i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9

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CFD model for charge and discharge cycle of adsorptive

hydrogen storage on activated carbon

Jinsheng Xiao a,b,*, Rong Peng c, Daniel Cossement b, Pierre Bénard b, Richard Chahine b
a
Hubei Key Laboratory of Advanced Technology for Automotive Components, School of Automotive Engineering, Wuhan University of
Technology, Hubei 430070, China
b
Hydrogen Research Institute, Université du Québec à Trois-Rivières, QC G9A 5H7, Canada
c
School of Materials Science and Engineering, Wuhan University of Technology, Hubei 430070, China

article info abstract

Article history: High surface area activated carbons and other microporous adsorbents have generated
Received 20 March 2012 a significant amount of interest over the past decade as storage media for hydrogen and
Received in revised form natural gas, due to their high storage capacity at low temperatures and their use in gas
13 October 2012 purification processes. This paper uses computational fluid dynamics (CFD) to simulate the
Accepted 31 October 2012 charging and discharging of a sorption-based hydrogen storage system. The CFD model is
Available online 5 December 2012 based on the mass, momentum and energy conservation equations of a system formed of
gaseous and adsorbed hydrogen, an activated carbon bed and steel tank walls. The
Keywords: adsorption process is modeled using the DubinineAstakov adsorption isotherms extended
Hydrogen storage to the supercritical regime. The model is implemented using Fluent. In our study, we can
Activated carbon obtain accuracy peak temperature of simulation due to a non-constant isosteric heat of
Adsorption adsorption is used, derived from the model isotherms. We adopt piecewise heat capacity to
Charge consider the heat capacity of the adsorbed phase of hydrogen. We can make a conclusion
Discharge that the simulated temperatures without consideration of heat capacity for hydrogen in
Computational fluid dynamics adsorbed phase (cpa), rise faster and reach higher peaks than the simulated temperatures
with consideration of cpa, and diverge more from experimental results. Also, we study the
changes of temperature, pressure and adsorption during the charging and discharging
processes as well as when the system is idle (which we define as dormancy) in the case of
room temperature water cooling. The results are compared with experimental data from
a storage unit cooled with room temperature water. The simulated pressure is in a good
agreement with the experimental values. The simulated temperature profiles are also
generally in good agreement with the experimental values, except close to the inlet and the
wall. In addition, we have studied the effect of quality of the mesh on the accuracy and
stability of the numerical computation and the influence of the mass flow rates on
temperature and adsorption capacity.
Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

