Available online at www.sciencedirect.

com

ScienceDirect
Solar Energy 131 (2016) 260–274
www.elsevier.com/locate/solener

Review

Experimental and numerical investigation of potential filler

materials for thermal oil thermocline storage
H. Grirate a,b, H. Agalit a, N. Zari a,⇑, A. Elmchaouri b, S. Molina c, R. Couturier c
a
Moroccan Foundation for Advanced Science Innovation and Research MAScIR, Avenue Mohamed El Jazouli, Rabat, Morocco
b
Faculty of Science and Technology, Laboratory of Physical Chemistry and Bioorganic Chemistry, Mohammedia, Morocco
c
CEA LITEN, National Institute of Solar Energy, Storage Systems Laboratory, Grenoble, France

Received 21 August 2015; received in revised form 25 January 2016; accepted 17 February 2016

Communicated by: Associate Editor José González-Aguilar

Abstract

A thermal energy storage system (TES) is a key technology to ensure continuous power supply from solar thermal power plants.
Choosing the appropriate storage method and the suitable material for energy storage remains a major challenge in research and devel-
opment in the solar power field. The sensible heat storage in solid media using thermocline system is a significant cost-effective option
when compared to liquid storage material in two tank system. An incorporation of this potential concept is the oil/rock thermocline
system which is based on the direct contact between natural rocks chosen as filler material and thermal oil as the heat transfer fluid
(HTF), and it is used in the Concentrated Solar Power (CSP) plants.
The present paper highlights the thermal energy storage potential of six rocks (quartzite, basalt, granite, hornfels, cipolin and marble)
proposed as filler material for thermal oil thermocline storage concept. These rocks were chosen according to their abundance in Mor-
occo. Different technical methods were performed in order to assess the rocks properties (physical, chemical and thermal) at temperatures
up to 350 °C (temperature operating conditions using linear Fresnel reflectors or parabolic trough). The thermal performances of the
studied rocks inside a thermocline storage system were evaluated using a validated numerical model. Based on the experimental inves-
tigation two rocks (Quartzite and Cipolin) were identified as the most suitable filler materials to be used in direct contact with the studied
HTF (synthetic oil). While, the numerical analysis revealed that Basalt rock has the best thermal performances inside the studied ther-
mocline storage system concept, but it isn’t chemically compatible with synthetic oil. Hence, it can be used advantageously with other
heat transfer medium (e.g. Air).
Ó 2016 Elsevier Ltd. All rights reserved.

Keywords: TES; CSP; Storage materials; Rocks; Thermocline

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
2. Experimentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
2.1. Material storage description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
2.2. Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264

⇑ Corresponding author.
E-mail address: n.zari@mascir.com (N. Zari).

http://dx.doi.org/10.1016/j.solener.2016.02.035
0038-092X/Ó 2016 Elsevier Ltd. All rights reserved.
 H. Grirate et al. / Solar Energy 131 (2016) 260–274 261

Nomenclature

k thermal conductivity (W/m K) V volume (m3)

U porosity (%) z axial coordinate (m)
qr rock density (g/cm3) U overall heat transfer coefficient (W/m2 K)
qb bulk density (g/cm3) t time (s)
Vr pure rock volume (m3) T temperature (K) or (°C)
Vb bulk rock volume (m3)
A surface area (m2) Acronyms
Cp specific heat capacity of oil at constant pressure CSP Concentrated Solar Power
(J/kg K) TES thermal energy storage
Cs specific heat capacity of the rock (J/kg K) HTF heat transfer fluid
C circumference of tank (m) TGA thermogravimetric analysis
D rock diameter (m) DSC Differential Scanning Calorimetry
hv volumetric convective heat transfer coefficient XRF X-ray Fluorescence Spectrometry
(W/m3 K) HCl hydrochloric acid
e void fraction (–) L.I Loss Ignition
v interstitial fluid velocity (m/s)

2.3. Analytical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265

3. Results and discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
3.1. Petrographic study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
3.2. Physical performances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
3.3. Chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
3.4. Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
3.4.1. Mass loss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
3.4.2. Thermal capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
3.4.3. Thermal conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
3.5. Performance analysis of rocks thermocline energy storage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272

