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OVERVIEW OF MOLTEN SALT STORAGE SYSTEMS AND

MATERIAL DEVELOPMENT FOR SOLAR THERMAL POWER PLANTS

Thomas Bauer Nils Breidenbach


Institute of Technical Thermodynamics Nicole Pfleger
German Aerospace Center (DLR) Doerte Laing
Linder Höhe, 51147 Köln, Germany Markus Eck
e-mail: thomas.bauer@dlr.de Institute of Technical Thermodynamics
German Aerospace Center (DLR)
Pfaffenwaldring 38-40, 70569 Stuttgart, Germany
e-mail: nils.breidenbach@dlr.de

ABSTRACT plants. At these temperatures molten salts are attractive


candidates because they have advantages in terms of a high
This paper gives an overview of thermal energy storage heat capacity, high density, high thermal stability, relatively
(TES) systems based on molten salts. It summarizes state- low cost and low vapor pressure. The low vapor pressure
of-the-art molten salt TES systems. Storage systems in a results in storage designs without pressurized vessels. In
research stage, such as the thermocline and floating barrier general there is experience with molten salts from a number
concepts, are also discussed. The paper summarizes of industrial applications related to heat treatment,
previous work on molten salt material investigations at electrochemical reactions and heat transfer. The application
DLR. Experimental results of novel salt formulations with of salts requires the consideration of the lower temperature
melting temperatures well below 100 °C are presented. An limit defined by the melting temperature. One major
overview of temperature dependent thermophysical property difficulty with molten salts is unwanted freezing during
values of Solar Salt is given. The thermal stability of operation. Freezing must be usually prevented in the piping,
nitrate/nitrite mixtures was examined by dynamic the heat exchanger and in the storage tanks using auxiliary
thermogravimetry and static measurements at constant heating systems. Hence, salt mixtures with a low melting
temperature. We discuss in this paper the impact of the temperature are developed. At high temperatures, salt
atmospheric conditions (partial oxygen pressure) and salt stabilities and corrosion aspects play a major role. For solar
composition on the stability of nitrate salts. At DLR, a thermal power plants, a non-eutectic salt mixture of 60 wt%
molten salt test loop is in the design stage. A scheme of the sodium nitrate and 40 wt% potassium nitrate is typically
test loop and the options for experiments are presented. utilized. This mixture is commonly called Solar Salt.

1. INTRODUCTION 2. MOLTEN SALT STORAGE SYSTEM OVERVIEW

Solar thermal power plants are a key technology for 2.1. State of the art storage systems
electricity generation from renewable energy resources.
Thermal energy storage (TES) makes it possible to meet the At present, the two-tank molten salt storage is the only
intermediate load profile with dispatchable power, a benefit commercially available concept for CSP plants with a large
that has a high value to power utilities. Most commonly thermal capacity requirement. This storage system
three types of TES systems are distinguished. These are essentially consists of two tanks filled with molten salt at
sensible heat, latent heat and thermochemical heat storage. different temperature and fill levels. The two major types
The two groups of sensible heat storage are solids (e.g. are direct and indirect TES systems. Figure 1 shows the
concrete, rock, ceramics) and liquids (e.g. water, molten scheme of a direct system. In this system, the salt is at the
salt) [1]. same time the heat transfer fluid (HTF) and the storage
The presented paper focuses on high-temperature (> 250 °C) medium. The first larger two-tank molten salt storage
molten salt storage for concentrated solar power (CSP) system was demonstrated in the Solar Two Project at Sandia

