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international journal of hydrogen energy 34 (2009) 5466–5475

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A lumped-parameter model for cryo-adsorber

hydrogen storage tank

V. Senthil Kumara,*, K. Raghunathana, Sudarshan Kumarb

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

article info abstract

Article history: One of the primary requirements for commercialization of hydrogen fuel-cell vehicles is
Received 24 March 2009 the on-board storage of hydrogen in sufficient quantities. On-board storage of hydrogen by
Received in revised form adsorption on nano-porous adsorbents at around liquid nitrogen temperatures and
30 April 2009 moderate pressures is considered viable and competitive with other storage technologies:
Accepted 1 May 2009 liquid hydrogen, compressed gas, and metallic or complex hydrides. The four cryo-
Available online 2 June 2009 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
Keywords: slower processes i.e. discharge, dormancy and venting are expected to have negligible
Hydrogen storage modeling temperature gradients within the bed, and hence are amenable to a lumped-parameter
Cryogenic adsorption analysis. Here we report a quasi-static lumped-parameter model for the cryo-adsorber fuel
Metal-organic frameworks 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.
ª 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction In this work we assume that the operating pressure of the

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.
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.: þ91 80 41984567; fax: þ91 80 41158262.

E-mail addresses: senthil.vadivelu@gm.com, senthil.v.kumar@gmail.com (V. Senthil Kumar).
0360-3199/$ – see front matter ª 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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international journal of hydrogen energy 34 (2009) 5466–5475 5467

Nomenclature Nu, Bi, Re, Pr Nusselt, Biot, Reynolds and Prandtl numbers
vw ; vs Mean specific volumes of the steel and
T, P Temperature and pressure, K, bar
adsorbent, m3/kg
ms, Vb Skeletal mass and volume of the adsorbent bed,
aPg ; kTg Isobaric thermal expansion coefficient and
kg, m3
isothermal compressibility, 1/K, 1/bar
mw Mass of tank wall, typically steel, kg
Hg, Hq, Hs, Hw Specific enthalpy of gas, adsorbate, adsorbent
m_ f;m
_ Inlet and outlet gas mass flow rates, kg/s
(‘‘solid’’) and steel components (‘‘wall’’), J/kg
3p, 3b, 3t Pellet, bed and total porosities, 3t ¼ 3b þ (1  3b)3p,
CPg, CPs, Cpw Specific heat capacity of gas, adsorbent and
m3/m3
steel, J/kg/K
rs, rp, rb Skeletal, pellet and bed densities, rp ¼ rs(1  3p),
Q_ l ; Q_ h Heat leak rate, heat addition rate into the
rb ¼ rp(1  3b), kg/m3
tank, W
rg, vg Gas density and specific volume vg ¼ 1/rg, kg/m3,
q, q* Excess adsorbate concentration and its
m3/kg
equilibrium value, kg H2/kg adsorbent
mg, kg, ks Gas viscosity, gas thermal conductivity and
qm, b The two Langmuir adsorption isotherm
adsorbent thermal conductivity, Pa s, W/m/K,
parameters, kg/kg, 1/bar
W/m/K
DHa Heat of adsorption, J/kg H2 adsorbed
dp Pellet diameter, m
Hsys Enthalpy of the inner thermal masses, J
U Superficial bed velocity, m/s
TN Ambient temperature, K
hg Convective heat transfer coefficient on the surface
Reff Effective resistance for heat leak into the
of a pellet, W/m2/K
inner thermal masses, K/W

 Dormancy & Venting – While the vehicle is parked, its pres- excess adsorption data can be fitted to a Langmuir isotherm of
sure builds up to vent pressure, say 25 bar, due to contin- the following form:
uous heat leak into the fuel tank, and gas is vented to the
bP
fuel cell or atmosphere. The process of venting is also called q ðT; PÞ ¼ qm ; (1)
1 þ bP
boil-off, by analogy with liquid hydrogen storage systems.  
The time period until the start of venting is called B
b ¼ b0 exp ; (2)
dormancy. T