1. Introduction
In a world increasingly subject to limits on carbon emis-
sions, solar energy technologies represent one of the clean-
est ways to produce electricity. Life cycle assessments
(LCA) have shown that solar energy has a reduced carbon
footprint compared to fossil fuels (Rhone, 2007). In fact,
concentrating solar power (CSP) is one of the most promis-
ing solar energy technologies for reduction of electric sector
greenhouse gas (GHG) emissions and for rapid capacity
expansion (Heath et al., 2009). CSP can be combined with
thermal energy storage (TES) systems which provides the
ability to dispatch energy after sunset or during intermit-
tent cloudy weather conditions (Relloso and Garcı́a,
2015). Furthermore, TES is widely recognized as the most
practical way to integrate renewable energies into the elec-
tricity production mix on the generation side (Fernandes
et al., 2012; van der Linden, 2006). Comparing with other
renewable energy technologies such as wind and photo-
voltaic (PV). TES allows an advantageous process opti-
mization in CSP power plant by offering an interface
between the solar field and the power block. The capability
of providing dispatchable energy, extending the generation
time beyond sunset and avoiding fluctuations associated
with the intermittent solar rays. This allows correcting
the mismatch between energy demand and supply.
Developing a high-temperature heat storage technology
depends on the properties of the heat storage medium and
the process design. TES systems are classified into three
types: sensible, latent and thermochemical (Dincer and
Dost, 1996). Today, molten salt is the most widely used
storage material in large-scale CSP systems, while systems
with latent heat, thermochemical, and other sensible heat
materials are still under development (Kuravi et al.,
2013). In addition to the storage media, there are different
methods to store energy. Nowadays, The two-tank storage
system using molten salt as the storage material is the only
one commercially applied in many CSP plants, including
the 19.9 MW Gemasolar power tower plant in Spain, the
Andasol (1–3) parabolic trough power plants (50 MW per
plant) in Spain, and the 280 MW Solana parabolic trough
power plant in America (Xu et al., 2012a, 2012b). How-
262 H. Grirate et al. / Solar Energy 131 (2016) 260–274
ever, the two storage tanks system are constructed from
stainless steel which is immune to the molten salt corrosion
(Strasser and Selvam, 2014), therefore, they have a rela-
tively high capital cost and very limited space for cost
reduction. These issues make it hardly to meet the require-
ments of significantly lowering the levelized cost of electric-
ity (LCOE) of CSP (Wu et al., 2014).
In order to reduce the cost of the TES section, the two-
tank configuration can be substituted by a single tank ther-
mocline system. The concept is based on hot and cold tem-
perature regions superposed in a single tank. A portion of
the medium is at high temperature and a portion is at low
temperature, separated by a temperature gradient called
thermocline. Compared to the two-tank configuration,
the single tank TES system can save up to 35% of invest-
ment cost (Gil et al., 2010; Kearney et al., 2004). Pacheco
et al. tested a small pilot-scale (2.3 MW h) thermocline
indirect storage system and reported that cost was about
2/3 of the cost in a two-tank molten salt system for CSP
power plants (Pacheco et al., 2002). Nonetheless, the tem-
perature stratification in a thermocline tank is hard to
reach if the used material storage is only HTF, due to the
fluid thermal convection. Thus, other materials can be used
to maintain the stratification in the tank. It can also
enhance the thermocline effect and at the same time dis-
place higher-cost liquid since most of the expensive storage
fluid can be replaced by a low cost filling solid material
(Brosseau et al., 2005; Gil et al., 2010). Concerning the
environmental impacts, Heath et al. (2009) compared the
LCA of different systems: two tank, indirect molten salt
and indirect thermocline. This study focused on estimating
the emissions embodied in the production of the materials
used in the TES system. They deduced that the embodied
emissions of GHG for the thermocline system are less than
half of those for the two tanks. Another study conducted
by Oró et al. (2012), using the LCA methodology to com-
pare three types of TES systems, showed that the system
based on solid media presents the lowest environmental
impact per kW h stored. By contrast to the liquid media
(molten salts) which shown the highest impact per kW h
stored, because it needs complex equipment and more
material.
The solid materials that can be used for high tempera-
ture heat storage are metals, sand, bricks, rocks, concrete
and ceramic (Hasnain, 1998). After the test performed at
the Almeria Solar Platform Center in Southern Spain, CIE-
MAT and DLR reported that the castable ceramic and
concrete are characterized by higher strength and easier
handling (Laing et al., 2006). Nevertheless, the use of these
materials requires heat exchanger pipes between the heat
transfer fluid (HTF) and the storage material which
increases the investment cost (Libby, 2010). Furthermore,
the separation between the HTF and the TES material
through the tube interface leads to poor heat transfers
characteristics. As an alternative to concrete, natural rocks
can be chosen as solid filler materials and can be used
directly in contact with the HTF. Rocks are considered
as earth-abundant materials, non-flammable and act both
as heat transfer surface and storage medium (Singh et al.,
2010). However, they are not all suitable for high tempera-
ture storage. The compatibility between the HTF and the
material storage remains always as an important factor
to ensure a chemically stable TES system (Allen, 2010).
The approach of thermocline system using rocks as mate-
rial storage and the thermal oil as HTF is not new at all.
It was installed at the historic Solar One pilot (170 MW ht)
plant in Daggett, CA (1982–1988). Solar One used a water-
steam receiver and an oil-rock thermocline storage system
with heat exchanger between the steam and the oil. Rocks
were used in order to reduce the price of the plant, as the
oil is more expensive than rocks, Caloria HT-43 costs
$530/ton versus granite, which cost $70/ton (Laurent,
2000). Solar Two has substituted molten salt as the HTF
instead of water-steam and also molten salt as the storage
medium instead of the mineral oil in order to reduce cost
by avoiding heat exchangers and also insuring more effi-
ciency (Laurent, 2000). Caloria HT-43 reaches only 310 °
C which decreases the efficiency and revealed a chemical
degradation in direct contact with rocks (Gordon, 2013;
Laurent, 2000). Ever since, the most studies focused on
the compatibility between rocks and molten salt used as
HTF. Pacheco et al. demonstrated that silica sand, quart-
zite rock, and taconite were compatible with molten salt
used as HTF (Pacheco et al., 2002). Other studies have
evaluated the charge/discharge performance of molten salt
thermocline thermal energy storage (Angelini et al., 2014;
Bayón et al., 2014; Gil et al., 2010; Pacheco et al., 2002;
Yang and Garimella, 2010) and demonstrated that the
quartzite rock and silica sand are able to withstand the
molten salt environment quite well. Indeed, direct contact
between HTF and rock must be evaluated to improve the
performance of the thermocline TES system. In recent
years, several HTF have been proposed. Molten salt has
received more attention because of its many advantages
(Blake et al., 2002), such as large heat capacity and high
working temperatures (450–500 °C) (Kearney et al.,
2004). Also, it has dual function of heat storage medium
and heat transfer fluid. However, molten salt with high
freezing point presents a major inconvenience that leads
to complications related to freeze protection in the solar
field (Brosseau et al., 2005). Air is also proposed as HTF
because it is non-degradable and free. However, its density
is low at high temperatures, which influence its volumetric
flow (become very high) and may require significant pump-
ing power compared to the energy produced (Allen, 2010).
In many plants, the synthetic oil Therminol VP1 is the ear-
liest and most widely used HTF. This fluid may reach a
high temperature of about 393 °C and offers a low freezing
point (<12 °C) which prevents the pipes clogging during
the solar plant operation. However, Therminol VP1 exhi-
bits a high vapor pressure at elevated temperatures,
approximately 10 bar at 390 °C because of its low boiling
point (257 °C) (Justin and David, 2012). These gases lead
to significant heat losses in the receiver tubes. For this pur-
 H. Grirate et al. / Solar Energy 131 (2016) 260–274 263

Table 1
Specifications of studied rocks.
Rocks Type Porosity (%) Density Isobaric specific heat Conductivity Thermal capacity
(kg m
3 at 20 °C) capacity (J kg
1 K
1 at 20 °C) (W/m K at 25 °C) (kJ m
3 K
1)
Quartzite (Qtz) Metamorphic 0.40–0.65 2510–2860 700–1000 7. 7 3822
Granite (Grt) Igneous 0–1 2530–2690 600–1200 2.2 1440–2880
Marble (Mar) Metamorphic 0.65–0.81 2610–2670 1470 2.9 1680–2520
Basalt (Blt) Igneous 0.22–22.1 2210–2770 800–900 2 1750–2500
Hornfels (Hor) Metamorphic 0.8–2.5 2400–2800 700–900 1.5 2560–2880
Cipolin (Cip) Metamorphic 0.6–0.8 2610–2870 800–1470 3.2 1680–2520

pose and as an alternative organic HTF, commercial for-
mulations based on terphenyl-derived aromatics with high
boiling points (359 °C) were proposed by several industri-
als. The hydrogenated terphenyl is one of the suggested
fluids.
With the aim of selecting the right energy storage mate-
rial, Ismail and Stuginsky Jr. (1999) presented a detailed
report on the effects of various parameters influencing the
sensible heat storage performance. They concluded that
the relevant thermo-physical properties of storage material
are thermal capacity, thermal conductivity and particle
size. The density and the specific heat capacity affect the
thermal behavior of the packed bed storage material caus-
ing a greater storage capacity and increasing the rate of
charging (Aly and El-Sharkawy, 1990). In addition to the
parameters discussed above, the porosity, the hardness,
the mineralogy and the chemical composition are consid-
ered as decisive criteria to choose the best rock which will
be in direct contact with the synthetic oil used as HTF.
Screening studies on candidate filler materials showed that
quartzite rock and silica sand were tested using air as HTF
(Audi, 1992; Fricker, 1991; Waked, 1986; Zanganeh et al.,
2012). There are few experimental results which highlight
the performance of rocks to be used in contact with the
thermal oil since the last experience carried out by Sandia
National Laboratories (FAAS, 1982).
The purpose of this work is to carry out the thermal and
physical characterization of six varieties of rocks (quartzite,
basalt, granite, hornfels, cipolin and marble) selected
according to their abundance in the Moroccan geological
heritage, and which could be used as filler materials in ther-
mal energy storage. Thus, the study focused on comparing
material storage (rocks) properties. The efficiency of the
chosen storage materials is accomplished through the
numerical investigation performed in a thermocline storage
system using synthetic oil as HTF.
2. Experimentation
2.1. Material storage description
Morocco is distinguished by a rich geological heritage in
many ways: various geological structures, diversified land-
scapes, varied rocks, mineral associations, remnants of
oceanic crust among the oldest ones in the world (800my)
(Elhadi and Tahiri, 2012).
The rock specimens used in this study are recognized as
a variety of rocks available profusely in Morocco (Elhadi
and Tahiri, 2012) and especially in the most relevant CSP
expected lands in the country (ONE, 2009). They are con-
sidered to be the best in terms of strength and resistance.
According to the literature, some of these rocks (metamor-
phic rocks) are issued from the contact metamorphism
occurring as a result of a high geothermal gradient: the
rocks are produced locally around the intruding magma.
Others (igneous) are originally igneous rocks, formed
through the cooling and solidification of magma (Allen
et al., 2014; Audi, 1992; Dupin, 2009). The specifications
of studied rocks given in the literature are summarized in
Table 1 (Gokhale, 2010; Jaeger, 1979; Schumann, 2002).
The map below shows where potentially the suitable
rocks are found extensively and sampled (Fig. 1).

