Applied Thermal Engineering 213 (2022) 118622

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Heat and mass transfer characteristics of charging in a metal hydride-phase

change material reactor with nano oxide additives: The large
scale-approach
Atef Chibani a, c, *, Slimane Merouani a, Cherif Bougriou b, Aissa Dehane a
a
Laboratory of Environmental Process Engineering, Department of Chemical Engineering, Faculty of Process Engineering, University Salah Boubnider Constantine 3, P.O.
Box 72, 25000 Constantine, Algeria
b
Department of Mechanical Engineering, Faculty of Technology, University of Mostefa Ben Boulaid, Batna 2, 05000 Batna, Algeria
c
Faculty of Sciences and Applied Sciences, Department of Process Engineering, Larbi Ben M’hidi University, 04000, Oum El Bouaghi, Algeria

A R T I C L E I N F O A B S T R A C T

Keywords: Integrating metal hydride (MH) for hydrogen storage with phase change materials (PCMs) received increasing
Metal hydride (MH) attention today to ensure effective thermal management in MH-storage reactors and reduce the operating cost of
Hydrogen storage the process. This study revealed the first coupling approach (at large scale) of hydrogen storage in LaNi5 alloys
Phase change material (PCM)
with heat recovery by using a PCM loaded with nanoparticles (i.e. the MH-nano-PCM system) in a cylindrical
Nano-PCM
MH-nano-PCM reactor
MH-tank reactor (diameter: 1 m) equipped with four tubes of nano-PCM. Mass and heat transfer phenomena
Heat and mass transfer were computationally analyzed in the diverse regions of the reactor. The temporal temperature profiles (average
and contours), the MH-hydrogenation efficiency, the velocity contours and PCM-liquid fraction were established
in the presence (at 5% v/v) and absence of four types of nano-oxides (Al2O3, MgO, SnO2 and SiO2). Significant
results were obtained. The nano-PCM system efficiently recuperates the heat lost from the exothermal absorption
reaction; however, a slight reduction in the latent energy storage unit’s performance is obtained compared to
pure paraffin, probably due to the thermo-transfer resistant created by the nano-particles agglomeration during
the melting cycle. The PCM-tube position plays a crucial role in the PCM melting rate, where the tube located
above the H2-charging pipe melts more quickly than the other tubes.

hydrogen storage technique owing to its large volume and safety,

1. Introduction
Hydrogen is seen as the clean energy of the world today [1].
Hydrogen is a secondary renewable energy produced via pyrolysis and
reforming of hydrocarbons, electrolysis, coal gasification and biomass
[1–3]. As an energy carrier, hydrogen may be used with renewable
energy sources like wind and solar [4]. Furthermore, fuel cells or in­
ternal combustion engines can easily convert hydrogen to energy or heat
[5]. So, an emphasis is now made on hydrogen energy. Hydrogen
technology, i.e. production, storage, transport and application, is an
issue of research [6]. Hydrogen storage is an essential part of the pro­
cess, but it is also the bottleneck of large-scale application [6]. It is
possible to store hydrogen in three ways: high-pressure gas-state, low-
temperature liquid-state, and chemical adsorption solid-state [7].
Among these, solid-state storage technology has emerged as a potential
particularly if metal hydride (MH) materials are used [8,9]. These ma­
terials include intermetallic compounds, magnesium-based alloys and
other metals hydriding with hydrogen. Because of its high storage ca­
pacity (wt%: 1.4%), rapid absorption kinetics, and reversible hydrogen
storage aptitude at room temperature, LaNi5 has become a typical metal
hydride alloy that has been widely studied as a potential hydrogen
storage material [10]. In addition to increasing the kinetics and cycle
stability of LaNi5, researchers also worked to reduce material costs.
According to Corre et al. [11], crushing of LaNi5 to a finer particle size
enhanced the hydrogen absorption rate. Besides, The partial replace­
ment of Ni with Al in LaNi5 improved the melting cycle and lowered the
reaction equilibrium pressure [12].
Metal hydride is often used in packed bed form (cylindrical, square,
etc.) [13]. The higher MH temperature (i.e. resulting from the
exothermic absorption) will slow the reaction rate [13]. Hydrogen

Abbreviations: Amush, Mushy zone constant; Tm, Phase change temperature, K; K, permeability, m2; ε, porosity; μ, viscosity, Pa s; τ, stress tensor, Pa; σslp, slope
factor; σhys, hysteresis factor; χ, hydrogen concentration; a, absorption; d, desorption.
* Corresponding author.
E-mail address: chibaniatef@gmail.com (A. Chibani).