* Corresponding author. Hydrogen Research Institute, Université du Québec à Trois-Rivières, QC G9A 5H7, Canada. Tel.: þ1 819 376
5011x4478; fax: þ1 819 376 5164.
E-mail addresses: Jinsheng.Xiao@uqtr.ca (J. Xiao), Pierre.Benard@uqtr.ca (P. Bénard), Richard.Chahine@uqtr.ca (R. Chahine).
0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2012.10.119
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9
Nomenclature
cpa heat capacity of hydrogen in adsorbed phase, J/
kg K
cpg heat capacity of hydrogen in gas phase, J/kg K
C2 inertial resistance coefficient, m1
Dp average diameter of particles, m
Eg energy of hydrogen gas, J/kg
Es energy of solid, J/kg
DH isosteric adsorption heat, J/mol
hi species enthalpy along i direction, J/kg
! j!
Ji diffusion flux of species i, kg/m2 s
keff effective thermal conductivity of the medium, W/
mK
kg hydrogen gas thermal conductivity, W/m K
ks solid medium conductivity, W/m K
m distribution parameter of isotherms
MH2 molecular mass of hydrogen gas, kg/mol
na absolute adsorption amount per mass of
adsorbent, mol/kg
n0 limit adsorption, mol/kg
p static pressure or equilibrium pressure of gas, Pa
1. Introduction
Hydrogen is a renewable and potentially low emission energy
vector currently being considered as a replacement fuel for
fossil sources. Its efficient and safe storage is a challenge that is
being addressed through four approaches: liquefaction,
compression, absorption in metal hydrides and adsorption in
high surface area nanoporous materials [1]. Each method has
its own advantages and limitations, and probably their own
niches. For example, liquid hydrogen has the advantages of
light weight, but it consumes a lot of energy during liquefac-
tion and lost some hydrogen mass during dormancy.
Hydrogen physisorption has been considered as one of the
most promising storage methods for meeting the goals of the
US Department of Energy (DOE) hydrogen plan for fuel cell
powered vehicles [2,3]. Hirscher and Panella [4] reported that
the maximum storage capacity for an activated carbon with
a BET (BrunauereEmmetteTeller) surface area of 2560 m2/g at
77.4 K was 4.5 wt%. Kojima et al. [5] studied hydrogen
adsorption and desorption in different carbon materials at 296
and 77 K. They claimed that superactivated carbon having
specific surface area (SSA) of 3220 m2/g, adsorbed and desorbed
1.3wt% of hydrogen at 296 K and 5 wt% of hydrogen at 77 K.
The porous high surface area activated carbon (AC) has
been proposed as storage media for hydrogen as it is an
effective and low-cost adsorption material [6]. A number of
research studies about adsorptive hydrogen storage on acti-
vated carbon have been carried out in recent years. Paggiaro
et al. [7] formulated a two-dimensional model to study the
thermal effects during high pressure filling of a cryo-
adsorptive hydrogen storage tank. The adsorbent is
powdered activated carbon. They obtained a good agreement
between experiments and simulations. Momen et al. [8] used
1451
p0 saturation pressure of the vapor at temperature T
or limit pressure, Pa
R universal gas constant, 8.314 J/mol K
Q energy source term, W/m3
!
F momentum source term, N/m3
Fi component of momentum source term in i
direction, N/m3
Sm mass source term, kg/m3 s
!u physical velocity, m/s
!v superficial velocity vector, m/s
vj magnitude of velocity vector, m/s
vi component of velocity in i direction, m/s
Greek symbols
1/k viscous resistance factor, m2
a enthalpic factor, J/mol
b entropic factor, J/mol K
εb bed porosity
m dynamic viscosity of hydrogen gas, Pa s
rg hydrogen gas density, kg/m3
rp particle density of activated carbon, kg/m3
rs solid density, kg/m3
s stress tensor, Pa
a numerical model based on the solution of the 2D transport
equations for mass, momentum and energy in porous media
to investigate hydrogen charging in packed bed storage tank.
Results show that the capacity limitation due to thermal
heating can be avoided by using high thermal conductivity
packed bed. Xiao et al. [9] used a finite element model to
simulate the heat and mass transfer in activated carbon
hydrogen storage tank. The heat capacity of adsorbed phase,
the contact thermal resistance between the AC bed and the
steel wall, and the inertial resistance of the high speed
charging hydrogen gas are considered in the model.
The computational fluid dynamics (CFD) is performed
based on the finite control volume (FCV) method. Recently, the
CFD was widely used to simulate the hydrogen storage system
based on activated carbon [1,6,10e12]. Among these works,
Herosilla-Lara et al. [1] studied the hydrogen storage in tank
packed with activated carbon at room temperature by
carrying out experiments and simulations. They built an
axisymmetrical geometry used for simulations of the charging
of the tank. However they only considered the charging
process. Xiao et al. [13] studied the heat and mass transfer in
a hydrogen storage system packed with activated carbon at
room temperature (295 K) and medium storage pressure
(10 MPa) by using the Fluent, overall good agreement is found
between computation and experimental data published by
Hermosilla-Lara et al [1]. However，they only considered the
charging process and the thermal capacity of gas phase
hydrogen, and used the constant isosteric heat of adsorption.
Xiao et al. [14] developed a finite element model for simulating
the whole cycle of charge and discharge processes in an
activated carbon hydrogen storage tank by using the Comsol.
In their work, they only considered the thermal capacity of gas
phase hydrogen.
1452 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9