Table 2
Results of macroscopic examination of the varieties of rocks studied.
Rocks Macroscopic description Hardness Test HCl
Qtz Massive rock, locally heterogeneous and micro cracked. It has a light gray to yellow color and Very high Very low
presents also iron oxide and fine grain to invisible
Grt Massive rock with gray, clear color and rough surface. Grains are joined and present an average size High Very low
between 1 and 4 mm
Mar Massive and compact rock with pinkish gray color. Average grain size from 1 to 2 mm. It presents Low to Medium
a meshed appearance and bright surface medium
Blt Massive and homogeneous rock with a black to dark green color. This rock presents a few vacuoles, Medium to Very low
very fine grained and shiny and sometimes oriented high
Hor Massive and heterogeneous rock with green color and cornel appearance. Some visible crystals appear Medium Very low
on a very fine-grained and glossy background
Cip Massive and compact rock with a gray to greenish color. The grains are joined and very intertwined Very high Very low
264 H. Grirate et al. / Solar Energy 131 (2016) 260–274

Fig. 1. Location of rocks sampled on the map of Morocco.

2.2. Sample preparation
For a suitable sample preparation, the macroscopic
sample identification of raw materials was performed.
The examination was made on the basis of visible criteria
(shape, color, grain size. . .). Then, the rocks hardness was
determined according to the Mohs scale which classifies
mineral hardness ranging from the softest (talc; N°1) to
the hardest mineral (diamond, N°10). The test of
hydrochloric acid (10–20% w/v) was performed in order
to distinguish carbonate rocks of clay minerals, gypsum
and siliceous. The carbonate minerals (Calcite or Dolo-
mite) will react to release the carbon dioxide gas which
appears as bubbles (Sicree, 2012).
The reaction is shown below:
CaCO3 þ 2HCl ! CO2 þ H2 O þ Caþþ þ 2Cl


The sample preparation depends on the type of study
that will be conducted. The thin sections are studied under
the light microscope to identify the rocks texture and the
mineral arrangement. Sections with a thickness ranging
from 1 mm and 3 mm were used for the thermal conductiv-
ity measurement. Its preparation starts with cutting a chip
from the rock specimen, impregnation, lapping, grinding,
and then bonding with glass slide. At the last step, the lap-
ping and polishing are done when required.
The cubes (3  3 cm) were prepared from large blocks
using the diamond saw. This operation was performed in
order to identify the rocks physical features.
To carry out thermal and chemical studies, the large
blocks were crushed to reduce the sample size and the
grains were finely ground using a crusher with tungsten
beads in order to obtain a very fine powder in the range
of particle diameter situated between 15 nm and 25 nm.
 H. Grirate et al. / Solar Energy 131 (2016) 260–274 265

Fig. 2. Microphotographs of the selected rocks. (A: Granite, B: Basalt, C: Quartzite, D: Marble, E: Hornfels, F: Cipolin).

2.3. Analytical methods
The polarizing microscope was used for the thin sec-
tions petrographic characterization. Major minerals, tex-
tural and structural characteristics (microblastic,
granoblastic. . .) were determined. The test of physical
properties was carried out on the saw-cut specimens
according to ASTM C373-88 (2006). The X-Ray Fluo-
rescence Spectrometry (XRF) was applied to determine
the geochemistry of samples. The thermogravimetric
analysis (TGA instrument model Q 500) was used to
define their weight losses at high temperature and the
Modulated Differential Scanning Calorimetry (MDSC
instrument model Q 100) was performed to measure
the specific heat capacity (Cp) of the selected rocks.
These measurements were made by varying the tempera-
ture in the range from 25 °C to 300 °C under a N2 flow
of 60 ml/min (O2 of 10 ml/min for TGA) and a heating
rate at 10 °C/min. Samples mass was kept between 10
and 20 mg. Finally the laser flash method (LFA 447
NanoFlash) was used to determine the thermal conduc-
tivity. The samples were prepared and adjusted accord-
ing to the sample carrier (squares perfectly flats with
1 mm < thick < 3 mm and sides of 25 mm). Indeed, the
laser flash method is used to measure the thermal diffu-
sivity of the material. The thermal conductivity is then
calculated automatically by entering the specific heat
capacity and the density of the material.

Fig. 3. Physical properties measurements.

266 H. Grirate et al. / Solar Energy 131 (2016) 260–274

Table 3
Geochemistry of rocks studied given in weight percentage (%).
SiO2 Al2O3 CaO Fe2O3 MgO Na2O TiO2 MnO2 P2O5 K2O L.I
Qtz 94.50 1.0 0.3 0.5 0.3 0.7 – 0.6 – 1.3 0.8
Grt 69.74 14.30 1.71 4.05 0.82 3.18 0.62 0.06 0.13 4.74 0.87
Mar 0.76 1.10 54.75 0.4 – – – – – – 43.05
Blt 47.27 17.46 13.39 10.92 1.83 3.08 2.12 0.28 0.25 1.02 0.37
Hor 65 22.4 0.12 5.24 0.59 1.64 0.36 - 0.17 1.76 2.50
Cip 52.5 20.5 14 5.63 2.93 2.85 0.50 0.34 0.20 0.05 0.13

Each analysis was conducted three times on different mass (M) and the bulk rock volume (Vb) including the vol-
samples for checking the result reproducibility. ume of all cavities in the rock. Then, the porosity U can be
calculated from rock and bulk density as follows:
3. Results and discussions