https://doi.org/10.1016/j.applthermaleng.2022.118622
Received 7 September 2021; Received in revised form 18 February 2022; Accepted 3 May 2022
Available online 12 May 2022
1359-4311/© 2022 Elsevier Ltd. All rights reserved.
A. Chibani et al.
Nomenclature
− 1 − 1
CP specific heat, J⋅kg ⋅K
A,B van’t Hoff constants
C reaction rate constant, s− 1
ΔH molar enthalpy of reaction at standard conditions, J⋅mol− 1
ΔS molar entropy of reaction under standard conditions,
J⋅mol− 1⋅K− 1
E activation energy, J mol− 1
h convection heat transfer coefficient, W⋅m− 2⋅K− 1
M molar mass of hydrogen, kg.mol− 1
P hydrogen pressure, Pa
T temperature, K
t time, s
R universal gas constant, J⋅mol− 1⋅K− 1
S source term from reaction, kg⋅m− 3⋅s− 1
→u velocity in the metal bed, m⋅s− 1
V velocity, m⋅s− 1
wt maximum weight percentage of hydrogen into material, %
storage performance is seriously influenced by heat transfer character­
istics [10,14,15]. Thermal management in storage reactors has so been a
research focus. Helical coil, straight-tube and micro-channel heat ex­
changers have all been employed to discharge the reaction heat [16-21].
Adding fins to heat exchangers may also improve heat transfer in re­
actors [22,23]. However, most of these studies use heat transfer fluid
(HTF) to extract the reaction heat and give it back to the environment.
Consequently, an external heat source is needed to deliver heat for the
dehydrogenation step. This could increase the global cost of the metal
hydride storage system.
Recently, using Material Phase Change (PCM) as a heat exchanger to
absorb reaction heat in MH reactors provides an elegant solution for
effective thermal management. PCM is a type of excellent heat storage
material [24,25]. It possesses a lot of latent heat, allowing it to absorb
and retain (store) heat before desorption. Current research focuses on
the thermos-physical characteristics of PCMs and different designs of
PCM-based reactors [26–28]. Globally, most commercial PCMs used in
latent thermal energy storage units have low thermal conductivity,
which alters heat transmission from the HTF to the PCM or vice-versa
[25]. To overcome this problem, the use of highly conductive porous
material, including metal foams [29–31], and the dispersion of nano­
particles in the PCM matrix [32,33] are among the newest utilized
strategies.
Several studies integrating an MH storage system with a PCM (MH-
PCM) are available in the literature [13,27,34–40]. Even though these
studies are based on different metal hydrides, PCMs, reactor shapes/
dimensions and working conditions, they agree that integrating PCM
with a MH reactor is an efficient way to operate the MH storage system.
Garrier et al. [41] examined the combination of PCM with a magnesium
hydride storage bed experimentally. The findings indicated that
charging and discharging took three hours with a storage efficiency of
70%. Mellouli et al. [26] performed numerical research to compare the
cylindrical and spherical configurations of a metal hybrid reactor
equipped with PCM. The spherical shape was proven to be 20% quicker
than the cylindrical form in storing 80% of hydrogen. Mghari et al. [27]
discovered that integrating PCM with an MH reactor increased the time
required for hydrogenation/dehydrogenation. They determined that the
latent heat of the PCMs was more important than their thermal con­
ductivity in determining the overall system performance. On the other
hand, Nyamsi et al. [42] discovered that the thermal conductivity of the
PCM was more essential than its latent heat. LiNO3-3H2O PCM was
explored by Maad et al. [43,44] in LaNi5 MH-reactor. The authors
concluded that a reasonable storage period and capacity need an
2
Applied Thermal Engineering 213 (2022) 118622
Greek
β thermal expansion coefficient (K− 1)
µ dynamic viscosity (kg⋅m− 1⋅s− 1)
∅ volume concentration of nano-particles
ρ density (kg m− 3)
Subscripts
i initial
l liquefied phase
s solidified phase
pc phase change
np nano-particles
pcm base paraffin
npcm nano-PCM
ref reference
HTF heat transfer fluid
PCM phase change material
SENS sensible
LAT latent
appropriate melting point, thermal conductivity, and latent heat. Yao
et al. [45] performed a numerical analysis of the significant design and
operating variables, such as the absorbing pressure and the physical
characteristics of the used PCM (Na2HPO3..7H2O) for the purpose of
optimizing the performance of a LaNi5H2 MH-reactor. On the other
hand, metal foams can effectively improve the thermal conductivity of
the PCM matrix, thereby enhancing the heat absorption from the
exothermal hydriding process [39,46]. A study by Tong et al. [36]
looked at how hydrogen was released from a MH tank that is equipped
with a PCM-jacket and coiled-tube heat exchanger. The dehydriding rate
of the MH was improved with the heat transmission between the MH and
the circulating heating water in the coiled tube [36]. Ye et al. [47] built a
reactor with layered sandwich MH-PCM modules. The sandwich unit has
a quicker heat transmission and response rate than the PCM surrounding
design. The reaction heat in the PCM-based MH reactor, on the other
hand, is solely transmitted to PCM. To absorb all of the adsorption heat,
a substantial quantity of PCM is required, which considerably increases
the weight and volume of the reactor, resulting in reducing the volu­
metric and gravimetric storage capacity. Similar promising findings
have been reported by Alqahtani et al. [34] who showed that the vertical
sandwich configuration of the MH-PCM system (i.e. MH reactor encir­
cled by a cylindrical sandwich bed packed with PCM) improved the heat
transfer rate which accordingly reduced the time duration of the hy­
drogenation and dehydrogenation processes by 81.5% and 73%,
respectively, compared to a conventional MH-PCM system that includes
only a single PCM bed. Ye et al. [13] have proposed a new hydrogen
storage reactor that incorporates a concentric finned tube heat
exchanger and utilizes phase change materials (PCM) to increase heat
transfer and hydrogen storage performance. The transportation and
reaction in two reactors, with or without PCM, are analyzed using a
numerical model. Results showed that the reactor surrounded by PCM
had a quicker heat discharge and hydrogen absorption rate and a 50%
reduction in absorption time.
Although various MH-PCM reactors have been designed, there is a
noticeable lack of large-scale research. The design and modelling of
large-scale MH-PCM reactors give more insight to use PCMs as a thermal
controller in MH systems at an industrial scale, especially if the nano-
PCM technology is the researched strategy for improving the MH-PCM
system’s thermal efficiency. Based on published studies, it appears
that the nano-PCM-enhancing thermal efficiency in latent thermal en­
ergy storage units (without MH) is reliant on reactor design [48]. Khan
et al. [49] found that 1–5% of MgO in paraffin had a negligible impact
on the thermal efficiency of a lab-scale shell-and-tube PCM tank. Ebadi
A. Chibani et al. Applied Thermal Engineering 213 (2022) 118622