In this work, the computational fluid dynamics (CFD) 2.2. Momentum conservation equation
method is used to simulate charge and discharge cycle of
adsorptive hydrogen storage on activated carbon with room The momentum equation can be expressed as [15]:
temperature water cooling. In our study, non-constant isos-
v
!
 !
teric heat of adsorption is used, derived from the model rg v þ V$ rg !
v!v ¼ Vp þ V$s þrg !
g þ F (4)
vt
isotherms. The range of isothermal heat of adsorption is huge
due to the great variation of hydrogen adsorbed by the acti- where s is the stress tensor and the momentum source term
!
vated carbon, during the charge and discharge cycle of F (N/m3) is based on the Ergun equation and includes viscous
adsorptive hydrogen storage on activated carbon. So that and inertial losses. Its component in i direction, “Fi”, for simple
a non-constant isosteric heat of adsorption is used. When the homogeneous porous media, can be written as [15]:
charging mass flow rate at entrance is large, we have to
m 1
consider the heat capacity of the hydrogen adsorbed by the Fi ¼  vi  C2 rg j!
v jvi (5)
k 2
activated carbon because the great variation of the adsorbed
where m (Pa s) is the dynamic viscosity of hydrogen gas, 1/k (1/
phase of hydrogen in a short time. But we can not use the user
m2) is the viscous resistance coefficient, C2 (1/m) is the inertial
defined function (UDF) in Fluent to define the heat capacity. In
resistance coefficient, j!v j is the magnitude of the velocity
order to solve this problem, we adopt piecewise heat capacity
vector and vi is the velocity component along the i direction.
to consider the heat capacity for hydrogen in adsorbed phase
(cpa). The quality of the mesh plays a significant role in the
accuracy and stability of the numerical computation. We 2.3. Energy conservation equation
attempt to search for the optimum cell number to obtain the
accurate and stable results of numerical computation. The energy equation expresses the balance between the
On that basis, we study the changes of temperature, energy amount accumulated in the tank and the energy
pressure and adsorption during the charging and discharging changes due to convective flow, pressure work, conductive
processes as well as when the system is idle (which we define and thermal dispersion fluxes and heat release due to
as dormancy) in the case of room temperature water cooling. adsorption. It can be expressed as [15]:
Also, the effects of the isosteric heat of adsorption, the heat
vh i h
i
capacity and the mass flow rates on the hydrogen storage εb rg Eg þ ð1  εb Þrp Es þ V$ !
v rg Eg þ p
properties (pressure, temperature and adsorbed density vt
 

distributions) are studied during the charging, dormancy and ¼ V$ keff VT þ V$ s $! v þQ (6)
discharging processes.
where E is the sum of internal energy and kinetic energy and
expressed by enthalpy h as:
2. CFD model for hydrogen storage system
p v2
E¼h þ (7)
2.1. Mass conservation equation r 2

So the pressure work is considered in the terms of left hand

In porous media, the mass conservation equation can be side of the energy conservation equation. The potential
written as [15]: energy by gravity may be neglected here. It is obvious that the

 viscous dissipation F is included in the term V$ðs $!
v Þfrom the
v εb rg

þ V$ rg !
following relations:
v ¼ Sm (1)
vt



where Sm (kg/m3 s) is the mass source term. The source term v ¼!
V$ s $! v $ V$ s þ s : V!
v ¼!
v $ V$s þ F (8)
models the mass transfer between the gas phase and the
absorbed phase per unit volume per second. It can be written The energy source term Q in the energy conservation
as: equation can be expressed as [13]:

v 
Sm ¼  rb qa (2) Q ¼ DHSm =MH2 (9)
vt
Note that the bed density can be expressed with bed where Sm (kg/m3 s) is the mass source term, DH (J/mol) is the
porosity and particle density: rb ¼ ð1  εb Þrp ðkg AC=m3 Þ, and isosteric heat of adsorption which relate to the absolute
the mass ratio of adsorbate to adsorbent can be expressed as: adsorption. Q (W/m3) is the energy source term, which models
qa ¼ MH2 na ðkg H2 =kg ACÞ, so that the mass source term can the generated heat per unit volume.
also be written as [13]:

vna vna 2.4. Adsorption model

Sm ¼ rb MH2 ¼ ð1  εb Þrp MH2 (3)
vt vt
where εb is the bed porosity, rb (kg/m3) is the bed density and The adsorption sub-models used in this work include models
rp (kg/m3) is the particle density of activated carbon, na (mol/ for the adsorption isotherms and the isosteric heat of
kg) is the absolute adsorbed amount per unit adsorbent and adsorption. A modified DubinineAstakhov (DeA) adsorption
MH2 (kg/mol) is the molecular mass of hydrogen. model is used to describe the adsorption isotherms in
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9 1453