M
qr
qb Vr

VMb ðV b
V r Þ
U¼ ¼ M ¼ ð1Þ
3.1. Petrographic study qr Vr
Vb

The petrographic study is subdivided into two main
parts: macroscopic and microscopic observation. The main
macroscopic features of the studied samples are reported in
Table 2. According to the macroscopic description, it
appears that all rocks have a solid appearance excluding
marble, which present a low to medium hardness. This
characteristic can lead to an early degradation. On the
other side, the cipolin and the quartzite present very high
hardness with very low carbonate content (HCl test,
Sicree, 2012).
In addition to the sample macroscopic observation,
Fig. 2 shows their microscopic description according to
the texture and constituent minerals.
On the basis of microscopic observation, it is noted that
hornfels and granite are composed of hydrothermal miner-
als (muscovite and biotite), which can deteriorate at high
temperature. This theory is thereafter proved by the ther-
mogravimetric analysis. Basalt shows a massive structure.
However, it contains a fine and dark grain that can affect
the HTF causing its deterioration.
In general, the petrographic study shows that the poros-
ity of rocks is not significant (the minerals show a welded
aspect). The exact value of the porosity will be reported
in the next part (porosity measurement). Indeed, if the
porosity is important, the impregnation of the oil in the
rocks porosity will precipitate their deterioration.
The quartzite and cipolin revealed a cemented aspect, a
compact structure and high hardness. Quartzite is com-
posed mostly of quartz which is known by its high thermal
conductivity (7 W/m K).
3.2. Physical performances
The measurements of density, porosity and water
absorption are summarized in terms of their mean values
in Fig. 3 According to (Vosteen and Schellschmidt, 2003),
rocks density (qr) is defined as the ratio of the dry rock
mass (M) and the pure rock volume (Vr) excluding cavities.
By contrast, bulk density (qb) is the ratio of the dry rock
In the present work, density was determined for all
rocks samples. Porosity and water absorption were calcu-
lated according to Eq. (1)and ASTM C373-88. In fact,
there are different types of porosity: connected porosity,
total porosity and open porosity (Chaki et al., 2008). In
this part, the open porosity available on rock surface was
measured. It should be pointed out that open porosity
can also report the cracks of the rock. This theory was
proved by a study of rocks thermal damage which was per-
formed by Chaki et al. (2008). The study revealed that open
porosity increases with temperature and the microscopic
examination showed some cracks appearing on the surface
of the samples.
The results obtained show that the porosity varies for
the studied rock samples from 0.2% to 1.2% given by a vol-
umetric % (Fig. 3). They also show a low water absorption
(0.1% and 0.4%, given by a weight %), and thus, the oil
penetration is prevented. In addition, they present a high
density (2.7 and 3 g/cm3) that will increase the thermal
capacity of the energy storage according to the work of
Aly and Sharkawy which aims to study the effects of stor-
age media properties (Aly and El-Sharkawy, 1990).
3.3. Chemical composition
Table 3 shows the average contents of major oxides ele-
ments in samples. These analyses were carried out to high-
light the presence of the elements precursors of corrosion.
The results obtained reveal that the majority of rocks are
distinguished by a predominantly alumina–silicate compo-
sition, with alumina content up to 22% and iron content of
about 5%. The quartzite shows an important content in
SiO2. This improves the mineralogy of quartz deducted
from a thin section of quartzite. It is also noticed that
basalt presents a high amount of iron oxide of about
10% which is confirmed by the literature (Guezal et al.,
2011). Accordingly, the iron can be combined with hydro-
xyl element, causing the decomposition of the HTF. On the
other hand, chemical composition of marble shows a high
 H. Grirate et al. / Solar Energy 131 (2016) 260–274 267

Fig. 4. Thermogravimetric analysis curves.

quantity of CaO of about 54% and also a striking percent-
age of combustion elements (loss on ignition (L.I)
= 43.05%) that lead to exhaust emissions. This feature
causes an increase in pressure inside the thermal energy
storage tank leading to severe damage.
Through this study it is demonstrated that quartzite
contains a very large amount of silica, which is known by
its high thermal conductivity. Basalte and marble present
an unfavorable potential to be used as filler material for
TES in direct contact with thermal oil.
3.4. Thermal properties
The thermal properties of rocks depend generally upon
their structure, mineral composition, porosity, density,
temperature and pressure.
268
4000
-1
Volumetric heat capacity KJ m K
3800
3
3600
3400
3200
3000
2800
2600
2400
2200
2000
0 50 100
Temperature (°C)
Fig. 5. Thermal capacity of rocks at high temperature.
3.4.1. Mass loss
TGA analysis demonstrates that granite and marble
(quantities in mg) shows a weight loss at high temperature
of about 3.3% and 2.9% respectively as seen in Fig. 4.
Granite has lost water from its hydrated minerals, intersti-
tial pore spaces or water trapped within its crystalline
structure. It should be stressed that granite has revealed
low porosity and high hardness. In this case, water lost is
not derived from water trapped in the rock. It’s due to
the decomposition of hydrated minerals ((muscovite and
biotite), observed in the petrographic study). These miner-
als are composed from hydroxyl bonds that brake at high
temperatures. This result is in accordance with a study con-
ducted to choose a suitable rock for thermal energy storage
(Allen et al., 2014). Ignous, sedimentary and metamorphic
rocks (dolorite, weathered and unweathered granite, sand-
stone and hornfels) were tested in thermal cycling (950
cycles) between average temperatures of 350 °C and 500–
530 °C, at rates of 2 °C/min. Both types of granite (frag-
ments about 10 cm of length) have shown significant disin-
tegration (29% of mass loss), which validate the result
obtained by the thermogravimetric analysis.
Considering the marble composition (carbonate mate-
rial with calcite as dominant mineral), the loss observed
is due to the fragmentation of organic material causing
the carbon dioxide (CO2) exhaust. The fragmented mole-
cules ejected from the calcite mineral are presented in Eq.
(2):
CaCO3 ðsÞ ! CaOðsÞ þ CO2 ðgÞ
Other samples which are not impaired by the variation of
the temperature (25–400 °C) are primarily silicates (quartz,
feldspars, and dehydrated material). Reported to Homand-
Etienne and Troalen (1984), granite and marble, which is
originally limestone, have shown serious thermal cracking
when heated above 150–200 °C. Consequently, the granite
and marble are not compatible for high temperature energy
storage.
H. Grirate et al. / Solar Energy 131 (2016) 260–274
quartzite
8
granite
Thermal conductivity (W/m K)
marble
basalte
hornfels
6
cipolin
4
quartzite
granite
marble
basalte 2
hornfels
cipolin
150 200 250 300 0
0 50 100 150 200 250
Temperature (°C)
Fig. 6. Thermal conductivity of the studied rocks.
3.4.2. Thermal capacity
After the thermogravimetric analyzes previously con-
ducted, it is interesting to analyze the volumetric heat
capacity (q  Cp) which is considered as an important
parameter to assess the energy storage material. The volu-
metric heat capacity is the product of density q and specific
heat capacity Cp. Cp was determined in the temperature
range between 20 and 300 °C for each rock sample using
a dynamic differential heat flow calorimeter (DSC). The
volumetric heat capacity was calculated using the Cp
obtained from the DSC as a function of the temperature.
The density was determined previously at the ambient tem-
perature, it should be noted that the density of a solid
material changes only slightly with changing in tempera-
ture (Fauduet, 2011). Hence, the values of the rocks density
were used to calculate the volumetric heat capacity of each
rock. Fig. 5 shows the results obtained for the studied rocks
at temperatures up to 300 °C. The thermal capacity of
rocks increases with increasing temperature and it ranges
from 2.2 MJ m
3 K
1 to 3.8 MJ m
3 K
1, Basalt and cipo-
lin present the highest values. The results achieved are
slightly different (deviation: 0.1–0.7 at 20 °C) from those
obtained by Waples and Waples (2004). Indeed, the varia-
tions of the measured heat capacities between rock types or
within the same type are influenced by the mineral compo-
sition, structure, texture and saturation with water which
all depend on the sampling area (Hanley and Dewitt,
1978). Therefore, the measurements given in this section
should be considered as representative values as long three
ð2Þ samples of each type of rocks was tested. The standard
deviation for all measurements is situated between
0.01 J g
1 K
1 and 0.05 J g
1 K
1, which seems to be
caused by heterogeneity of rock samples. Thus, the average
values are presented.
Özkahraman et al. (2004) suggest that the thermal
capacity of the rocks must be greater than 1 MJ m
3 K
1
for thermal storage applications. Thus, all rocks tested
are considered as competitive material storage since the
average volume specific heat capacity is greater than
 H. Grirate et al. / Solar Energy 131 (2016) 260–274
2 MJ m
3 K
1 and similar to molten salt (3 MJ m
3 K
1)
which is currently the most advantaged storage material
(Gil et al., 2010).
3.4.3. Thermal conductivity
During the discharge phase, the rocks may transfer
energy stored during daytime to the HTF. Therefore, the
knowledge of the thermal transport properties is required
to choose the best filler material for TES system. In the
presence of all environmental conditions like fluid satura-
tion, it is difficult to make an exact measurement of thermal
conductivity of rocks (Hussain et al., 2012). Indeed, the
conductivity depends on various factors for any given rock
type (Clauser et al., 1995) such as the natural variation of
rock’s mineral content as well as to several physical and
diagenetic factors. For many volcanic and plutonic rocks
(Clauser et al., 1995; Hussain et al., 2012), the thermal con-
ductivity is isotropic. In contrast, the thermal conductivity
of sedimentary and metamorphic rocks is strongly
anisotropic.
In order to have an expected reproducibility criteria, the
measurements of the thermal conductivity were performed
using the two structural arrangements of the rock (speci-
mens with thickness 1 mm). Because of the sample thick-
ness is the only parameter involved, the laser-flash is highly
precise, with a 3% nominal error (Hofmeister, 2006). The
results obtained are presented in Fig. 6 with the standard
deviation of 0.003–0.079 W/mK, this is due the heterogene-
ity of the studied materials.
At ambient temperature, the thermal conductivities val-
ues of rocks are ranging from 1.5 W/mK to 6.3 W/mK and
vary inversely with temperature. These results are in accor-
dance with the literature (Troschke and Burkhardt, 1998)
in which rocks thermal conductivities are ranging from
0.5 W/mK to 5 W/mK depending on the rock type.
In fact, the thermal conductivity of rocks with pure
quartz (siliceous composition) can reach 7.5 W/mK
(Clauser et al., 1995; Özkahraman et al., 2004). By referring
to the FX analysis, hornfels, quartzite and granite have the
highest silica content, so they should present the higher
thermal conductivities. This theory has been verified exper-
imentally (Fig. 6).
Otherwise, the best material storage should have the
highest thermal conductivity in order to easily transfer
the energy. When the thermal conductivity is low, the sys-
tem storage charging and discharging becomes slower
(Allen, 2010). However, Hänchen et al. have studied the
thermocline system performance of four different materials
(rock, steatite, steel and aluminum) which differ signifi-
cantly in their thermal conductivities (0.48 W/m K,
2.5 W/m K, 50 W/m K, 204 W/m K respectively)
(Hänchen et al., 2011). It has been concluded that both
rock and aluminum revealed slightly higher overall efficien-
cies compared to steatite and steel (Hänchen et al., 2011).
Thus, the thermal conductivity has a minor influence as
long as rock and aluminum have shown the extreme values
269
of the thermal conductivity (0.48 W/m K and 204 W/m K
respectively).
The most relevant property to ensure high efficiency
energy storage is the volumetric heat capacity (Hänchen
et al., 2011). In the next part, the performance of the ther-
mocline energy storage will be studied based on the param-
eters measured experimentally to choose the suitable rock
for energy storage.
3.5. Performance analysis of rocks thermocline energy
storage
In order to assess the thermal performance of the stud-
ied rocks when they are used as filler materials in the Ther-
mocline storage system, a simulation tool was developed in
Matlab R2011b based on the previously validated model of
(Bruch et al., 2014). A brief description of the model is
given in this paper; and more details about the physical
correlations used within this work are given in (Bruch
et al., 2014), and about the computational procedure
(Agalit et al., 2015).
The main performance indicators equations are listed
below:
The maximal stored energy: indicates the maximal theo-
retical capacity of the TES tank, if we consider that it is
fully charged i.e. T = TCharging in every point in TES tank.
It is given by the following Eq. (3):
 
