (5 kg, 25 bar). The point marks the end of 100 days of
isobaric venting.
Fig. 9 Hydrogen load evolution during isobaric venting at
25 bar for different initial loads.
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and apply to either mode of heat addition. Here we consider
only a constant discharge and not a real drive cycle with rapid
variations in fuel-cell hydrogen demand, since the latter case
requires a more detailed system level simulation including
valves and controllers.
Figs. 11 and 12 show the temperature and pressure evolu-
tions during discharge at different rates of heat input for
a typical constant discharge of 2 g/s. If we assume that all the
discharged hydrogen is desorbed, the required rate of heat
input is
_
Q
h
z2 10
3
kg=s 2 10
6
J=kg 4 kW. Since this
estimate does not include the heat required to increase the
temperature of the adsorbent and structural components
within the insulation layer, the required heat input rate is
generally higher than 4 kW (the value can be lower if gas is
withdrawn from the gas phase rather than the adsorbed
phase). In Figs. 11 and 12, for a given constant peak discharge
of 2 g/s, we have considered heat input rates from 3 to 7.3 kW.
At low heat input rates, both the tank temperature and pres-
sure decrease monotonically due to the process of endo-
thermic desorption and gas discharge. The lower bound of
3 kWheat input rate was chosen, for this particular discharge,
so that the nal tank pressure does not fall below the atmo-
spheric pressure. At higher heat input rates, the tank pressure
may rise due to temperature rise, even though gas is being
discharged continuously. The upper bound of 7.3 kW heat
input rate was chosen to ensure that the system pressure
never rises above the vent pressure 25 bar. At 7.3 kW heat
input rate, the tank temperature increases monotonically and
a maximum is observed in the pressure evolution due to the
interplay between pressure increase due to temperature rise
and pressure decrease due to discharge. At heat input rates
well above 7.3 kW, simulations show that the tank pressure
increases monotonically, and exceeds the vent pressure.
Those results are not shown in Fig. 12. Thus we identify the
operating range of heat input rates (for a given discharge)
based on the tank pressure bounds.
9. Summary
The four cryo-adsorber fuel-tank processes occur over
different time scales: refueling over a few minutes, discharge
over a few hours, dormancy over a few days, and venting over
a few weeks. The slower processes i.e. discharge, dormancy
and venting are expected to have negligible temperature
Fig. 10 Discharge by hot gas recirculation.
Fig. 11 Tank temperature evolution during a constant
discharge of 2 g/s, at different rates of heat input.
Fig. 12 Tank pressure evolution during a constant
discharge of 2 g/s, at different rates of heat input.
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gradients within the bed and are hence amenable to a lum-
ped-parameter analysis. We have developed a quasi-static
lumped-parameter model for the fuel tank and discussed the
results for the slower processes. We have also described an
alternative solution method for dormancy and venting based
on the thermodynamic state description.
Acknowledgments
The authors would like to thank Michael Herrmann, Scott
Jorgensen, Ulrich Eberle, Dieter Hasenauer, Rainer Immel,
Gregory Meisner, Anne Dailly and Eric Poirier for technical
data and/or valuable suggestions during the course of model
development.
Appendix
Thermophysical properties
The properties of hydrogen are taken from the NIST web book
[11], maintained as look-up tables, and interpolated during the
simulation. The steel used is assumed to be the austenitic
steel, type 316 or 316L. The temperature-dependence of steels
specic heat capacity is considered, since it is important for
dormancy calculations, and is available at the NIST cryogenics
site [19] as a correlation of the form
log
10
C
p

8
n0
c
n
_
log
10
T
_
n
: (60)
For the in-house specic heat capacity data of MOF-5,
Meisner and Yang [20], the same form was tted with
(c
8
,.,c
0
) (0.4472, 5.8880, 32.9149, 101.7242, 189.5527,
217.2841, 148.0616, 51.5601, 6.7148), whereC
p
is inJ kg
1
K
1
.
To compute the enthalpy of inner thermal masses, H
sys
,
equation (29) is rearranged as
dH
sys
T; P m
w
dH
w
m
s
dH
s
m
s
d
_
qH
q
_
V
b
3
t
dr
g
H
g
: (61)
Using equations (30), (39) and (40) and rearranging give
dH
sys
T; P m
w
C
Pw
m
s
C
Ps
dT m
w
v
w
m
s
v
s
dP
m
s
d
_
qH
g
qDH
a
_
V
b
3
t
dr
g
H
g
(62)
Assuming some reference temperature and pressure, and
integrating gives
H
sys
T;PH
sys
T
r
;P
r