Fig. 1 e Geometric model (a) and grid (b) of hydrogen storage tank.

activated carbons. The absolute adsorption isotherm is
modeled using [16]:
  m   mocouples distributed along the vertical axis and the radius.
RT m p0
na ¼ n0 exp  ln
a þ bT p
where n0 (mol/kg) is the limiting adsorption, the values of n0 is
71.6 mol/kg, m is a number generally close to a small integer
and equal to 2 for most activated carbons. R is the universal
gas constant, p is the equilibrium pressure, p0 is the saturation
pressure. The value of p0 is 1.47e9 Pa. The parameters a and b
are the enthalpic and the entropic factors, equal to 3080 J/mol
and 18.9 J/(mol K), respectively.
The adsorption amount has significant effect on isosteric
heat of adsorption, which decreases during adsorption while
increasing during desorption. Based on the model isotherms
of Equation (10), the heat of adsorption can be obtained using
the following equation [14]:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
DH ¼ a lnðn0 =na Þ
Note that the low coverage limit exhibits a weak singularity
associated with the absence of a proper Henry’s law limit for
the Dubinin adsorption isotherms. This weak singularity has,
however, little effect in the high pressure behavior.
of Maxsorb and submerged in a Dewar flask. The tempera-
ture evolution inside the tank is measured using eight ther-
The hydrogen inflow and outflow rates are quantified with
(10)
flow meters. Before starting the tests, the Dewar flask
enclosing the storage tank was filled with room temperature
water. Then, the tank was filled with hydrogen at the specified
flow rate. The dynamic pressures, temperatures, and flow-
rates of the system were monitored during the charging and
discharging processes as well as when the system is idle. The
detail description and some illustrations of the experimental
system were shown in [17].
3.2. Geometry model
The Commercial CFD software Fluent is used to simulate the
hydrogen adsorption process during charging, dormancy and
discharging. Fig. 1(a) shows the geometric model of the
(11) hydrogen storage tank. The gray area (except the pipe) corre-
sponds to the tank packed with activated carbon. The
temperature monitor points are shown as red dots, distributed
along the axial and radial directions. Fig. 1(b) shows the grid of
the hydrogen storage tank, which has 5377 nodes. The
dimensions of the geometry model and the location of the
monitoring points are given in Table 1.

3. Model parameters of hydrogen storage 3.3. Material properties

system
The material properties of hydrogen storage tank are given in
3.1. Experimental system for model validation
Table 2. The effective thermal conductivity is computed as the

The experiments were performed at the Hydrogen Research

Institute of the University of Quebec at Trois-Rivieres [17]. The
Table 2 e Material properties.
experiments were performed with a 2.5 L tank filled with 671 g
Activated carbon Density (kg/m3) 517.6
Specific heat capacity (J/kg K) 825
Thermal conductivity (W/m K) 0.646
Table 1 e Geometric parameters and coordinates. Porosity 0.49
Hydrogen Density Ideal gas
Parameter Value (mm) Parameter Value (mm)
Specific heat capacity (J/kg K) 14,700
Inner radius of tank 46.9 Point C2 (143.75, 0) Thermal conductivity (W/m K) 0.206
Thickness of tank wall 3.9 Point C3 (188.75, 0) Viscosity (Pa s) 8.411e-6
Length of tank 400 Point C4 (233.75, 0) Viscous resistance coefficient (m2) 8.29055e7
Inner radius of pipe 4 Point C5 (278.75, 0) Inertial resistance coefficient (m1) 7586
Length of pipe 53.75 Point C6 (323.75, 0) Steel wall Density (kg/m3) 7830
Thickness of pipe wall 1 Point Cr (248.75, 23.5) Specific heat capacity (J/kg K) 468
Point C1 (98.75, 0) Point Cw (233.75, 46.9) Thermal conductivity (W/m K) 13
1454 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9

Table 3 e Values of qaand c0ps .