et al. [50] made the same findings for the cylindrical nano-PCM-tank. In
LaNi5 + 3H2 →LaNi5 H6 ΔHreaction = 30.1kJ/mol (1)
contrast, Chibani and Merouani [51] found that a rectangular nano-PCM
system significantly improved the heat exchange and the melting rate Tables 1 and 2 regroup the characteristics of the different materials
compared to pure paraffin. used in the present numerical study (paraffin, nano-oxides and LaNi5).
In this work, a two-dimensional numerical model was established to
track the heat transfer and hydrogen absorption process in a large-scale 2.1. Governing equations for PCM and nano-PCM systems
MH-PCM reactor (diameter: 1 m) with nano-oxide additives (Al2O3,
MgO, SiO2, SnO2, all at 5%), using a novel reactor geometry. To the best Commercial ANSYS Fluent 14.0 CFD software is used throughout this
of our knowledge, the MH-nano-PCM process was not assessed previ­ numerical study. Voller’s enthalpy-porosity formulation provided by the
ously, neither experimentally nor numerically (even for lab-scale pro­ software is used for simulating phase transitions. This model simplifies
cesses). Most of the existing investigation is for lab-scale MH-PCM the phase change problem by providing the following benefits: (i) the
systems (without nanomaterial). Therefore, this is the first coupling governing equation is equivalent to the equation for a unique phase, (ii)
approach in solid-state hydrogen storage with heat recovery using nano- absence of condition to meet the interface and (iii) the enthalpy
PCMs. The research findings provide further insight (and data) into the formulation declares a mixing zone between phases, permitting us to
use of nano-PCMs as a thermal regulator in big-MH storage follow the solidification/melting front easily.
constructions. →
Massconservation : ∇ .→
v =0 (2)
2. Reactor geometry and model formulation
• Momentum conservation
Fig. 1 shows the cross-section of the cylindrical MH-PCM tank
[ → ]
reactor. The reactor diameter is Ø = 1 m. It is equipped with a charging ∂ v →̅→→ → ( ) →
ρref v − ρref →
+( v ∇. v ) = − ∇ P +∇ μnp ∇.→ g (1 − β.(T − Tm ))+ S
hydrogen tube of Ø = 20 cm located at the tank center and surrounded ∂t
by four tubes (Ø = 14 cm) in which nano-PCMs are loaded. The PCM (3)
tubes form a rhombus around the H2-charging tube. The external wall of
The phase change is evaluated via the porosity model that treats the
the reactor is in aluminium (1 mm of thickness) and is maintained at
transition zone as a porous zone with a liquid percentage of 0 to 1. In Eq.
adiabatic conditions. The thermo-physical properties of the aluminum
(3), the source term is defined as:
wall of the reactor are calculated automatically by the software (Ansys-
Fluent 14.0). The hydrogen pressure supply is 50 bars. Paraffin C13-C24 → (1 − f l )2 →
is used as a PCM, it is selected due to its very narrow melting temper­ S = A→
v = − Amush 3 v (4)
f l + 0.001
ature (295.5–297.5 K) and high thermal latent heat (189,000 J/kg)
[52,53]. For the nano-PCM system, the nanomaterial oxide (each of where Amush refers to the consecutive number in the mushy region. This
Al2O3, MgO, SnO2 and SiO2) is assumed to be perfectly mixed with constant is often between 105 and 107 [48]. The approximation of
paraffin matrix with a proportion of 5% nano-oxide and 95% paraffin. Boussinesq is utilized, and Amush is taken as 105 [48].
The reactor is filled with LaNi5 in a packed bed. The H2-absorption re­
action is [13]: • Energy equations

Fig. 1. Reactor geometry with boundary conditions.

3
A. Chibani et al. Applied Thermal Engineering 213 (2022) 118622

Table 1
Properties of paraffin and nano-oxides used in the present numerical study [48,51–53].
ρ λ Tm * (K) Cp L μ
(Kg/m3) (W/m K) (J/Kg K) (J/Kg) (kg/m s)

Paraffin C13-C24 770/(0.001 × (T-297.15) + 1) 0.21 295.15–297.15 2100 189,000 0.001 × exp(− 4.25 + 1790/T)

Nanoparticle materials
Aluminium oxide (Al2O3), 20 nm 3980
Magnesium Oxide (MgO), 35 nm 3580
Silicon Oxide (SiO2), 10–20 nm 2650
Tin Oxide (SnO2), 100 nm 5560
38.493 – 778 – –
61.923 – 921 – –
11.715 – 753 – –
31.380 – 343 – –

*Melting temperature.

Table 2 (1 − ∅)ρpcm cppcm + ∅ρnp cpnp

Thermo-physical properties of hydrogen and metal hydride (LaNi5) [10,56]. Cpnpcm = (10)
ρnpcm
Parameter Value

Metal density, kg/m3 8300 (1 − ∅)ρcm Lpcm

Lnpcm = (11)
Metal specific heat, J/kg K 419 ρnpcm
Metal effective thermal conductivity of, W m− 1 K− 1
2.4
Metal porosity 0.5 (1 − ∅)ρpcm βpcm + ∅ρnp βnp
Activation energy, J mol− 1 21179.6 βnpcm = (12)
Entropy of formation, J mol− 1 K− 1 108 ρnpcm
Enthalpy of formation, J mol− 1 30,800
Reaction constant, s− 1 59.57 where Ø is the volume fraction of nano-oxides, subscripts np and pcm
Permeability of metal hydride, m2 10− 8 refer to the nanoparticle and pure PCM, respectively. The effective nano-
Specific heat of hydrogen gas, J kg− 1⋅K− 1 14890
Thermal conductivity of hydrogen, W m− 1 K− 1 0.24
PCM-thermal conductivity knpcm is calculated using [54]:
Molecular weight of hydrogen, kg kmol− 1 2.016 ( )
knp + 2kpcm − 2 kpcm − knp ∅
Density of hydrogen gas, kg m− 3 0.0838 knpcm = ( ) kpcm
Ambient temperature, K 295.15 knp + 2kpcm + kpcm − knp ∅
Initial bottle temperature, K 295.15 √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ (13)
Hydrogen dynamic viscosity, Pa s 8.411 × 10− 6 4 KB Tpcm
+ 5.10 ρpcm ∅cppcm f(T, ∅)
ρnp dnp
( )
ρ
∂hsens (T)
+ ∇.hsens (T)ρ→
( )
v = ∇ λnp ∇T − ρ
dhlat → ̅→
+ V . ∇. hlat (5) KB is the constant of Boltzmann (1.381 × 10− 23 J K− 1), dnp is the
∂t dt diameter of particles and f(T,∅) is the correction factor, is as [54]:
The sensible heat hsens(T), i.e. heat stored in the form of temperature ( ) Tnpcm
f(T, ∅) = 2.8217 × 10− 2 ∅ + 3.917 × 10− 3
increase in the liquid or the solid phase, is given as [33]: Tref (14)
( )
∫T + − 3.0669 × 10− 2 ∅ − 3.91123 × 10− 3
hsens (T) = href + CP dT (6)
Tref The effective dynamic viscosity of the nano-PCM was evaluated
based on that of the pure PCM using [55]:
href is the reference enthalpy at Tref = 273 K and Cp is the specific heat
capacity at constant pressure. The energy stored during PCM phase μnpcm = 0.983e(12.958.∅) .μpcm (15)
transition, hlat(T), is given as [33]:

hlat (T) = f(T)Â⋅ΔhS− L (7) 2.2. Governing equations for the metal hydride (MH)

where ΔHS-L is the total latent heat of the solid–liquid phase transition • General form of equations
and ‘f’ is the liquid fraction (0 ≤ f ≤ 1). f is given as [49]:
⎧ The following transport equation is used to account for heat and mass
⎪ 0T ≤ TS
⎪
⎪
⎨ transfer in the LaNi5:
T − Ts
f= Ts ≤ T ≤ Tl (8) ∂(ρϕ)
⎪
⎪ Tl − Ts + ∇.(ρuϕ) = ∇(Γ∇ϕ) + Sh (16)
⎪
⎩
1T ≥ Tl ∂t

subscripts s and l denote the PCM solid and liquid phases, respectively. • Continuity equation

• Nano-PCM thermophysical properties Continuity and Darcy equations are utilized to account for mass
transfer, such as:
The nano-PCM thermophysical properties (i.e. density ρnpcm, latent
∂ ̅→( )
heat Lnpcm, specific heat capacity Cpnpcm, and coefficient of thermal ε ρg + ∇. ερg →
v = sm (17)
expansion βnpcm) were determined using the following correlations ∂t
[51,54]: The hydrogen gas density (ρg) is obtained from the ideal gas law as:

ρnpcm = (1 − ∅)ρpcm + ∅ρnp (9) P.MH2

ρg = (18)
Rg .T

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A. Chibani et al. Applied Thermal Engineering 213 (2022) 118622

The term mass source Sm in Eq. (17) is a function of the absorption The adsorption/desorption reaction rates are given as a function of
reaction rate ddtχ and the metal porosity (ε): temperature (T), H2 pressure (P) and equilibrium pressure (Peq) as [14]:

dχ – For adsorption:
Sm = ±ρS .wt.(1 − ε) (19)
dt ( ) ( )
dχ P − Peq Ea
Sm is calculated via a UDF module linked to the reactive domain. In Eqs. = Ca . .exp − .(1 − χ) (27)
dt Peq RT
(16)–(19), P and T are the gas pressure and temperature, MH2 is the H2
molecular weight, Rg is the universal constant of ideal gases, ρs is the
solid (metal hydride) density, wt% is the metal storage capacity and χ is
the ratio of the instantaneous storage capacity of the metal (wt%) to the – For desorption:
maximum storage capacity [(wt%)max = 1.4%] (i.e. χ is denoted in the ( ) ( )
dχ P Ed
manuscript as hydrogenation efficiency). = Cd .ln .exp − .χ (28)
dt Peq Rg T
• Momentum equation
where Ca and Cd are the adsorption/desorption rate constants and Ea and
Ed is the activation energy.
Because the solid medium (MH) is porous and permeable, the
Brinkman equation has been used for momentum equation [10,56]:
• Initial and boundary conditions
ρg ∂→
u μ Sm
= − ∇p + ∇τ − → u − 2→ u + ρg →
g (20)
ε ∂t K ε The hydrogen supply pressure is 50 bars. The initial temperature of
all the system (MH-nano-PCM) is 295.15 K. At t = 0, the following initial
In the hydrogen buffer region, Eq. (20) (Navier-Stokes equation)
conditions were adopted:
with laminar flow is utilized [57]:
[
( ) 2
] P(x, y, 0) = Pi (29a)
∂u
ρ = ∇ − pI + μ ∇u + (∇u)T − μ(∇u)I + F (21)
∂t 3
ρ(x, y, 0) = ρi (29b)

• Equation of energy conservation T(x, y, 0) = Ti (29c)

Heat transfer boundary of MH and nano-PCM:
The collective energy equation for the hydride bed and hydrogen gas
is as follows [56,57]: λMH ∇TMH →
.n = λnpcm ∇Tnpcm →
.n = 0 (30)

∂T ( ) [ ]
ρCP + ∇ ρg CgP →
u T = ∇ λeff ΔT + ST (22) 3. Validation of the model
∂t

in which [56,57]: Confronting numerical and experimental outputs for the temperature
profiles inside MH-reactor tanks is a viable technique to validate models
ρCP = ε ρg CgP + (1 − ε)ρm CmP (23) treating solid-state hydrogen storage processes, either with or without
PCM-heat recovery systems [59]. The plan is to create the identical
λeff = ελg + (1 − ε)λm (24) reactor design (as the experiment) using the Gambit-Fluent® program,
λeff is the effective thermal conductivity. The change in λeff due to the inputting the same experimental parameters, but using our generated
variation in the temperature system, i.e. resulting from the exothermic/ model (that will be employed for the simulation of our large-scale nano-
endothermic character of the reaction system during the adsorption/ PCM-MH reactor). This approach is widely reported in the domain of
desorption processes, is not considered [56,57]. In fact, the change in λeff numerical modelling for energy storage processes
could not be significant due to the high density of the metal (solid phase) [10,14,51,54,55,60–69], where different validations are built on tem­
because λ of hydrogen-gas was practically unaffected by the temperature perature, liquid fraction and hydrogen pressure.
change between 20 and 40 ◦ C, which is the range of temperature vari­ In the current work, the developed mathematical model was vali­
ation during our reaction system. dated using the data of Busqué et al. [57] for H2 adsorption and that of
The source term ST in Eq. (22) is given by: Muthukumar et al. [67] for H2 desorption (both in MH-systems). In both
investigations, no PCM was used for recovery/releasing heat from/to the
ST = ±
ΔH.Sm
(25) MH-system. Busqué et al. [57] investigated, experimentally and
MH2 computationally, the hydrogen storage in a lab-scale LaNi5 cylinder.
Temperature variations at a point of coordinates r = 20 mm and z = 80
• Equilibrium pressure mm in metal-bed were obtained for natural and forced convection sing
h1 = 5 W m− 2 K− 1 (natural convection) and h2 = 10 W m− 2 K− 1 (forced
The pressure at equilibrium Peq was calculated using the following convection). Muthukumar et al. [67], on the other hand, measured the
formula, which is based on a temperature-dependent Van’t Hoff law average MmNi4.6Fe0.4-bed temperature during hydrogen desorption in a
[58]: cylindrical tank. The conditions of Busqué’s and Muthukumar’s are
( ) given in the captions of Fig. 2(a) and (b), which include both experi­
A mental and numerical findings. Our model suited the absorption data
Peq = p0 .exp − B + σslp (χ − χi ) + σhys (26)
T quite well (Fig. 2(a)), with a maximum divergence of less than 2%.
Additionally, our model predicts the actual profile with greater accuracy
where p0 is the reference pressure and χi is the initial hydrogenation across the whole charging period (10,000 s) than Busqué’s model. On
degree of the metal hydride. the other hand, although the consistency during the desorption phase is
less satisfactory (Fig. 2(b)), the simulation results often fit the experi­
• Reaction kinetics mental data well by accurately capturing the experimental trends during
hydrogen desorption cycles (500 s).