Emax
Stored ¼ qs;T mean ð1
eÞVcs;T mean T charging
T ambient
 
þ qf ;T mean eVcf ;T mean T charging
T ambient ð3Þ
The values of qs, cs, qf, cf, Tmean is the mean value of the
working temperatures range, and it is equal to 175 °C.
The stored energy at each instant (t) is given by the fol-
lowing Eq. (4):
8t 2 ½t0 ; tmax  EtStored
(
X N h

¼ ADz qs cs;T mean ð1
eÞ T ts;n
T ref
n¼1

i
þqf ;T mean cf ;T mean e T tf ;n
T ref
X
N h


ADz qs cs;T mean ð1
eÞ T ts;n
0

T ref
n¼1

io
þqf ;T mean cf ;T mean e T tf0;n
T ref ð4Þ
where N is the number of subdivision done through the
flow axis, and Dz = H/N is the spatial increment. A is the
cross section area.
During the charging cycle the nest input energy to TES
tank is calculated at each time step using the following
Eq. (5):
270 H. Grirate et al. / Solar Energy 131 (2016) 260–274

400 During the discharging cycle the recovered energy at

each time is calculated using the following Eq. (7):
380
X
t

Fluid temperature (°C)

8t 2 ½t0 ;tmax  EtRecovered ¼ _ f ;T mean T tf ;1
T ref Dt

mc
360 j¼t0

X
t

340
_ f ;T mean T tf ;N þ1
T ref Dt ð7Þ
mc
j¼t0
Exp t= 0
Exp t= 30 mn

320 Exp t= 1h
Exp t= 1h30mn The discharging efficiency is given by the following
Exp t= 2h
M t= 0
M t= 30 mn
Eq. (8):
300 M t= 1h
M t= 1h30mn EtRecovered
Disch
M t= 2h gDischarging ¼ tDisch ð8Þ
0 1 2 3 4 5 6
EStored þ EtPump;Discharging
Disch

Height (m) where tDisch is the duration of the discharging cycle.

The overall efficiency of each cycle (Charging/
Fig. 7. Comparison of the simulation tool results with experimental data
Discharging) is calculated using the following Eq. (9):
from Pacheco et al. (2002). Exp: Experimental results, and M: Modeling
results. gOverall ¼ gCharging gDischarging ð9Þ

Table 4
The wall losses at each time step is calculated using the
Dimensions of this pilot scale storage tank STONE and the following Eq. (10):
operation parameters used in the simulation study. 8t 2 ½t0 ; tmax  EtwallLoss
Geometry t X
X N
Tank height (m) 3 ¼ U wall;T mean CDzðT fj;n
T 1 Þ ð10Þ
Tank radius (m) 0.5
j¼t0 n¼1
Rock diameter (m) 0.03
where Uwall,Tmean is the global heat transfer coefficient of
Operation parameters
tCharging (h) 3
wall losses, and it is calculated at the Tmean using the cor-
TCharging (°C) 250 relation given in Bruch et al. (2014).
tDischarging (h) 3 The capacity ratio indicates to which extent the maximal
TDischarging (°C) 100 theoretical storage capacity of the TES has been exploited,
m_ (kg/h) 1000 and it is calculated using the following Eq. (11):
Void fraction 0.27
EtStored
8t 2 ½t0 ; tmax  r¼ ð11Þ
Emax
Stored
8t 2 ½t0 ; tmax  EtNetInput ¼ EtInput
EtOutflow
The governing energy conservation equations are Eqs.
X t
 (12) and (13):
j
¼ _
mDtc f ;T mean T f ;0
T ref For the fluid phase:
j¼t0
 