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National Laboratories, commissioned in 1996 with a tower Table 1 shows that both systems have similar thermal
power plant. The operation time was 14 months and the salt capacities. On the other hand, the salt mass of the direct
mass was about 1400 tones (Figure 1) [2]. In 2011 the storage system is considerably lower compared to the
commercial solar tower power plant Gemasolar in indirect system. This is due to the fact that the capacity of a
Andalusia was commissioned. Table 1 shows the main molten salt storage is proportional to the temperature
characteristics of this storage system. difference between the hot and the cold tank. In other
In an indirect storage system, the thermal storage is de- words, the low temperature difference between the cold and
coupled from the HTF loop of the solar receiver via a heat hot tank of the described indirect system leads to a large
exchanger (Figure 2). The first commercial system with sized TES system.
indirect heat exchange has been in operation in the solar
thermal power plant Andasol 1 since 2009 [3]. Table 1 2.2. Storage systems in a research stage
compares commercial direct and indirect large-scale two-
tank molten salt TES systems. Several concepts for molten salt storage try to minimize
costs by using a single-tank system. A single tank requires
stratification with defined hot and cold temperature zones
and free convection is undesired. Free convection can be
suppressed by a floating barrier within the volume or
additional filler materials. The floating barrier concept was
examined by the company Sener [7]. The filler material
approach is commonly called thermocline concept. An
additional major advantage of the thermocline system would
be that molten salt volume is replaced by inexpensive filler
materials. Sandia National Laboratories performed material
investigations of the compatibility of filler materials and
molten nitrate salt, as well as modeling and experiments on
Fig. 1: Scheme with two-tank direct storage system [2]. a system level [4,8,9]. Yang et al. modeled heat transfer
aspect of the thermocline concept [10,11]. Another paper
discusses further details of commercial and non-
commercial molten salt TES systems [12].

3. MATERIAL REVIEW AND EXAMINATIONS

3.1. Thermophysical Properties of Solar Salt

Previous work at DLR focused on temperature dependent


thermophysical properties of NaNO 3 [13]. In the present
paper, literature values of the density ρ, heat capacity c p ,
thermal diffusivity a and thermal conductivity k of Solar
Fig. 2: Scheme with two-tank indirect storage system [4]. Salt are compared. Reliable thermophysical properties are
important for the modeling and dimensioning of molten salt
storage systems. Previous authors focused mainly on single
TABLE 1 : COMMERCIAL TWO-TANK SYSTEMS thermophysical property values. We verified several
literature values using the correlation k = a · ρ · c p . Another
paper discusses details of the methodology, literature
Direct storage [5,6] Indirect storage [3]
sources and correlations between single salt and Solar Salt
System name Gemasolar Andasol 1
properties [14]. Figure 3 includes consistent correlations of
Thermal capacity ~ 1000 MWh # 1010 MWh
thermophysical properties of Solar Salt. Results show that
Inventory 8500 tones 28500 tones these properties differ in terms of the uncertainty. Density
Cold tank temp. 290 °C 292 °C values show the lowest scattering. Heat capacity data vary
Hot tank temp. ~565 °C 386 °C slightly more than ± 5 % compared to the average value.
#
Estimated from ΔT = 275 K, 8500 tones, 1.55 kJ kg-1 K-1 Thermal diffusivity and thermal conductivity values showed
the strongest variations (± 15 %).

2
1.95
Murgulescu 1959 (Interpolation)
1.9 Murgulescu 1969 (Interpolation)
ρ in g·cm-3

Polyakov 1955 (Interpolation)


1.85 Pacheco 1995, Zavoico 2001 (SolarTwo)
Janz recom. 1972 (with +/-1.5 % error bar)

1.8 Janz extrapolated


Bradshaw 2009 (Molar volume addition)

1.75 ρ (g·cm-3) = 2.1060 - 6.6795E-04· T(°C)

1.7
1.7 Rogers 1982 (Calc. from single salts)
Zavoico 2001 (SolarTwo)

1.65 Takahashi 1988 (Calc. from single salts)


Carling 1983 (Calc. from single salts)
cp in J·g-1·K-1

Gustafsson 1968 (Calc. from single salts)

1.6 Jriri 1995 (Calc. from single salts)


Bradshaw 1987
Average without Zavoico

1.55

1.5 ±5 % error bar of average


cp (J·g-1·K-1) = 1.5404 + 3.0924E-5· T(°C)
1.45
0.22
Gustafsson 1968 (Interpolation)
0.21
a in mm²·s-1

Ohta 1990 (Interpolation)


0.2
0.19 Kato 1983 (Interpolation)

0.18 Knothe 1985 (Interpolation)

0.17 Calculated using data by Janz and


average values
0.16
a = k / (cp·ρ)
0.15 ± 15 % error bar of average
0.14
0.65
k (W·m-1·K-1) = 0.3804 + 3.452E-04 · T (°C)
0.6 ±15 % error bar of average
k in W·m-1·K-1