These 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. When
the molecular transport processes are fast, slower processes like
discharge, dormancy and venting are expected to have negli-
gible internal gradients and are generally amenable to a lum-
ped-parameter analysis. In this report we describe a quasi-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.
Section 2 describes the adsorption data for MOF-5. Section 3
describes a fuel tank design considered in this study. Section 4
identifies the assumptions involved in the 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 directly taken from existing databases, some are computed
in this work; these details are given in the appendix.
qm0
qm ¼ ; (3)
f ðTÞ
where we have assumed
f ðTÞ ¼ 1 þ AT2 : (4)
For the hydrogen adsorption data in AX-21, Benard and
Chahine [4] use
f ðTÞ ¼ 1 þ AT: (5)
However, for the MOF-5 data in the considered range of
temperature and pressure, we find that equation (4) gives
a good fit. Fig. 1 shows the Langmuir fit for data in the range
1–30 bar and 60–125 K, with the following parameters :
b0 ¼ 2.8164  103 bar1, B ¼ 332.0158 K, qm0 ¼ 11.7134  102
kg H2/kg MOF and A ¼ 131.3231  106 K2. At 20 bar and 77 K,
these parameters give q* ¼ 0.0532 kg H2/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 densified
MOF-5 adsorption data, we assume that MOF-5 pellets have
same density as the powder. Hence, ‘solid’ density
rs ¼ 1780 kg/m3, pellet porosity 3p ¼ 0.662, and pellet density
 
rp ¼ rs 1  3p ¼ 601:64 kg=m3 : (6)

2. Adsorption data Assuming a dense random packing of spheres gives a bed

porosity of 3b ¼ 0.36, bed density
Zhou et al. [3] have reported the adsorption data for MOF-5
rb ¼ rp ð1  3b Þ ¼ 385:05kg=m3 (7)
powder over a wide range of temperature and pressure. Over
the range of 60–125 K temperature and 1–30 bar pressure, their and total porosity
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5468 international journal of hydrogen energy 34 (2009) 5466–5475
Fig. 1 – Langmuir fit (lines) for MOF-5 excess adsorption
data (symbols) of Zhou et al. [3].
3t ¼ 3b þ ð1  3b Þ3p ¼ 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 4.7–5.2 kJ/mol, and Zhou et al. [3] report an
‘initial’ heat of adsorption of about 4.8 kJ/mol. Here we assume
a constant average heat of adsorption DHa ¼ 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. A header
distributes the hydrogen feed stream to a packed bed of cryo-
adsorbent pellets. The bed adsorbs hydrogen, the unadsorbed
gas flow gets collected and flows out of the tank. Hydrogen gas
flowing out of the tank can be cooled and recirculated for
further adsorption.
Fig. 2 – Fuel-tank details: longitudinal (left) and cross-
sectional (right) views.
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,
mH2 ðT; PÞ ¼ ms q ðT; PÞ þ Vb 3t rg ðT; PÞ: (9)
3
At 20 bar and 77 K, rg ¼ 6.4851 kg/m . Using these values in
Equation (9) gives an adsorbent mass of 75.3 kg. Allowing
a 20% excess gives ms ¼ 90.37 kg and Vb ¼0.2347 m3 ¼ 234.7 l.
The bed volume will be significantly lower for densified
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
equilibrium states. The adsorbents typically offer large specific
internal surface area, leading to intimate gas–solid contact.
Hence, at any location within the bed, there is negligible
temperature difference between the solid and the gas i.e.
Ts ð!
r ; tÞzTg ð!
r ; tÞhTð!
r ; tÞ; (10)
and the adsorbate loading is close to its equilibrium value i.e.
qð!
r ; tÞzq ½Tð!
r ; tÞ; Pð!
r ; tÞ: (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
and across-the-bed lumping of temperature, pressure and solid-
phase concentration fields. The intra-pellet lumping of
temperature and concentration can be systematically justified
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 ¼ hgdp/kg ¼ 2 we get the convective heat
transfer coefficient as hg ¼ 246.65 W/m2/K. Huang et al. [12]
report an effective thermal conductivity of ks z 0.32 W/m/K for
MOF-5. Using all these data we compute the Biot number of
a spherical pellet as Bi ¼ hgdp/6ks ¼ 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].
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international journal of hydrogen energy 34 (2009) 5466–5475 5469