X
t
 @T f @T f @2T f
j eAqf cp;f þv ¼ Ahv ðT s
T f Þ þ k f A 2

_
mDtc f ;T mean T f ;N
T reef ð5Þ @t @z @z
t¼t0
þ U wall CðT 1
T f Þ ð12Þ
where Dt is the time increment, and m_ is the mass flow rate.
The charging cycle efficiency is calculated using the fol- For the solid phase:
lowing Eq. (6): @T s @2T s
ð1
eÞAqs cs ¼ Ahv ðT s
T f Þ þ k s;eff A 2 ð13Þ
EtStored
Ch
@t @z
gCharging ¼ tCh ð6Þ
ENetInput þ EtPump;charging
Ch
The developed simulation tool was validated using the
experimental data of Pacheco et al. (2002). The experiment
where tCh is the duration of the charging cycle.
consists of 2 h discharging process of a storage tank which
Table 5
Experimentally measured thermophysical properties of the six candidate rocks evaluated at the average temperature of 175 °C.
Rocks Density (kg/m3) Thermal conductivity (W/m K) Heat capacity (J/kg K) Thermal capacity q  Cp (MJ/m3 K)
Qtz 2570 3.5 1185 3
Grt 2820 3.1 1105 3.1
Mar 2680 2.2 1128 3
Blt 3020 2.2 1193 3.6
Hor 2740 5.2 1040 2.8
Cip 2800 1.6 1136 3.1
 H. Grirate et al. / Solar Energy 131 (2016) 260–274 271

has been previously charged by the same duration. Dimen-

1700
1800 (a)
sions, operating conditions, and thermophysical properties

1540
1510
1480

1470
1600

1400
of the fluid and the filler material were taken from Van
Lew et al. (2011). As shown in Fig. 7, the temperature pro- 1400

files generated by the simulation tool match the experimen-

Energy (MJ)
1200
tal recorded data. 1000

8753
874

8597
8534
8480

859
8488
853
848

848

8308
88

830

86
86
86

85

84
Using the developed simulation tool, the six candidates
800
natural rocks, namely: quartzite, granite, marble, basalte,
hornfels, and cipolin, were compared as filler material of 600

the storage tank ‘‘STONE” (Bruch et al., 2014). This stor- 400
age system uses thermal oil as a heat transfer fluid and rocks 200
as storage material. Dimensions of the pilot scale storage
0
tank ‘‘STONE” and the operation parameters used in the Quartzite Granite Marble Basalte Hornfels Cipolin
simulation study are listed in Table 4. In the scope of the Maximal storage capacity Recovered energy
simulation tool, the six rocks differ with respect to density, Net input energy Stored energy
thermal conductivity, and heat capacity. These thermo-
physical properties were experimentally measured in the 200

6
temperature range (25–300 °C). The results were presented (b)

18
180

9
8

16
16
5
in previous sections and evaluated by interpolation at the

16

2
16

8
15
160
average temperature of operation (175 °C), see Table 5.
140
Fig. 8 shows the temperature distribution of the filler
material across the storage height at the end of charging 120

98 9

,9

,9
98 8
98 7
98 5

99 9
,8
,7
,5

97 9
0

0
,9
and discharging periods of the 5th cycle for the six candi-

,
,
,
,

,
10

10

10

10

99
98

99
98
98
98

99
97
100
date rocks of Table 5. 80
It has been found that the temperature profiles depend

59
57

57
60

56

55
51
mainly on the thermal capacity of rocks, with hornfels tem-
40
perature profile being the furthest advanced in the storage
tank during the charging phase. 20
Fig. 9 shows the performance indicators of the studied 0
rocks. It has been observed that all calculated parameters Quartzite Granite Marble Basalte Hornfels Cipolin

are classified with regard to the thermal capacity of rocks. Capacity ratio (%) Charging efficiency (%)
Overall efficiency (%) Discharging efficiency (%)
Indeed, the rocks with the highest thermal capacity Outflow temperature of discharge (°C)
(basalte > cipolin > granite > quartzite > marble > horn-
fels) have the lowest capacity ratio (i.e. stored energy/stor- 10000
age capacity). These results show an under-utilization of (c)
00

00

00

00

00
90
85

85

85

85

85
84

the tank storage capacity under the given operating condi-

8000
tions. Hence, the unexploited storage volume can be
Energy (kJ)

6000
260
98
40 59
58

40 47

4 0 35
95

44
44
44

quartzite
44

44
95
43

63
52
42

41

04
40
40

40

240 granite 4000

marble
Fluid temperature (°C)

220
basalte 2000
200 hornfels

cipolin
180 0
Quartzite Granite Marble Basalte Hornfels Cipolin
160 Overall Wall losses Charging wall losses
Discharging wall losses
140
Fig. 9. (a–c) Performance parameters for the six storage rocks.
120