Time (s) 0e953 953e3822 3822e4694 4694e6000 Table 5 e Initial and environmental conditions.
qa 0.0168027 0.0168027 0.0090476 0.0012925 Test No. pi (MPa) Ti (K) Tf (K) h (W/(m2 K)
c0ps (J/kg K) 1072 1072 958 844
18 0.032 301.5 301.7 36
19 0.049 302 302.5 36
20 0.032 302.4 302.5 36
volume average of the fluid (hydrogen) conductivity and the
solid (activated carbon) conductivity, and it may be expressed
as [15]:

keff ¼ εb kg þ ð1  εb Þks (12) 4. Results and discussions

where kg and ks (W/m K) are, respectively, the thermal
conductivities of hydrogen and activated carbon.
The CFD software Fluent normally considers only two
components for the mixture properties of porous media. The
specific heat is written as a volumetric average of the gas
phase and the solid phase:
 
rcp m ¼ εb rg cpg þ ð1  εb Þrp c0ps
where the modified specific heat for the solid phase includes
the contribution of the adsorbed phase of hydrogen, and is
given by:
c0ps ¼ cps þ qa cpa zcps þ qa cpg
where qa ¼ na MH2 , we set c0ps as the specific heat for the solid
phase (adsorbent and adsorbate) in the Fluent. We calculate
the average values of na at the end of the charging and dis-
charging according to the values of experimental temperature
and pressure. Then, we calculate the different values of c0ps
during the processes of charging, discharging and dormancy.
The values of c0ps at the end of the charging and discharging are
1072 J/(kg K) and 844 J/(kg K). The different values of c0ps during
the charging, discharging and dormancy processes are given
in Table 3.
3.4. Boundary and initial conditions
Boundary and initial conditions of the three tests are given in
Table 4 and Table 5. The boundary and initial conditions used
in this section are based on Test No. 20, which was performed
at the Hydrogen Research Institute of the University of Quebec
at Trois-Rivieres. The pressure is easier to measure accurately
than the mass flow rate. Therefore, we correct the intake and
output hydrogen flow rates based on the measured pressure
profile.
The computational fluid dynamics (CFD) method is used to
simulate the charging and discharging of a sorption-based
hydrogen storage system. In our study, we adopt piecewise
heat capacity to consider the heat capacity of the adsorbed
phase of hydrogen and non-constant isosteric heat of
adsorption. On that basis, we study the changes of tempera-
ture, pressure and adsorption during the charging, dormancy
(13)
and discharging processes. Also, the effects of the isosteric
heat of adsorption, the heat capacity and the mass flow rate
on the hydrogen storage properties (pressure, temperature
and adsorbed density distributions) are studied during the
charging, dormancy and discharging processes.
(14)
4.1. Mesh sensitive analysis
The quality of the mesh plays a significant role in the accuracy
and stability of the numerical computation. The cell shape
and cell size have an important impact on the accuracy and
stability of the numerical solution. The finer meshes can
result higher accuracy of solution but will cost more computer
memory and more CPU (Central Processing Unit) time. We
attempt to find the optimum mesh size by which we can get
more accurate numerical solution in shorter CPU time. In
order to study the effect of mesh quality on solution, we
consider three cases: (1) finer mesh: 19,671 cells and 20,654
nodes, (2) intermediate mesh: 4885 cells and 5377 nodes, (3)
coarser mesh: 3126 cells and 3520 nodes. We exam the effects
of the cell size on the accuracy of simulation pressure and
simulation temperature at C4 respectively. When the finer
mesh is adopted, the accuracy almost has no more increase
but it doubles the run time. If we use coarser mesh, the
stability of the numerical computation will decrease. So that
the intermediate mesh is adopted in our study.
4.2. Mass balance analysis