The pressure drop across a bed of highly porous pellets is    

drg vrg dT vrg dP
¼ þ : (15)
often negligible, and it can be easily shown using an Ergun dt vT P dt vP T dt
equation analysis or see for example the results of Sankararao
The isobaric temperature derivative of density is related to
and Gupta [15], justifying an across-the-bed pressure lumping.
the isobaric thermal expansion coefficient aPg according to
For example at 80 K and 20 bar, the hydrogen gas density and
viscosity are 6.2069 kg/m3 and 3.7453  106 Pa s, NIST web book    
1 vvg 1 vrg
[11]. We assume a particle diameter of dp ¼ 0.5 mm and a bed aPg ¼ ¼ (16)
vg vT P rg vT P
porosity of 3b ¼ 0.36. For a particular design of 0.5467 m diam-
eter, a 60 g/s flow of 80 K 20 bar gas corresponds to a superficial The isothermal pressure derivative of density is related to
velocity of U ¼ 0.041181 m/s. Using these values in the Ergun the isothermal compressibility factor according to
equation DP/L ¼amgU þ brgU2, where a ¼ 150ð1  3b Þ2 =33b d2p and    
1 vvg 1 vrg
b ¼ 1:75ð1  3b Þ=33b dp , Bird et al. [14], gives DP/L ¼ 0.013 bar/m, kTg ¼  ¼ ; (17)
vg vP T rg vP T
which is negligible compared to the feed pressure of 20 bar.
Across-the-bed lumping of temperature and concentration see Smith et al. [18], page 62. Using these results, the time
fields is intuitively assumed for the slower tank processes: derivative of density is given by
discharge, dormancy and venting. For a fast process like
drg dT dP
refueling, however, we anticipate significant temperature ¼ rg aPg þ rg kTg : (18)
dt dt dt
gradients within the bed for which higher dimensional
models are being currently developed. The quasi-static approximation for the adsorbate
concentration

qðtÞ ¼ q ½TðtÞ; PðtÞ (19)

5. Model development
gives
The quasi-static lumped-parameter model contains transient    
dq dq vq dT vq dP
mass and energy balances, resulting in two equations. For ¼ ¼ þ : (20)
dt dt vT P dt vP T dt
a given bed and feed flow (when present), there are three
unknowns: the tank temperature, pressure and mass outflow The temperature-dependence of q* comes from that of the
rate. Closure is achieved by specifying one of these three two Langmuir parameters: b(T ) and qm(T ). Using Equations (2)
unknowns: and (3), and simplifying give

   0 
1. During discharge the mass outflow rate is specified by the vq f ðTÞ B
¼ q þ : (21)
fuel-cell demand. Hence, the model is solved for tempera- vT P f ðTÞ ð1 þ bPÞT2
ture and pressure.
The pressure dependence of q* is only due to the explicit P
2. During dormancy the outflow is zero by definition. Hence,
terms. Hence, from Equation (1) we get
the model is solved for temperature and pressure.
 
3. The vent is typically operated by a pressure controller. vq q
¼ : (22)
Therefore neglecting valve transients, venting can be vP T ð1 þ bPÞP
treated as an isobaric process. Hence, the model is solved
Using Equations (21) and (22) in (20) we get
for mass outflow rate and temperature.