_
T
Tr
m
w
C
Pw
m
s
C
Ps
dTm
w
v
w
m
s
v
s
PP
r
m
s
_
qH
g
qDH
a
_

T;P
Tr;Pr
V
b
3
t
r
g
H
g

T;P
Tr ;Pr
m
w
C
Pw
m
s
C
Ps
TT
r
m
w
v
w
m
s
v
s
PP
r
m
s
_
qH
g
qDH
a
_

T;P
Tr ;Pr
V
b
3
t
r
g
H
g

T;P
Tr;Pr
; (63)
where C
px

_
T
Tr
C
px
dT=TT
r
are the mean heat capacities. We
assume arbitrary reference values of T
r
77 K, P
r
20 bar, and
set H
sys
(T
r
, P
r
) 0, since only the difference in enthalpies and
not their absolute values is relevant in the calculations. As T, P
varies, the mass of hydrogen in the tank varies, see equation
(9). Hence, the values of H
sys
at different T, P do not correspond
to same mass of hydrogen in the tank.
r e f e r e n c e s
[1] Satyapal S, Petrovic J, Read C, Thomas G, Ordaz G. The US
department of energys national hydrogen storage project:
progress towards meeting hydrogen-powered vehicle
requirements. Catal Today 2007;120:24656.
[2] Zhou L. Progress and problems in hydrogen storage methods.
Renew Sustain Energ Rev 2005;9:395408.
[3] Zhou W, Wu H, Hartman MR, Yildirim T. Hydrogen and
methane adsorption in metal-organic frameworks: a high-
pressure volumetric study. J Phys Chem C 2007;111:161317.
[4] Benard P, Chahine R. Determination of the adsorption
isotherms of hydrogen on activated carbons above the
critical temperature of the adsorbate over wide temperature
and pressure ranges. Langmuir 2001;17:19505.
[5] Panella B, Hirscher M, Putter H, Muller U. Hydrogen
adsorption in metal-organic frameworks: CuMOFs and
ZnMOFs compared. Adv Funct Mater 2006;16:5204.
[6] Dailly A, Vajo J, Ahn CC. Saturation of hydrogen sorption in
Zn benzene-dicarboxylate and Zn naphthalene-
dicarboxylate. J Phys Chem B 2006;110:1099101.
[7] Kaye SS, Long JR. Hydrogen storage in the dehydrated
prussian blue analogues. J Am Chem Soc 2005;127:65067.
[8] Wakao N, Kaguei S, Funazkri T. Effect of uid dispersion
coefcients on particle-to-uid heat transfer coefcients in
packed beds correlation of Nusselt numbers. Chem Eng Sci
1979;34:32536.
[9] Wakao N, Funazkri T. Effect of uid dispersion coefcients
on particle-to-uid mass transfer coefcients in packed
beds correlation of Sherwood numbers. Chem Eng Sci 1978;
33:137584.
[10] Mota JPB, Rodrigues AE, Saatdjian E, Tondeur D. Dynamics
of natural gas adsorption storage systems employing
activated carbon. Carbon 1997;35:125970.
[11] NIST web book. http://webbook.nist.gov/chemistry/uid/.
[12] Huang BL, Ni Z, Millward A, McGaughey AJH, Uher C,
Kaviany M, et al. Thermal conductivity of a metal-organic
framework (MOF-5): part II. Measurement. Int J Heat Mass
Transfer 2007;50:40511.
[13] Incropera FP, DeWitt DP, Bergman TL, Lavine AS.
Fundamentals of heat and mass transfer. 6th ed. John Wiley
& Sons; 2006.
[14] Bird RB, Stewart WE, Lightfoot EN. Transport phenomena.
2nd ed. John Wiley & Sons; 2002.
[15] Sankararao B, Gupta SK. Modeling and simulation of xed
bed adsorbers (FBAs) for multi-component gaseous
separations. Comput Chem Eng 2007;31:128295.
[16] Sircar S. Gibbsian surface excess for gas adsorption
revisited. Ind Eng Chem Res 1999;38:367082.
[17] Ahluwalia RK, Peng JK. Dynamics of cryogenic hydrogen
storage in insulated pressure vessels for automotive
applications. Int J Hydrogen Energy 2008;33:462233.
[18] Smith JM, Van Ness HC, Abbot MM. Chemical engineering
thermodynamics. 6th ed. New Delhi: Tata McGraw Hill; 2003.
[19] NIST Cryogenics web site. http://cryogenics.nist.gov/
NewFiles/material_properties.html.
[20] Meisner GP, Yang J. Unpublished results. General Motors NA
R&D; 2004.
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