Foosnæs 1982 (Interpolation)


McDonald 1970 (interpolation)
0.55 Omotani 1982 (Interpolation)
Tufeu 1985 (Interpolation)
Bloom 1965 (Interpolation)
0.5 White 1967 (Interpolation)
Zavoico 2001
Santini 1984 (Interpolation)
0.45 Kitade 1989 (Interpolation)
Turnbull 1961 (Interpolation)
Average without Zavoico
0.4
0 50 100 150 200 250 300 350 400 450 500 550 600
Temperature in °C
Fig. 3: Temperature dependent thermophysical data of Solar Salt

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3.2. Literature review of alkali nitrate/nitrite salt mixtures 3.3. Development of low melting temperature mixtures

Table 2 presents a systematic list of the melting Bradshaw et al. published data of the quaternary reciprocal
temperatures of single salts and the minimum melting system K,Li,Na//NO 2 ,NO 3 with a minimum melting
temperature of salt systems with the cations calcium (Ca), temperature of about 75 °C (Table 1) with the composition
potassium (K), lithium (Li) and sodium (Na) (Table 2 33.5 mol% Li+, 47.9 mol% K+, 18.6 mol% Na+ and a
vertical) and the anions nitrate (NO 3 ) and nitrite (NO 2 ) nitrate/nitrite ratio of 0.56 [16]. Own work focuses on phase
(Table 2 horizontal) using various literature sources [15]. diagram determinations of this system using a heat flux type
The melting temperatures of the listed single salts range differential scanning calorimeter (DSC) and a melting point
from 220 °C (LiNO 2 ) to 561 °C (Ca(NO 3 ) 2 ). Salt mixtures, apparatus (MPA). A previous paper discusses details of the
rather than single salts, have the advantage of a lower experimental method [15]. Figure 4 shows DSC and MPA
melting temperature. These mixtures can have similar measurement results of the liquidus temperature of the
thermal stability limits as the single salts. Hence, salt system K,Li,Na//NO 2 ,NO 3 with a fixed NO 3 /NO 2 ratio of
mixtures, such as eutectics, can have a wider temperature about 0.56. The measurement points are marked by an
range compared to single salts. Table 2 shows commonly asterisk symbol. The mixture with the lowest liquidus
considered salt systems for solar applications in grey temperature had the composition: Li+ 33 mol%, K+ 48 mol%
background. These are the binary K,Na//NO 3 system with a and Na+ 19 mol% with a ratio NO 3 /NO 2 = 0.56. Figure 5
common anion (containing Solar Salt), the ternary shows DSC measurements of this mixture. It can be seen
reciprocal systems K,Na//NO 3 ,NO 2 (containing a mixture that a minimum melting mixture rather than a mixture with
called Hitec) and the two ternary additive systems with a a melting range was successfully identified [15].
common anion Ca,K,Na//NO 3 (HitecXL) and K,Li,Na//NO 3 .
Table 2 clearly shows the tendency of melting temperature
depression from the left to right hand side, as well as from
the top to the bottom of the table. Hence, it can be expected
that systems with a liquidus temperature lower than 80 °C
are feasible.

TABLE 2 : MATRIX OF (MINIMUM) MELTING


TEMPERATURE OF SUBSYSTEMS OF THE QUINARY
RECIPROCAL SYSTEM Ca,K,Li,Na//NO 2 ,NO 3 [15]

NO 2 NO 3 NO 2 , NO 3
Single salts and binary systems with common cation
Ca 398 °C# 561 °C# 393 °C
K 440 °C 334 °C 316-323°C
Li 220 °C 254 °C 196 °C
Na 275 °C 306 °C 226-233 °C Fig. 4: Part of liquidus phase diagram K,Li,Na //
Binary systems with common anion and ternary reciprocal NO 2 ,NO 3 ; the minimum is marked red
Ca,K 185 °C 145-174 °C 130 °C
7
Ca,Li 205-235 °C 235 °C 178 °C 85
Liquidus temperature