 0   
dq f ðTÞ B dT q dP
¼ q þ 2
 þ  : (23)
5.1. Transient mass balance dt f ðTÞ ð1 þ bPÞT dt ð1 þ bPÞP dt

The rate of change of hydrogen content of the tank balances Using equations (18) and (23) in equation (13) and rear-
the net flow into the tank. Hence the transient mass balance ranging, the transient mass balance takes the form
for hydrogen is given by
dT dP
a11 þ a12 ¼ b1 ; (24)
dmH2 dt dt
_ f  m:
¼m _ (12)
dt with
Using Equation (9) we get  0 
f ðTÞ B
a11 ¼ ms q þ  Vb 3t rg aPg ; (25)
dq drg f ðTÞ ð1 þ bPÞT2
ms þ Vb 3t _ f  m:
¼m _ (13)
dt dt
ms q
Now, expressions are developed for the two time deriva- a12 ¼ þ Vb 3t rg kTg ; (26)
ð1 þ bPÞP
tives in the above equation. Assuming that the gas phase is in
equilibrium at the corresponding temperature and pressure and
gives
_ f  m:
b1 ¼ m _ (27)
rg ðtÞ ¼ rg ½TðtÞ; PðtÞ: (14)
Note that the dimensions of a11, a12and b1 are mass/
Then, temperature, mass/pressure and mass/time, respectively.
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5470 international journal of hydrogen energy 34 (2009) 5466–5475

5.2. Transient energy balance dHw dHs  dH

g dq dP
mw þ ms þ ms q þ Vb 3t rg þ ms DHa  Vb 3t
dt dt dt dt dt

  
The thermal masses associated with the fuel tank are the gas ¼m _ f Hg Tf ; Pf  Hg ðT; PÞ þ Q_ l : ð33Þ
phase, adsorbed phase, adsorbent, pressure vessel including
Note that the reference state used in computing the gas
the bed restrainers and other bed internals, insulation layer,
phase enthalpy does not determine the system evolution,
outer shell and ambient, as shown in Fig. 2. The insulation
since the gas enthalpy appears as a difference between two
layer isolates the inner thermal masses (gas, adsorbed phase,
states on the right hand side of equation (34). Hence, as
adsorbent, and pressure vessel) from the outer ones (shell and
expected, the energy balance and the results deriving from it
ambient). When the fuel-tank processes are slow, a single
are independent of the reference state used in computing the
lumped temperature can be used for the inner thermal
gas phase enthalpy.
masses. Sircar [16] shows that any adsorption measurement
Now, using quasi-static approximations, all the time
directly gives only the Gibbsian surface excess adsorption and
derivatives are expressed in terms of the time derivatives of
not the absolute adsorption, and suggests using mass and
temperature and pressure. For the time derivatives of rg and q
energy balances with excess adsorption to simulate practical
equations (18) and (23) are used. The time derivative of Hg(T, P)
adsorption systems. The transient energy balance for the
is expanded as
inner thermal masses (‘system’) is given by
   
dHg vHg dT vHg dP
dHsys   dP ¼ þ ; (35)
_ g ðT; PÞ þ Q_ l þ Vb 3t :
_ f Hg Tf ; Pf  mH
¼m (28) dt vT P dt vP T dt
dt dt
see for example Section 2.1 of Ahluwalia and Peng [17].
Computation of Hsys is elaborated in the appendix. Each
Using the thermodynamic identities
term in the above equation is analyzed below, and the time
derivatives of temperature and pressure are collected    
vHg vSg
explicitly. ¼T ¼ Cpg (36)
vT P vT P
The differential change in the enthalpy of inner thermal
masses is defined as and

      
  vHg vSg vvg  
dHsys ðT;PÞ ¼ dðmw Hw Þ þ dðms Hs Þ þ d ms qHq þ d Vb 3t rg Hg : (29) ¼ vg þ T ¼ vg  T ¼ vg 1  aPg T ; (37)
vP T vP T vT P
All the steel components in the inner thermal masses see Smith et al. [18], page 191 we have,
(distribution tubes, restrainers, holding plates and pressure
vessel) are accounted as a steel ‘wall’ of mass mw. For dHg dT  dP
¼ CPg þ vg 1  aPg T : (38)
a particular design for example we had mw z 125 kg. Adsor- dt dt dt
bate enthalpy is obtained from the definition of heat of For the solid phases (pressure vessel and adsorbent),
adsorption as neglecting the thermal expansion of the material, similar
equations are written as
Hq ¼ Hg þ DHa : (30)
dHw dT dP
This study assumes a constant average heat of adsorption, ¼ CPw þ vw ; (39)
dt dt dt
independent of temperature and pressure. Hence, dHq ¼ dHg,
and and

 dHs dT dP
dHsys ðT; PÞ ¼ mw dHw þ ms dHs þ ms q þ Vb 3t rg dHg ¼ CPs þ vs ; (40)
dt dt dt
 