100 reduced and the related cost can be economized by adapt-

0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 ing the operating conditions.
Height (m) The hornfels storage presents thermal loss fraction
Fig. 8. Temperature distributions of the filler material across the storage
(overall wall losses/net input energy) slightly higher than
height at the end of the 5th charging and discharging periods for the six the other rocks, but it didn’t exceed 1% of the input energy.
candidate rocks. The discharging efficiency approaches 100% in all cases, so
272 H. Grirate et al. / Solar Energy 131 (2016) 260–274
the overall and charging efficiencies are equal throughout
the cyclic process. The latter discussed parameter is almost
equal for all rocks except hornfels overall efficiency, which
is lower by 1% due to thermal losses. The outflow temper-
ature of discharging is equal to 158 °C in the case of horn-
fels and reaches 168 °C with basalt. Thus, rocks with high
volumetric heat capacity deliver energy with a high temper-
ature for a longer time during discharging.
Finally, all results discussed show that the volumetric
heat capacity is the most determining factor for the thermal
performances of the TES system. Consequently, basalte
remains the most potential storage material.
4. Conclusion
In the present paper, different experimental and numer-
ical methods have been implemented to quantify petro-
graphic, physicochemical, thermal properties and
thermocline performances of rocks selected as a good can-
didate for thermal energy storage in the temperature range
between 250 °C and 350 °C.
Firstly, the petrographic and geochemical studies were
performed in order to determine the mineralogy, structural
aspects and composition of the studied rocks. The result
obtained shows that quartzite contains a significant percent-
age of quartz which is characterized by a high thermal con-
ductivity of about 7.7 W/m K. Thin sections have shown a
massive structure with joined crystals in all rocks. This fea-
ture will prevent the oil infiltration into the rock surface as
they will be in direct contact. Furthermore, physical studies
have been demonstrated that all rocks present a high density
(2570 kg/m3 and 3020 kg/m3) and a low porosity (0.2% and
1.2%).
Thermal analysis showed more pronounced weight loss
in the case of granite and marble. This is due to water evap-
oration derived from hydrothermal minerals (biotite) pre-
sent in granite and CO2 exhaust from carbonate rock in
particular marble. The exhaust gas will produce pressure
increases in the storage tank. DSC analysis showed that
basalte possesses the highest specific heat capacity which
has been approved by the numerical investigation; the ther-
mal conductivity of rocks has only a minor effect, whereas
the volumetric heat capacity is considered as the most rele-
vant property of the storage material. Thus, basalte remains
as the best material storage for CSP power. However, this
rock contains a large amount of mafic minerals, which
allows to triggering corrosion phenomena in direct contact
with the thermal oil. Hence, it can be used advantageously
with other heat transfer medium (e.g. Air). Otherwise, the
hardness evaluation showed that cipolin and quartzite have
a very high hardness compared to the other rocks. Hornfels,
basalt, granite and marble are removed from the proposed
list of potential filler material in order to avoid any damage
during storage unit operations.
Based on the results obtained, it has been demonstrated
that cipolin and quartzite are the good candidates to be
used as materials energy storage in direct contact with
thermal oil. Other studies have proven that quartzite
behaves well as energy storage material (Agalit et al.,
2015; Brosseau et al., 2005; Zanganeh et al., 2012). Some
additional work is needed at the laboratory scale for testing
chemical interaction that can occur during direct contact
between the materials chosen and the HTF.
Acknowledgement
We express our thanks to all members of the laboratory
team MAScIR for their help to use the analytical tech-
niques and especially Soumia MAZZI.
References
Agalit, H., Zari, N., Maalmi, M., Maaroufi, M., 2015. Numerical
investigations of high temperature packed bed TES systems used in
hybrid solar tower power plants. Sol. Energy 122, 603–616. http://dx.
doi.org/10.1016/j.solener.2015.09.032.
Allen, K.G., 2010. Performance Characteristics of Packed Bed Thermal
Energy Storage for Solar Thermal Power Plants. University of
Stellenbosch.
Allen, K.G., von Backström, T.W., Kröger, D.G., Kisters, a.F.M., 2014.
Rock bed storage for solar thermal power plants: Rock characteristics,
suitability, and availability. Sol. Energy Mater. Sol. Cells 126, 170–
183. http://dx.doi.org/10.1016/j.solmat.2014.03.030.
Aly, S.L., El-Sharkawy, a.I., 1990. Effect of storage medium on thermal
properties of packed beds. Heat Recover. Syst. CHP 10, 509–517.
http://dx.doi.org/10.1016/0890-4332(90)90201-T.
Angelini, G., Lucchini, A., Manzolini, G., 2014. Comparison of thermo-
cline molten salt storage performances to commercial two-tank
configuration. Energy Proc. 49, 694–704. http://dx.doi.org/10.1016/
j.egypro.2014.03.075.
Audi, M.S., 1992. Experimental study of a solar space heating model using
Jordanian rocks for storage. Energy Convers. Manag. 33, 833–842.
http://dx.doi.org/10.1016/0196-8904(92)90011-K.
Bayón, R., Rivas, E., Rojas, E., 2014. Study of thermocline tank
performance in dynamic processes and stand-by periods with an
analytical function. Energy Proc. 49, 725–734. http://dx.doi.org/
10.1016/j.egypro.2014.03.078.
Blake, D.M., Jane, M., Price, H., Kearney, D., Herrmann, U., 2002. New
heat transfer and storage fluids for parabolic trough solar thermal
electric plants, pp. 4–8.
Brosseau, D., Kelton, J.W., Ray, D., Edgar, M., Chisman, K., Emms, B.,
2005. Testing of thermocline filler materials and molten-salt heat
transfer fluids for thermal energy storage systems in parabolic trough
power plants. J. Sol. Energy Eng. 127, 109. http://dx.doi.org/10.1115/
1.1824107.
Bruch, A., Fourmigué, J.F., Couturier, R., 2014. Experimental and
numerical investigation of a pilot-scale thermal oil packed bed thermal
storage system for CSP power plant. Sol. Energy 105, 116–125. http://
dx.doi.org/10.1016/j.solener.2014.03.019.
Chaki, S., Takarli, M., Agbodjan, W.P., 2008. Influence of thermal
damage on physical properties of a granite rock: porosity, permeability
and ultrasonic wave evolutions. Constr. Build. Mater. 22, 1456–1461.
http://dx.doi.org/10.1016/j.conbuildmat.2007.04.002.
Clauser, C. et al., 1995. Thermal Conductivity of Rocks and Minerals.
Rock Physics and Phase Relations. American Geophysical Union,
Hannover, Germany, pp. 105–125.
Dincer, I., Dost, S., 1996. A perspective on thermal energy storage
systems for solar energy applications. Int. J. Energy Res. 20, 547–557.
http://dx.doi.org/10.1002/(SICI)1099-114X(199606)20:6<547::AID-
ER173>3.0.CO;2-S.
Dupin M, T.P., 2009. L’origine des cornéennes et des schistes tachetés,
Geology course, Sciences de la Vie et de la Terre, Académie CAEN.
 H. Grirate et al. / Solar Energy 131 (2016) 260–274
Elhadi, H., Tahiri, A., 2012. Geological heritage of Morocco. In:
Conference on Techniques for Nuclear and Conventional Analysis
and Applications, Morocco, p. 130.
FAAS, S.E., 1982. 10-MWe Solar Thermal Central Receiver Pilote Plant,
Report, Systems Evaluation Division, Sandia National Laboratories,
Livermore.
Fauduet, H., 2011. Mécanique des fluides et des solides appliquée à la
chimie. Lavoisier, Paris, France.
Fernandes, D., Pitié, F., Cáceres, G., Baeyens, J., 2012. Thermal energy
storage: ‘‘How previous findings determine current research priorities”.
Energy 39, 246–257. http://dx.doi.org/10.1016/j.energy.2012.01.024.
Fricker, H.W., 1991. High-temperature heat storage using natural rock.