Hydrogen exists in the storage tank in both adsorbed and

gaseous phases. Fig. 2 shows the mass balance of hydrogen in
the system. The ma represents the mass of hydrogen adsor-
Table 4 e Inlet boundary conditions.
bed by the activated carbon. The amount of hydrogen is
Test No. Charge period Discharge period calculated by use of the modified DubinineAstakhov (DeA)
_ (kg/s) Tin (K) Time (s) m
Time (s) m _ (kg/s) Tin (K) adsorption model. The mg represents the mass in the gas
phase. The mt is the total mass of hydrogen present in tank.
18 0e196 9.556e-5 294.9 2828e3616 2.171e-5 297.7
Fig. 2 shows the total amount of hydrogen stored equals the
19 0e442 4.355e-5 296.1 3046e3907 2.186e-5 298.0
20 0e953 2.048e-5 297.6 3822e4694 2.186e-5 297.7
sum of hydrogen in adsorbed phase and gaseous phase in the
adsorbent bed.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9
Fig. 2 e Mass balance analysis of gaseous (mg), adsorbed (ma), and total (mt) hydrogen masses.
4.3. Comparison of pressures
Fig. 3 shows a comparison of the pressure obtained from the
simulations with the experimental data obtained for the
system modeled. In general Fig. 3 shows good agreement with
the experimental results, although the equilibrium pressures
after charge are slightly higher than the experimental result.
4.4. Distributions of temperature and adsorption
density
Fig. 4 (a) and (b) show the temperature distributions in the
tank at 953 s and 4694 s respectively. At 953 s, the temperature
Fig. 3 e Pressure comparison in hydrogen storage tank.
1455
is higher in the center of the tank and lower close to the
entrance and the walls. At 4694 s, the situation is reversed: the
temperature is lower in the center of the tank and higher close
to the system boundaries.
The absolute adsorption density at different locations
remains almost uniform during charging and discharging.
Fig. 4 (c) and (d) show contours of absolute adsorption in the
tank at 953 s and 4694 s respectively. At 953 s, the largest
absolute adsorption is observed close to the wall of the tank,
whereas the smallest absolute adsorption is located at the
center of the tank. At 4694 s, the situation is reversed and the
largest absolute adsorption is observed near the center of the
tank and the smallest close to the wall of the tank. This is
because the absolute adsorption depends on the local pres-
sure and temperature. As the pressure distribution is uniform
throughout the tank while the temperature distribution var-
ies at different places, the absolute adsorption amount is
largest where the temperature is lowest and the absolute
adsorption amount is lowest where the temperature is
largest.
4.5. Comparison of temperatures
Fig. 5 compares the temperature obtained numerically with
the experimental data. In general, all the simulated temper-
ature curves agree well with the experimental curves.
However, the temperatures at C1 and Cw are affected by the
inlet boundary condition and the thermal exchanges with the
wall, respectively. We used a more realistic geometric model
(Fig. 1) to replace the simplified wide-open geometric model
for obtaining good agreement temperature at point C1 with
the experimental.
1456 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9
Fig. 4 e Contours of temperature (K) at (a) 953 s and (b) 4694 s, and absolute adsorption (mol/kg) at (c) 953 s and (d) 4694 s.
4.6. Velocity field analysis
Fig. 6 shows the velocity magnitude distributions along axis at
different time during charge and discharge respectively. Fig. 7
shows the velocity distributions at 50 s and 4644 s respec-
tively. Generally speaking, the maximum magnitude of the
velocity is observed near the entrance. During charge, the
maximum magnitude of the velocity at C1, C2 and C3 are
0.09 m/s, 0.056 m/s and 0.047 m/s respectively. During
discharge, the maximum magnitude of the velocity at C1, C2
and C3 are 0.089 m/s, 0.055 m/s and 0.046 m/s respectively.
The maximum magnitude of the velocity at C1, C2 and C3
during charge and discharge are almost the same, but in
opposite directions.
5. Parametric study
The parameters used for this study are based on the operating
conditions of the experiments (namely Test No. 18, 19 and 20),
which were performed at the Hydrogen Research Institute of
the University of Quebec at Trois-Rivieres. The boundary and
initial conditions used in previous section are based on Test
No. 20. The pressure is easier to measure accurately than the
mass flow rate. Therefore, we correct the intake and output
hydrogen flow rates based on the measured pressure profile.
5.1. Effective heat capacity on temperature
In order to study the effect of the effective heat capacity of
adsorptive system on temperature variations, we simulated the
system without and with consideration of the heat capacity of
hydrogen in adsorbed phase. Three cases related to Test No. 18,
19 and 20 which have nominal charging flow rates of 60, 30 and
15 SLPM (standard liters per minute) are adopted for the study.
Fig. 8 shows the effect of the effective heat capacity on
temperature at C4 when the charging mass flow rate at entrance
is (a) 9.556  105 kg/s (Test No. 18), (b) 4.355  105 kg/s (Test
No. 19) and (c) 2.048  105 kg/s (Test No. 20), respectively Fig. 9.
The simulated temperatures without consideration of heat
capacity for hydrogen in adsorbed phase (cpa), rise faster and
reach higher peaks than the simulated temperatures with
consideration of cpa, and diverge more from experimental
results. These differences are more significant for higher
charging mass flow rates, for example, 4.355  105 kg/s or
9.556  105 kg/s. In general, the inclusion of the heat capacity
of hydrogen in adsorbed phase leads to better experimental
agreement as it pertains to temperature.
5.2. Isosteric heat of adsorption on temperature
The value of the isosteric heat of adsorption is determined by
a large number of experiments. The value of the isosteric heat
of adsorption is different in different literature due to different
experimental conditions and structure of activated carbon.
The range of isosteric adsorption heat is from 3000 J/mol to
10,000 J/mol in different literature. The value of the isosteric
heat of adsorption is 3300 J/mol in [10], 10,500 J/mol in [11].
In our study, we have considered the dependence of the
isosteric heat of adsorption on the adsorbed density. In order
to validate this approach we compare four cases: (1) the
isosteric heat of adsorption is set to a constant value of 3185 J/
mol; (2) the isosteric heat of adsorption is set to a constant value
of 7500 J/mol; (3) a constant value of 5250 J/mol is used, obtained
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9 1457