þms Hg þ DHa dq þ Vb 3t Hg drg : (31) Using equations (18), (23), (38)–(40) in equation (34), and
And its time derivative is rearranging the transient energy balance is in the form

dT dP
dHsys dHw dHs  dH
g
a21
dt
þ a22
dt
¼ b2 ; (41)
¼ mw þ ms þ ms q þ Vb 3t rg
dt dt dt dt
with
 dq drg
þms Hg þ DHa þ Vb 3t Hg : (32) 
dt dt a21 ¼ mw Cpw þ ms Cps þ ms q þ Vb 3t rg CPg
Substituting equation (32) in equation (28), and collecting  0 
f ðTÞ B
the terms containing Hg(T, P) on one side and the remaining ms q DHa þ 2
; (42)
f ðTÞ ð1 þ bPÞT
time derivatives on another side gives
  
dHw dHs  dH
g dq dP a22 ¼ mw vw þ ms vs þ ms q vg þ Vb 3t 1  aPg T
mw þ ms þ ms q þ Vb 3t rg þ ms DHa  Vb 3t
dt dt dt dt dt ms q DHa
  þ  Vb 3t ; (43)
  drg dq ð1 þ bPÞP
¼m_ f Hg Tf ; Pf  m_ þ Vb 3t þ ms  Hg ðT; PÞ þ Q_ l :
dt dt
and
(33)

From the mass balance equation (13), note that the coeffi-
  
_ f Hg Tf ; Pf  Hg ðT; PÞ þ Q_ l :
b2 ¼ m (44)
_ f . Then,
cient of Hg(T, P) in the above equation is m
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international journal of hydrogen energy 34 (2009) 5466–5475 5471