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A. Chibani et al. Applied Thermal Engineering 213 (2022) 118622

Fig. 2. Model validation with: (a) Busqué et al.

[57] absorption data for natural and forced
convective systems [conditions – MH: LaNi5, P
(pressure supply) = 0.65 atm, Tf (cooling fluid
temperature) = 297 K, Tamb = 296, Ca = 2 s− 1, Ea
= 27,200 J mol− 1, h = 5 and 10 W m− 2 K− 1], (b)
Muthukumar et al. [67] desorption data [condi­
tions – MH: MmNi4.6Fe0.4, Pd = 1 atm, Tf = 297 K,
Tamb = 310 K, Cd = 4.75 s− 1, Ea = 25,000 J mol− 1,
h = 1000 W m− 2 K− 1], (C) Al-Abidi et al. [70]
PCM-melting data [initial PCM temperature: 300
K, whereas, HTF Temperature: 363 K, HTF flow
rate was set at 8.3 L min− 1].

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A. Chibani et al. Applied Thermal Engineering 213 (2022) 118622

Moreover, we have also used Al-Abidi et al.’s [70] experimental data Table 3
to confirm our model. These researchers analyzed the average PCM Investigated cases of the MH-nano-PCM system.
temperature profile while evaluating the thermal energy storage in a Case System
PCM-based system (without MH). Fig. 2(c) compares our model findings
1. Tube 1 + paraffin pure
with those of Abidi et al. [70]. The description of Abidi et al.’s [70] 2. Tube 2 + paraffin pure
system is provided in the caption of Fig. 2. As seen in Fig. 2(c), our model 3. Tube 3 + paraffin pure
perfectly matched the experimental melting data of Abidi et al. [70], 4. Tube 4 + paraffin pure
with more accuracy than the authors-model itself. 5. Tube 1 + nano-PCM, 5%
6. Tube 2 + nano-PCM, 5%
As a result, our constructed model may be deemed accurate for 7. Tube 3 + nano-PCM, 5%
analyzing energy storage operations, whether for metal hydride pro­ 8. Tube 4 + nano-PCM, 5%
cesses (H2 charging/discharging) or for PCM-based heat recovery/ 9. MH-nano-PCM reactor
release in latent thermal systems.

(d) show the average temperature versus time profiles (for up 20,000 s)
4. Results and discussion
of the MH-bed and the nano-PCM systems in the fourth tubes are shown
for the nine cases illustrated in Table 3. We note that cases 1–4 in Table 3
4.1. Heat and mass transfer in the MH-system
denote tubes 1–4 filled with pure paraffin, cases 5–8 indicate tubes 1–4
filled with nano-PCM (5% for each nano-oxide), whereas case 9 repre­
The initial temperature of the block system is 295.15 K, the paraffin
sents the MH-nano-PCM system. Fig. 4 shows the MH-hydrogenation
in the tubes is in solid-state at this temperature (its melting temperature
kinetics for cases 1–8 of Table 3.
is 295.15–297.15 K). The hydrogen pressure supply is 50 bars. Fig. 3(a)–

(a) : Al2O3 (b) : MgO

(c) : SiO2 (d) : SnO2

Fig. 3. Temperature profiles (over time) in the MH-bed (case 9) and the nano-PCM tubes for different nono-oxides (cases 1 to 4 denote pure paraffin in tubes 1–4 and
cases 5–8 denote the nano-PCM (with 5% of each oxide) in tubes 1–4.