Fig. 5 e Temperature comparison at different monitoring

points along (a) axial and (b) radial positions. Fig. 6 e Velocity magnitude distributions along axis at
different time during (a) charge and (b) discharge.

by fitting the simulation data to the experimental results; and (4)

the isosteric heat of adsorption is calculated using Equation (9).
adsorbed by the activated carbon in three cases (Test No. 18,
The isosteric heat of adsorption is set to a constant value of
Test No. 19 and Test No. 20). The charging mass flow rates at
3185 J/mol in [13], the simulated temperature curves agree with
entrance in three cases are 9.556  105 kg/s, 4.355  105 kg/s
the experimental curves during charge. When the constant
and (c) 2.048  105 kg/s. Pressure up to the same value (about
value of 3185 J/mol is used in this paper, the simulated
9 MPa) at the end of charging in three cases.
temperature curves agree with the experimental curves during
Fig. 10(a) shows the effect of mass flow rates on the mass of
charge. However, the peak temperature of simulation is higher
hydrogen adsorbed by the activated carbon. The mass of
than the experimental results during discharge. When the
hydrogen adsorbed by the activated carbon in the Test No. 18
constant value of 5250 J/mol is used, obtained by fitting the
is lower than in the Test No. 20. This is because the absolute
simulation data to the experimental results, we can obtain
adsorption depends on the local pressure and temperature.
accurate peak temperature of simulation. However, we can
The temperature in the Test No. 18 is extremely higher than
obtain more accurately peak temperature of simulation, when
the Test No. 20.
non-constant isosteric heat of adsorption is used. When the
Fig. 10(b) shows the effect of mass flow rates on the
variational isosteric heat of adsorption which relate to the
temperature at C4. For higher charging mass flow rates, the
absolute adsorption is used, the value of isosteric heat of
temperature will reach the peak temperature in a short time.
adsorption varies from 9500 J/mol to 4500 J/mol during charge,
When the mass flow rates are 9.556  105 kg/s,
and from 4500 J/mol to 7500 J/mol during discharge.
4.355  105 kg/s and 2.048  105 kg/s, respectively, the
temperature will increase 48 K, 38 K and 15 K at the end of the
5.3. Effect of mass flow rates on adsorption filling process. The peak temperature in the Test No. 18 is
extremely higher than in the Test No. 20. When the mass flow
In order to study the effect of mass flow rates on adsorption, rates are large, the heat generated due to the adsorption and
we compare the temperature at C4 and the mass of hydrogen compression is not able to dissipate in time.
1458 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9