Note that the dimensions of a21, a22 and b2 are energy/ the tank i.e. m_f ¼m _ ¼ 0. Hence, the model equations reduce to
temperature and energy/pressure and energy/time b1 ¼ 0, b2 ¼ Q_ l . Therefore,
respectively.
We assume that the heat leak has the form dT Q_ l a12
¼ (50)
dt a11 a22  a21 a12
Q_ l ¼ ðTN  TÞ=Reff (45) and
We have assumed a typical value of Reff ¼ 74.0K/W, so that
dP Q_ l a11
the heat leak into the tank during typical dormancy condi- ¼ : (51)
dt a11 a22  a21 a12
tions is about 3 W. Engineering calculations show that with
a 1-inch multi layer vacuum super insulation and good Note that both dT/dt, and dP/dt are proportional to Q_ l . The
mechanical design such values of Reff are realistic. temperature and pressure evolution equations are solved
simultaneously with the initial conditions T0, P0 and the time
taken for the tank to reach the vent pressure gives the
5.3. Solution procedures
dormancy. Figs. 3 and 4 show that a full tank (5 kg load),
starting at T0 ¼ 85.6 K and P0 ¼ 20 bar (for a given pressure and
Solving equations (24) and (41) simultaneously, gives
hydrogen load the corresponding equilibrium temperature
dT b1 a22  b2 a12 can be got from equation (9)) reaches the vent pressure in 3.5
¼ ¼ f1 ðT; PÞ; (46)
dt a11 a22  a21 a12 days, and the temperature at that time is 90.4 K.
An alternate, quick but approximate, method to estimate
and
dormancy is as follows: The hydrogen content of the tank at
dP b1 a21 þ b2 a11 the beginning of the dormant phase is mH2 ðT0 ; P0 Þ. Let the
¼ ¼ f2 ðT; PÞ: (47)
dt a11 a22  a21 a12 temperature of the tank at the end of the dormant phase be
Tvent. By definition, hydrogen is not lost from the tank during
Among the coefficients appearing in these two equations
dormancy. Hence, Tvent is computed by solving the equation
only b1 contains m. _ Suppose m _ is known (as in the case of
discharge from the fuel-cell operation requirement or during mH2 ðT0 ; P0 Þ ¼ mH2 ðTvent ; Pvent Þ: (52)
dormancy where it is zero by definition), these two coupled
first order differential equations are solved with initial condi- Neglecting the temperature variation of Reff, the arithmetic
tions T(t ¼ 0) ¼ T0 and P(t ¼ 0) ¼ P0, to give the temperature and average heat leak during dormancy is
pressure evolution T(t) and P(t). For the isobaric processes of
CQ_ l D ¼ ½TN  ðT0 þ Tvent Þ=2=Reff : (53)
venting, equation (47) gives the isobaric criterion as
_f ¼m
For dormancy, setting m _ ¼ 0 in the transient energy
b1 a21 ¼ b2 a11 : (48) balance equation (28), and integrating over the dormant
Using the expression for b1 in the isobaric criterion and period gives
rearranging gives the isobaric mass outflow as
Hsys ðTvent ; Pvent Þ  Hsys ðT0 ; P0 Þ ¼ CQ_ l DDtdorm þ Vb 3t ðPvent  P0 Þ: (54)
a
m _ f  11 b2 :
_ ¼m (49) The appendix details the computation of Hsys(T, P). Since
a21
Tvent is already known, this equation is solved for Dtdorm. Note
Equation (46) is solved with the above isobaric flow rate to that this equation is exact with a time-averaged heat leak. But
get T(t). This formulation allows an elegant implementation
of isobaric or isothermal processes, by setting f1 or f2 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 unified 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 T0 and P0 respectively be the temperature and
pressure of the tank at the beginning. Let the vent pressure be
Pvent ¼ 25 bar. During dormancy, there is no flow into or out of
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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5472 international journal of hydrogen energy 34 (2009) 5466–5475
Fig. 4 – Temperature evolution during full load dormancy,
with a 1-inch multi layer vacuum super insulation. The
point marks the end of dormancy.
with an arithmetic average heat leak as defined above, this
equation is approximate. However, typically the temperature
range (T0, Tvent) 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 T0 and
P0, 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
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.
pressure rise required to reach the vent pressure. A half-full
tank (2.5 kg H2) 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 Tvent and Pvent be respectively the
temperature and pressure of the tank at beginning of venting
phase. During venting, there is no inflow i.e. m _ f ¼ 0. Hence,
the equations (27) and (44) reduce to, b1 ¼ m _ and b2 ¼ Q_ l .
The outflow is obtained from the isobaric criterion, equation
(49) as
 
a11
_ ¼ Q_ l
m : (55)
a21
The differential equation dT/dt is solved with the initial
condition T(t ¼ 0) ¼ Tvent to get the temperature evolution T(t)
and the tank loading at any time is computed as mH2 ½TðtÞ; Pvent .
The same results can be obtained by employing the ther-
modynamic state method. The temperature at any particular
loading is obtained by solving
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international journal of hydrogen energy 34 (2009) 5466–5475 5473

mH2 ¼ mH2 ðT; Pvent Þ: (56)

On simplification the differential equation becomes

dT Q_ l TN  T
¼ ¼ : (57)
dt a21 Reff a21

Rearranging and integrating over the period required to

reach that load gives
Z T Z Dtvent
a21 dT
Reff ¼ dt ¼ Dtvent : (58)
Tvent TN  T 0

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 K which is the temperature at the end
of full load dormancy calculated in the previous section. A full
load tank (5 kg H2), after 100 days of isobaric venting at 25 bar
has 1.10 kg of hydrogen for a 78% venting loss. Fig. 9 shows the
Fig. 8 – Load evolution during isobaric venting of a full load
hydrogen load evolution during the isobaric venting at
tank (5 kg, 25 bar). The point marks the end of 100 days of
different initial loads, at 25 bar vent pressure. A half load tank
isobaric venting.
(2.5 kg H2), after 100 days of isobaric venting at 25 bar has
0.85 kg of hydrogen for a 66% venting loss. Note that the rate of
hydrogen loss by venting decreases as initial load decreases.