7
A. Chibani et al.
Fig. 4. Kinetics of the average MH-hydrogenation degree for the different
nano-PCM matrices (5% of each nano oxide material). Pure indicates
pure paraffin.
In all situations of Fig. 3(a)–(d), a sudden increase in the bed tem­
perature is recorded due to the transient heat resealed from the rapid
exothermal hydrogen absorption in the MH-active sites. The MH-bed
temperature increased to 329.15 K within ~550 s (34 K of increase)
and then slowdowns progressively. The MH-temperature pic (of Fig. 3
(a)–(d)) is simultaneously accompanied by a rapid hydriding yield
(hydrogenation rate), where the complete hydrogenation of the MH-
block is achieved at around the pic temperature (550 s), as shown in
Fig. 4. The two rapid processes of temperature rise and MH-
hydrogenation are mainly due to the huge applied supplying pressure
(50 bar) as well as the adopted large-scale configuration. The same
behavior has been reported in [71] for lab-scale LaNi5-MH reservoir at
higher applied pressure (10 bar). It should be noted that the same sce­
nario has also been retrieved in [10] for a large-scale MH-reactor with an
HTF (heat transfer fluid) system. However, in our MH-PCM system, the
reactor cooling is ensured in a significant part by the PCM through
absorbing the released heat from the absorption process. Besides, the
excess of H2 gas (filling the porous media) of the MH contribute also to
the cooling process of the bed reactor. In fact, after the complete hy­
drogenation of the MH (achieved at about the MH-pic temperature,
~550 s, as shown in Fig. 4), the absorption process could be stopped, the
excess of H2 feeding the reactor (which has an initial temperature of
295.15 K and 50 bar of supplying pressure) turning its role to a
convective cooling system of the heated MH-bed. It should be noted that
the thermal equilibrium of the MH-system could not be achieved even at
20,000 s of operating time. Note also that the MH-bed temperature as
well as the MH-hydrogenation profiles (Fig. 4) were practically unaf­
fected by the type of the nano-oxide metal of the Nano-PCM filling the
tubes 1–4, as shown in Figs. 3(a)–(d) and 4, which is ascribed to the huge
surface occupied by the MH (0.692 m2) as compared to that reserved for
the nano PCM tubes (0.0615 m2). Therefore, the high surface ratio SMH/
Stubes = 11.24 causes less impact of the nano-PCM system on the overall
MH-hydrogenation and temperature evolutions. More interestingly, the
heat transfer (heat recovery) in the PCM systems is generally slow and
required a large time to occur, mainly due to the lower conductivity of
these systems, as illustrated in our previous investigations [48,51]. At
this level, it is also worthy to note that the influence of the pure-PCM
system (in tubes) on both the kinetics of MH-hydrogenation and its
thermal behavior is close to that of the nano-PCM. This has been
8
Applied Thermal Engineering 213 (2022) 118622
Fig. 5. Energy evolution of the MH-bed system for the different nano-PCM
matrices (5% for each nana oxide material). Pure indicates pure paraffin.
confirmed by the kinetical evolution of the MH-energy (Fig. 5) by using
pure-PCM or different nano-PCM matrices. As shown in Fig. 5, no effect
of the different PCM matrices is revealed during the MH-charging cycle
(0–500 s), whereas a little effect (unappreciable) is remarked after a long
operating time (>10,000 s). The energy profiles followed the early re­
ported temperature profiles (Fig. 3): a sudden increase to − 6.2661 × 07
J kg− 1 during the charging time (500 s) of MH, followed by a progressive
decrease after the pic point, 500 s (e.g. − 6.297 × 107 J kg− 1 at 8000 s).
For more explanation of the MH-system’s mass and heat transfer
results, the velocity contours versus time are established for the different
MH-nano-PCM systems (Fig. 6). The time points (100, 500 and 3600 s)
of Fig. 6 were selected to cover the whole period of the H2 charging cycle
(~550 s), Fig. 4. Depending on charging time, the Reynolds number for
the flow is Re = 210–2737. This interval was calculated from the Rey­
nolds contours (data not shown). A huge rate of hydrogen (~21.6 m s− 1)
is located around the charging tube of hydrogen at the initial stage of the
filling (100 s), as seen from Fig. 4. This remark is for all the nano- (and
pure) PCM systems. The H2 flux is oriented toward the bed inner while
its velocity decreases with going up in the bed bulk. The velocity at the
wall of the PCM tubes is null. At 500 s, the zone of H2 diffusion is
extended but the rate is significantly decreased to 2.97 m s− 1 (maximum
rate), practically due to the filling of the porous media (with non-
adsorbed gas) due to the saturation of active sites for hydrogen
adsorption (the charging point or full saturation time is 550 s, Fig. 4). As
the time goes up to 1 h, the saturation of bed-block sites is ultimately
reached; the gas velocity is shallow (~0.6–0.8 m s− 1) and explicitly
located around the central pipe of hydrogen supply. It is noticed from all
contours (of all the systems of Fig. 6) that, at 3600 s, the velocity vectors
are turned up from the upper part of the bed to the H2-tube, while some
amount of H2 continues to be diffused in the bottom part of the H2-tube.
This was ascribed to the massive compression of the H2 gas after the
LaNi5 hydriding, which causes an inability to receive more gas in the
upper part of the reactor. Also, it is worth mentioning that the same
orders of magnitude were recorded for the velocity distribution, either
the presence or absence of nano-oxides in the PCM (Fig. 6).
4.2. Heat transfer and melting analysis in the nano-PCM systems
Fig. 7(a)–(d) show the evolution of the average melting kinetics (for
20,000 s) of paraffin in the different nano-PCM tubes (tubes 1–4) under
A. Chibani et al. Applied Thermal Engineering 213 (2022) 118622

Time t = 100 s t = 500 s t = 3600

Pure
PCM

Al2O3
5%

MgO
5%

SiO2
5%

SnO2
5%

Fig. 6. Evolutions as function time of the velocity contours in the MH-nano-PCM systems.

the various scenarios at which the average temperature profiles of Fig. 3
(a)–(d) were established. The time to achieve the maximum melting
percentage is reported in Fig. 8 for cases 1–8 of Table 3.
Firstly, according to Figs. 3(a)–(d) and 7(a)–(d), the tube position
dramatically influences the melting process and its thermal behavior
resulting from the heat lost from the exothermal absorption of hydrogen
in the MH. Due to the symmetry in position between tube 1 and tube 3,
the same comportment (with the same value) is shown either for the
thermal or the melting processes (Figs. 3(a)–(d) and 7(a)–(d)). Tube 4,
located at the bottom of the reactor, showed the lowest performance;
however, tube 2 reveals the best heat recovery and melting rate per­
formance. The difference in thermal and melting performance between
tube 2 and tube 4 (located in the same vertical), is mainly ascribed to the
gravitational force effect. For analyzing the different scenarios, it is
better to divide the issue in two ways: the pure PCM system and the
nano-PCM one, and analysis will be conducted as a function of the po­
sitions of the tubes.
The PCM melts progressively over time for the pure paraffin (case
1–4), as seen in Fig. 7(a)–(d). A 50% of the initial PCM is melted at 3200
s for tubes 1 and 3 (cases 1 and 3) and 4500 s for tube 4 (case 4).