Fig. 9 e Effect of isosteric heat of adsorption on

temperature at C4 based on Test No. 20.

Fig. 7 e Velocity magnitude distributions along axial

positions with different radii at (a) 50 s and (b) 4644 s.

Fig. 8 e Effect of heat capacity of adsorbed hydrogen (Cpa) Fig. 10 e Effect of mass flow rate on (a) the absolute
on temperature at C4 under different charging flow rates. adsorption and (b) temperature at C4.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 5 0 e1 4 5 9
6. Conclusions
A CFD model was developed to simulate whole char-
geedischarge cycle of adsorptive hydrogen storage on acti-
vated carbon. We used the CFD software Fluent to simulate
the hydrogen adsorption process in a hydrogen storage unit
during charging and discharging, and when the system is idle
in the case of room temperature water cooling. In our study,
we adopt piecewise heat capacity to consider the heat
capacity of the adsorbed phase of hydrogen and non-constant
isosteric heat of adsorption. We study the changes of
temperature, pressure and adsorption during the charging
and discharging processes as well as when the system is idle.
Also, the effects of the isosteric heat of adsorption, the heat
capacity and the mass flow rates on the hydrogen storage
properties are studied during the charging, dormancy and
discharging processes.
The mesh sensitive analysis is made to obtain accuracy
and stable numerical solution in shorter run times. We have
tried to search for the optimum cell number, so that we can
get more accurate and stable numerical solution in shorter
run times.
The non-constant heat of adsorption which relate to the
absolute adsorption was adopted to achieve validity for the
whole cycle. We replaced the constant isosteric heat of
adsorption by the various heat of adsorption. We can obtain
the accuracy peak temperature of simulation when the
various heat of adsorption is used.
The heat capacity for hydrogen in adsorbed phase was
considered to improve accuracy in the whole cycle. We have
considered the effect of the heat capacity of the adsorbed
phase on the results. The simulated temperatures without
consideration of heat capacity for hydrogen in adsorbed phase
(cpa), rise faster and reach higher peaks than the simulated
temperatures with consideration of (cpa), and diverge more
from experimental results.
The model, implanted in Fluent, is well validated by
experiments and applied for parametric study. The simulation
results were compared with experimental measurements.
The simulated pressures showed good agreement with the
experimental values. Except for the monitoring points at C1
and Cw, the simulated temperatures were also in agreement
with the experimental data.
We have studied mass flow rates on the mass of
hydrogen adsorbed by the activated carbon. The mass of
hydrogen adsorbed by the activated carbon in the Test
No. 18 is lower than in the Test No. 20. This is because
the absolute adsorption depends on the local pressure
and temperature. The temperature in the Test No. 18 is
extremely higher than the Test No. 20. When the mass
flow rates are 9.556  105 kg/s, 4.355  105 kg/s and
2.048  105 kg/s, respectively, the temperature at C4 will
increase 48 K, 38 K and 15 K at the end of the filling
process. The larger flow rates result in less amount of
adsorption due to thermal effects.
1459
Acknowledgments
We wish to acknowledge the supports from the NSERC
Hydrogen Canada (H2CAN) Strategic Research Network and
the Natural Resources Canada (NRCAN).
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