 
m _ f Hg ðT; PÞ þ Q_ h :
_ f Hg Tf ; Pf ¼ m (59)
8. Discharge
Using equation (59), equations (27) and (44) reduce to
b2 ¼ Q_ h þ Q_ l and b1 ¼ m
_f m_ ¼ m _ o . The differential equa-
Recirculating hot hydrogen gas through the bed enhances
tions for T and P can be solved to compute temperature and
hydrogen desorption. This mode of heat transfer is preferred
pressure profiles during discharge. Since Q_ h and m _ o are
(as compared to an electrical heater surrounding or embedded
explicitly specified, Tf is not required in the solution proce-
in the bed) due to the high interfacial area between the gas and
_ be the total outflow from the bed at dure. Interestingly, Q_ h and Q_ l are treated identically in b2.
the adsorbent. Let m
Hence, when Q_ h is explicitly specified, in a lumped-parameter
temperature T. The outflow from the tank is split (at point A in
_ o the ‘output’ sent to the fuel cell, and the rest description the recirculation loop could be ‘absorbed’ into the
Fig. 10) into m
_f ¼m _ m _ o is recirculated as the ‘feed’, after it is heated up to bed and Q_ h could also represent a mode of heat transfer where
m
heat is directly added to the bed as in an electrical heater
a temperature Tf in an heat exchanger. Let us specify total
surrounding or embedded within the bed. The mathematical
heat added to the recirculation system including heat leak, the
equivalence of discharge by hot gas recirculation (when Q_ h is
pump work and heat added through the heat exchanger as Q_ h
specified) and the direct heat addition to the bed without
and use it as a design variable. The enthalpy balance across
recirculation allows a component level simulation of the
the pump and heat exchanger, assuming negligible pressure
former mode. Hence, the following results are quite generic,
drop (P z Pf), is

Fig. 7 – Temperature evolution during isobaric venting of

a full load tank (5 kg, 25 bar). The point marks the end of Fig. 9 – Hydrogen load evolution during isobaric venting at
100 days of isobaric venting. 25 bar for different initial loads.
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5474 international journal of hydrogen energy 34 (2009) 5466–5475
Fig. 10 – Discharge by hot gas recirculation.
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  103 kg=s  2  106 J=kg ¼ 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
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.
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 kW heat input rate was chosen, for this particular discharge,
so that the final 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
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international journal of hydrogen energy 34 (2009) 5466–5475
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 steel’s
specific 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
X
8
 n
log10 Cp ¼ cn log10 T :
n¼0
For the in-house specific heat capacity data of MOF-5,
Meisner and Yang [20], the same form was fitted with
(c8,.,c0) ¼ (0.4472, 5.8880, 32.9149, 101.7242, 189.5527,
217.2841, 148.0616, 51.5601, 6.7148), where Cp is in J kg1 K1.
To compute the enthalpy of inner thermal masses, Hsys,
equation (29) is rearranged as
 
dHsys ðT; PÞ ¼ mw dHw þ ms dHs þ ms d qHq þ Vb 3t dðrg Hg Þ:
Using equations (30), (39) and (40) and rearranging give
dHsys ðT; PÞ ¼ ðmw CPw þ ms CPs ÞdT þ ðmw vw þ ms vs ÞdP
 
þms d qHg þ qDHa þ Vb 3t dðrg Hg Þ
Assuming some reference temperature and pressure, and
integrating gives
Z T
Hsys ðT;PÞHsys ðTr ;Pr Þ ¼ ðmw CPw þms CPs ÞdTþðmw vw
Tr
5475
varies, the mass of hydrogen in the tank varies, see equation
(9). Hence, the values of Hsys at different T, P do not correspond
to same mass of hydrogen in the tank.
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