9
A. Chibani et al. Applied Thermal Engineering 213 (2022) 118622

(a) : Al2O3 (b) : MgO

(c) : SiO2 (d) : SnO2

Fig. 7. Variation, versus time, of the average PCM-liquid fraction (f) in the different nano-PCM tubes [Cases 1–4: pure paraffin in tubes 1, 2, 3 and 4. Cases 5–8: nano-
PCMs (5% of each nano-oxide) in tubes 1, 2, 3, and 4, respectively].

Pure Al O MgO SiO SnO

25000
90%

90%

72%
88%

93%

93%

75%
90%

85%

73%

70%
78%
82%

100%
100%

20000
Time (s)

15000
100%

100%
100%

100%
100%

10000

5000

0
Tube 1 Tube 2 Tube 3 Tube 4

Fig. 8. Time to achieve the maximum melting percentage, under different scenarios.

10
A. Chibani et al.
However, 100% of melt was reached rapidly in tube 2 (case 2, 8600 s),
against 18,000 s for tubes 1 and 3 and >20,000 s for tube 4 (case 4, only
77% was reached at 20,000 s), as obtained from Figs. 7 and 8. Therefore,
the melting rate increased in the order of tube 2 > tubes 1 and 3 > tube
4. This order is the same obtained for the PCM-temperature evolution in
the fourth tubes, as shown in Fig. 3(a)–(d). For example at t = 5000 s, the
average PCM temperature varied as 298.5 K in tubes 1 and 3 (case 1 and
3 of Fig. 3(a)–(d)), 301 K in tube 2 (case 2) and 296.5 K in tube 4 (case
4). The PCMs temperature made a plateau after 5000 K (at the above
mentioned temperatures) except for the case of tube 2 (case 2), where
the PCM temperature increased drastically and crosses the MH tem­
perature at about t = 9000 s (Fig. 3(a)–(d)). Above this instance, the
PCM temperature of case 2 continues its increase up to 320 K at 15,000 s
(the MH-temperature herein is 306 K). Ye et al. [13] have reported the
same intersection trend for lab-scale LaNi5-PCM-HTF reactor. This trend
is mainly attributed to the geometrical design (size and tubes position)
Time t = 500 s t=1h
PURE
Al2O3
5%
MgO
5%
SiO2
5%
SnO2
5%
Fig. 9. Evolutions as function of time (500 s, 1 h, 4 h and 5 h) of the temperature contours in the MH-nano-PCM system for the fourth nano-oxide materials.
11
Applied Thermal Engineering 213 (2022) 118622
of the adopted reactor, which affects the thermal energy localization in
the bed reactor, as it will be discussed in Section 4.3.
For the nano-PCM systems (cases 6–8), the average melting rates
(Fig. 7(a)–(d)) and PCM-temperatures (Fig. 3(a)–(d)) in the fourth tubes
are less than those discussed above for the pure paraffin, and this
statement is maintained for the fourth nano-oxides exanimated (Al2O3,
MgO, SiO2 and SnO2). Besides, it seems that there is no significant effect
of the type of the nanoparticles on the melting process of the paraffin,
which is following the results recently published by Chibani et al. [48]
for a large scale nano-PCM energy storage unit, using the same nano-
oxides used in our study. Fig. 8 clearly states the issue where nearly
similar times were found for achieving the maximum melting efficiency
(whatever the type of the nano-oxide). This trend is primarily due to the
low load of the nano-oxides (5%) in the PCM mass, which could not
affect the mean thermal conductivity of the nano-PCM matrix appre­
ciably. This last is the controlling factor of the heat transfer (mainly by
t=4h t=5h
A. Chibani et al.
conduction) and, therefore, the melting rate process. It should be noted
here that utilizing particles in concentrations >5% is not preferred due
to (i) the losing weight of PCM heat storage volume [72] and (ii) the vital
loss of heat exchange owing to the increased viscosity of the mixture
[73]. The cluster formed by the nano-particles agglomeration consti­
tutes a thermo-transfer resistance, thereby limiting thermal transfer in
PCM mass.
According to Fig. 7(a)–(d), melting efficiencies of 55% for cases 5
and 7, 63% for case 6 and 48% for case 8 were calculated at t = 5000 s,
showing reductions of 15%, 10% and 7.7% in the melting efficiency (i.e.
compared to pure paraffin) in tubes 1 (and 3), 2 and 4, respectively.
Correspondingly, the time of complete melting increased from 8500 s
(case 2) to 9500 s (case 6), whereas after 20 000 s, the nano-PCM system
reduced the melting degrees to 88% for cases 5 and 7 (instead of 100%
for case 1 and 3) and 73% for case 8 (instead of 78% for case 4). Overall,
depending on the PCM-tube position, the reduction between 5% and
15% in the melting performance is caused by adding nanomaterials.
Similarly, Mahdi and Nsofor [54] reported an insignificant impact of
Alumina particles addition on RT82 melting in a triplex-tube thermal
energy storage unit. The same trend is found by Sheikholeslami et al.
[74] on heat transfer during the solidification process in a PCM energy
storage system with 4% of nanomaterial. Chibani et al. [48] have
concluded that the enhancing/reducing impact of particles addition
depends on the reactor geometry and design, and for big-scale con­
structions, the nano-PCM approach may impact positively the heat
transfer and the melting performance only at the initial stage of the
process; however, for a large operation time, the performance of the
latent thermal energy storage could be reduced, due to the agglomera­
tion of the nanomaterial mass which increases the viscosity of the PCM
phase, thereby altering the heat dissipation from the HTF to the PCM.
Using 5% of each used nanoparticles in our configuration did not
enhance the melting process performance. However, the heat released
from the H2-absorption has been effectively recovered by using either
the pure PCM or the nano-PCM strategies.
4.3. Temperature distribution in the MH-nano-PCM reactor
For better clarifying the thermal comportment in the different parts
of the MH-nano-PCM rector (of Fig. 1), the temperature contours in the
entire system have been done in Fig. 9 for an applied supplying H2-
pressure of 50 bar. These contours were done for t = 500 s (time of
reactor filling) and t = 1, 4 and 5 h (charging times of the PCM). Upon
hydrogen adsorption, metal hydride emits heat to all tubes, whether
pure or including nanoparticles, and the temperature of the PCM layer
progressively rises. The latent heat absorbed during the phase change
process is crucial in the reaction process. The red and blue regions in
Fig. 9 represent the significantly heated and cooled regions, respec­
tively. The metal hydride transforms into a hydrogen storage alloy, the