Sol. Energy Mater. 24, 249–254. http://dx.doi.org/10.1016/0165-1633
(91)90065-S.
Gil, A., Medrano, M., Martorell, I., Lázaro, A., Dolado, P., Zalba, B.,
Cabeza, L.F., 2010. State of the art on high temperature thermal
energy storage for power generation. Part 1—Concepts, materials and
modellization. Renew. Sustain. Energy Rev. 14, 31–55. http://dx.doi.
org/10.1016/j.rser.2009.07.035.
Gokhale, B.V., 2010. Rotary Drilling and Blasting in Large Surface
Mines. CRC Press.
Gordon, J.M., 2013. Solar Energy: The State of the Art. Routledge.
Guezal, J., Baghdadi, M.E.L., Barakat, A., Rais, J., 2011. Le magmatisme
jurassique-crétacé de Béni-Mellal (Haut-Atlas central, Maroc): géo-
chimie et signification géodynamique. Bulletin Institut Scientifique,
Rabat, Science de la Terre. 33, 17–23.
Hänchen, M., Brückner, S., Steinfeld, A., 2011. High-temperature thermal
storage using a packed bed of rocks – heat transfer analysis and
experimental validation. Appl. Therm. Eng. 31, 1798–1806. http://dx.
doi.org/10.1016/j.applthermaleng.2010.10.034.
Hanley, E.J., Dewitt, D.P.R.F.R., 1978. The thermal diffusivity of eight
well-characterized rocks for the temperature range 300–1000 K. Eng.
Geol. 12, 31–47.
Hasnain, S.M., 1998. Review on sustainable thermal energy storage
technologies, Part I: heat storage materials and techniques. Energy
Convers. Manag. 39, 1127–1138. http://dx.doi.org/10.1016/S0196-
8904(98)00025-9.
Heath, G., Turchi, C., Decker, T., Burkhardt, J., Kutscher, C., 2009. Life
cycle assessment of thermal energy storage: two-tank indirect and
thermocline. In: ASME 2009 3rd Int. Conf. Energy Sustain, vol. 2, pp.
689–690. http://dx.doi.org/10.1115/ES2009-90402.
Hofmeister, A.M., 2006. Thermal diffusivity of garnets at high temper-
ature. Phys. Chem. Miner. 33, 45–62. http://dx.doi.org/10.1007/
s00269-005-0056-8.
Homand-Etienne, F., Troalen, J.-P., 1984. Behaviour of granites and
limestones subjected to slow and homogeneous temperature changes.
Eng. Geol. 20, 219–233. http://dx.doi.org/10.1016/0013-7952(84)
90002-4.
Hussain, S., Saneen, S., Ahmad, N., Javeed, M.A., Ali, S., 2012.
Calculation of thermal conductivity of diorite rocks and their
modeling. Int. J. Basic Appl. Sci. 12, 111–123.
Ismail, K.A.R., Stuginsky Jr., R., 1999. A parametric study on possible
fixed bed models for pcm and sensible heat storage. Appl. Therm. Eng.
19, 757–788. http://dx.doi.org/10.1016/S1359-4311(98)00081-7.
Jaeger, C., 1979. Physical and mechanical properties of rock material. In:
Rock Mechanics and Engineering. Cambridge University Press, pp.
35–84.
Justin, R., David, P., 2012. Inorganic salt heat transfer fluid.
US20140166924.
Kearney, D., Kelly, B., Herrmann, U., Cable, R., Pacheco, J., 2004.
Engineering aspects of a molten salt heat transfer fluid in a trough
solar field. Energy 29, 861–870. http://dx.doi.org/10.1016/S0360-5442
(03)00191-9.
Kuravi, S., Trahan, J., Goswami, D.Y., Rahman, M.M., Stefanakos, E.
K., 2013. Thermal energy storage technologies and systems for
concentrating solar power plants. Prog. Energy Combust. Sci. 39,
285–319. http://dx.doi.org/10.1016/j.pecs.2013.02.001.
273
Laing, D., Steinmann, W.-D., Tamme, R., Richter, C., 2006. Solid media
thermal storage for parabolic trough power plants. Sol. Energy 80,
1283–1289. http://dx.doi.org/10.1016/j.solener.2006.06.003.
Laurent, S.S., 2000. Thermocline Thermal Storage Test For Large Scale
Solar Thermal Power Plants, Report, Sandia National Laboratories,
Livermore.
Libby, C., 2010. Solar Thermocline Storage Systems, Final report, Electric
Power Research Institute, Palo Alto, CA.
ONE, 2009. Projet integré de production électrique solaire, Report, Office
National de l’Electricité, Morocco.
Oró, E., Gil, A., de Gracia, A., Boer, D., Cabeza, L.F., 2012. Comparative
life cycle assessment of thermal energy storage systems for solar power
plants. Renew. Energy 44, 166–173. http://dx.doi.org/10.1016/j.
renene.2012.01.008.
Özkahraman, H.T., Selver, R., Isß±k, E.C., 2004. Determination of the
thermal conductivity of rock from P-wave velocity. Int. J. Rock Mech.
Min. Sci. 41, 703–708. http://dx.doi.org/10.1016/j.ijrmms.2004.01.002.
Pacheco, J.E., Showalter, S.K., Kolb, W.J., 2002. Development of a
molten-salt thermocline thermal storage system for parabolic trough
plants. J. Sol. Energy Eng. 124, 153. http://dx.doi.org/10.1115/
1.1464123.
Relloso, S., Garcı́a, E., 2015. Tower technology cost reduction approach
after gemasolar experience. Energy Proc. 69, 1660–1666. http://dx.doi.
org/10.1016/j.egypro.2015.03.125.
Rhone, R., 2007. Les promesses de l’énergie solaire : Promouvoir une
énergie à faible teneur en carbone pour le xxie siècle. Chron. ONU
XLIV (2).
Schumann, W., 2002. Der neue BLV Steine- und Mineralienführer. Blv
Buchverlag.
Sicree, A.A., 2012. An Acidic Reaction, Hands-on Demonstrations of
Mineral Properties. Course, the Mineral Information Institute, Engle-
wood, USA.
Singh, H., Saini, R.P., Saini, J.S., 2010. A review on packed bed solar
energy storage systems. Renew. Sustain. Energy Rev. 14, 1059–1069.
http://dx.doi.org/10.1016/j.rser.2009.10.022.
Strasser, M.N., Selvam, R.P., 2014. A cost and performance comparison
of packed bed and structured thermocline thermal energy storage
systems. Sol. Energy 108, 390–402. http://dx.doi.org/10.1016/
j.solener.2014.07.023.
Troschke, B., Burkhardt, H., 1998. Thermal conductivity models fro two-
phase systems. Phys. Chem. Earth 23, 351–355. http://dx.doi.org/
10.1016/S0079-1946(98)00036-6.
van der Linden, S., 2006. Bulk energy storage potential in the USA,
current developments and future prospects. Energy 31, 3446–3457.
http://dx.doi.org/10.1016/j.energy.2006.03.016.
Van Lew, J.T., Li, P., Chan, C.L., Karaki, W., Stephens, J., 2011. Analysis
of heat storage and delivery of a thermocline tank having solid filler
material. J. Sol. Energy Eng. 133, 021003. http://dx.doi.org/10.1115/
1.4003685.
Vosteen, H., Schellschmidt, R., 2003. Influence of temperature on thermal
conductivity, thermal capacity and thermal diffusivity for different
types of rock. Phys. Chem. Earth Parts A/B/C (28), 499–509. http://dx.
doi.org/10.1016/S1474-7065(03)00069-X.
Waked, A.M., 1986. Solar energy storage in rocks. Sol. Wind Technol. 3,
27–31. http://dx.doi.org/10.1016/0741-983X(86)90045-7.
Waples, D.W., Waples, J.S., 2004. A review and evaluation of specific heat
capacities of rocks, minerals, and subsurface fluids. Part 1: minerals
and nonporous rocks. Nat. Resour. Res. 13, 97–122. http://dx.doi.org/
10.1023/B:NARR.0000032647.41046.e7.
Wu, M., Li, M., Xu, C., He, Y., Tao, W., 2014. The impact of concrete
structure on the thermal performance of the dual-media thermocline
thermal storage tank using concrete as the solid medium. Appl. Energy
113, 1363–1371. http://dx.doi.org/10.1016/j.apenergy.2013.08.044.
Xu, C., Wang, Z., He, Y., Li, X., Bai, F., 2012a. Sensitivity analysis of the
numerical study on the thermal performance of a packed-bed molten
salt thermocline thermal storage system. Appl. Energy 92, 65–75.
http://dx.doi.org/10.1016/j.apenergy.2011.11.002.
274 H. Grirate et al. / Solar Energy 131 (2016) 260–274

Xu, C., Wang, Z., He, Y., Li, X., Bai, F., 2012b. Parametric study and Appl. Energy 87, 3322–3329. http://dx.doi.org/10.1016/j.
standby behavior of a packed-bed molten salt thermocline thermal apenergy.2010.04.024.
storage system. Renew. Energy 48, 1–9. http://dx.doi.org/10.1016/j. Zanganeh, G., Pedretti, a., Zavattoni, S., Barbato, M., Steinfeld, a., 2012.
renene.2012.04.017. Packed-bed thermal storage for concentrated solar power – pilot-scale
Yang, Z., Garimella, S.V., 2010. Molten-salt thermal energy storage in demonstration and industrial-scale design. Sol. Energy 86, 3084–3098.
thermoclines under different environmental boundary conditions. http://dx.doi.org/10.1016/j.solener.2012.07.019.