solid density rises and the PCM transforms from a solid to a liquid. From
Fig. 9, the MH-temperature at t = 500 s is almost maximal (the pic
temperature of Fig. 1), 330 K, the PCM melting percentage at this instant
is ~5% for each tube, either in the presence or absence of nanoparticles
(Fig. 7(a)–(d)). The minor degree of melting is due to the lower thermal
conductivity of the paraffin, which could not allow recovering rapidly
the heat released from the MH. At t = 1 h, PCM tubes started to recu­
perate heat accumulated around the tubes and stocked it as latent heat.
The PCMs temperature is around 297 K. The PCM-fusion begins from the
inner layer of the PCM just adjacent to the heated external wall of the
tubes; however, the thermal energy recovery is strongly sensitive to each
tube position. The same heat flow distribution is observed for tubes 1
and 3 situated symmetrically; however, heat flux around tubes 2 and 4
(situated at the same vertical) is different. Higher thermal flux is located
around tube 2 against tube 4; nevertheless, the melting efficiency is
similar (at this instance, 1 h) for all tubes and under the different nano-
PCM cases (case 1–8 of Table 3). As the time goes to 4 h, the tube po­
sition effect is observed. While tube 2 is entirely surrounded by a high
12
Applied Thermal Engineering 213 (2022) 118622
thermal region, tubes 1–3 is encircled by two regions, a heated one (in
the right hand of tubes 1 and 3 and the bottom hand of tube 4) and a cold
one at the left hand of tubes 1 and 3 and the top hand of tube 4. At t = 1
h, the upper part of the MH-block reserves the highest temperature,
contrary to the lower part, where the MH heat is rapidly lost. As the
thermal condition is the main transfer mode in the MH, it is more
probably that the heat was easily transported from the bottom to the top
rather than the inverse. Additionally, it should not forget that this heat
will not be recuperated only by the PCM tubes, but the filling pipe of H2
could also be an outer of this heat. Therefore, based on the heat transfer
orientation approach (bottom to top), tube 4 will not retain a significant
part of the MH-heat as the major part around this tube could be evac­
uated from its upper-side to the H2-pipe; the trend which could not
happen in the case of tube 2. The scenario of tube 4 is presumably the
same for tubes 1 and 3, but with the least extent, as the relatively higher
melting rate reflected it in these tubes compared to tube 4 (please see
Fig. 7(a)–(d)). So, the only exception is tube 2, which could be sur­
rounded by a higher thermal layer even for an extended time, as shown
in contours registered at t = 5 h in Fig. 9. Since the melting temperature
of the PCM is in the interval 297.15–295.15 K, its complete melting in
this tube could be achieved rapidly (~2.3 h, as obtained in Fig. 7(a)–
(d)). Above this time, the liquid PCM stores the thermal energy as sen­
sible instead of latent; therefore, the liquid PCM temperature could be
increased as receiving heat from the top side of the MH reactor. This
scenario could justify the up-normal temperature profile retrieved for
case 2 in Fig. 3(a)–(d). However, this up-normal temperature profile is
found only for the pure paraffin case (case 2). In fact, the nano-PCM
temperature rest constant even after the complete melting for all
nano-PCM cases. This is due to the nano-PCM system’s high viscosity,
which could create a thermo-transfer resistant phase, thereby quenching
heat dissipation in the PCM matrix. The important heat surrounding
tube 2 in this case (case 6 of Fig. 3(a)–(d)) was evacuated by the H2-
fitting pipe as clearly stated in contours of Fig. 9 for all nano-oxides cases
after t = 1 h.
5. Conclusion
A numerical analysis has been conducted to study, for the first, the
performances of heat recovery from the exothermic adsorption of
hydrogen by using a nano-PCM strategy in a large-scale MH-PCM energy
storage reactor. Even though some researchers reported that the nano-
PCM strategy (isolated of MH) could be an improved strategy for ther­
mal energy storage in latent thermal units via increasing the thermal
conductivity of the PCM matrix, the present study showed that the issue
is not the same for a large scale process, where the reactor shape and
design can importantly alter the heat transfer in the nano-PCM mass. No
significant impact of the different nano-oxides additions at 5% is
revealed, meaning that the nano-PCM strategy is not an effective tool for
the process enhancement in large MH-PCM systems. However, the
melting process strongly depends on the position of the PCM tube (vis-
à-vis the H2-filling pipe). For all investigated cases (different pure and
nano-PCMs), the upper part of the reactor reserved higher thermal en­
ergy than its bottom. Therefore, during the heat recuperation period, the
PCM tubes at the upper part of the reactor could be exposed to higher
thermal flux, accelerating their thermal storage performances (melting
rate). This phenomenon was ascribed to the heat transfer orientation
within the MH-bed, which is from the bottom to the top, in addition to
the significant contribution of the H2-filling pipe in the heat receiving
after the complete fitting of the MH with hydrogen.
Finally, this work can be considered a base for hydrogen storage in a
large-scale metal hydride reactor, even though an economic assessment
of the PCM-nano samples is required to optimize the process cost. In
future projects, hydrogen storage (and destocking) in/from the reactor
configuration of Fig. 1 will be optimized in operational conditions and
MH thermos-physical characteristics (i.e. porosity, permeability, ther­
mal conductivity, etc.).
A. Chibani et al. Applied Thermal Engineering 213 (2022) 118622

Declaration of Competing Interest reactor, Energy 173 (2019) 443–456, https://doi.org/10.1016/j.

energy.2019.02.033.
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The authors declare that they have no known competing financial performance simulation of the spiral mini-channel reactor during H2 absorption,
interests or personal relationships that could have appeared to influence Int. J. Hydrogen Energy. 40 (2015) 13490–13505, https://doi.org/10.1016/j.
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