6 Heating rate 5 K/min


Ca,Na 200-223 °C 226-230 °C 154 °C Heating rate 2 K/min 84
K,Li 98 °C 126 °C 94 °C 5 Heating rate 1 K/min
DSC signal [μV/mg]

83
[°C]

K,Na 225 °C 222 °C 142 °C 4 82


Li,Na 151 °C 196 °C 126 °C 3 81
Ternary additive common anion and quaternary reciprocal 0 1 2 3 4 5 6
2 Heating rate [K/min]
Ca,K,Li N/A 117 °C N/A
1
Ca,K,Na N/A 130 °C N/A
Ca,Li,Na N/A 170 °C N/A 0

K,Li,Na N/A 119 °C 75 °C -1


Quaternary additive common anion and quinary reciprocal -50 0 50 100 150 200
Temperature [°C]
Ca,K,Li,Na N/A 109 °C N/A
#
Decomposition at the melting temperature Fig. 5: DSC measurement results of the mixture Li +
33 mol%, K + 48 mol% and Na + 19 mol%

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3.4. Thermal stability examination of nitrate/nitrite salts stability tests in an open-system in oxygen-nitrogen
atmospheres at ambient pressure.
Mass losses with gas evolution of alkali metal nitrate salts Static measurements at constant temperatures in synthetic
may occur due to three mechanisms: nitrite formation in the air atmosphere were performed. It is well known that molten
melt and oxygen release (1), alkali metal oxide formation in nitrates decompose to nitrites. The thermal dissociation is
the melt and nitrogen/nitrogen oxide release (2) and reversible and for NaNO 3 the equilibrium reaction can be
vaporization of the nitrate salts (3) [17,18]. The written as shown in Equation 1.
decomposition temperature depends on various aspects.
They include the definition itself, the experimental method NaNO3( l ) ⇔ NaNO2 ( l ) + 12 O2 ( g ) (1)
(e.g. heating rate), crucible material and atmosphere. A
comparison of results from different authors is usually We examined the kinetics of the nitrite formation in the
difficult, because these aspects differ among the authors. NaNO 3 melt in the temperature range 450 to 550 °C. A full
Hence, own measurements of single salts and selected salt discussion of these measurements is presented in [15].
mixtures were performed. Measurements parameters were Figure 7 plots static NaNO 3 measurements at the three
atmospheric pressure, dry nitrogen and a heating rate of temperatures 450, 500 and 550 °C. Synthetic air with a rate
10 K min-1. Another paper discusses further details of the of 100 and 600 ml min-1 was purged through the melt. The
experimental method [15]. Figure 6 presents results of figure shows the nitrite formation depending on the time
thermogravimetry (TG) measurement of single nitrate and with the salt temperature as a parameter. A simple empirical
nitrite salts, as well as four mixtures with a low melting exponential growth model was fitted to the measurements
temperature. with 100 ml min-1 using non-linear regression techniques.
Stern reports the decomposition pressure, or alternatively The model uses two parameters and can approximately
the equilibrium constant, in increasing order as follows describe the reaction kinetics. The three model curves show
KNO 3 < NaNO 3 < Ca(NO 3 ) 2 < LiNO 3 (highest stability for that the temperature level not only affects the amount of
KNO3). Nitrites are considered to be less stable than nitrates NO 2 - in equilibrium but also the decomposition rate. The
[18]. Own measurements show that mass losses occur equilibrium at 550 °C was quickly reached after several tens
mostly in a temperature range from 500 °C to 600 °C. Less of hours. On the other hand, at 450 °C the time constant was
stable salts were LiNO 3 and Ca(NO 3 ) 2 , as well as the much longer (several hundreds of hours).
mixture Ca,K,Na//NO 3 . The stabilities of the salt mixtures
K,Na//NO 3 (Eutectic) and K,Li,Na//NO 2 ,NO 3 (80 °C) were
similar to the single salt NaNO 3 . Hence, the novel low 0.045
Molar ratio NO2-/NO3- ,pO2=0.21(air)

550
550°C
°C100
100mlml·min
min-1 -1
melting salt mixture K,Li,Na//NO 2 ,NO 3 is a promising 0.040 500
500°C
°C600
600mlml·min
min-1 -1(Experiment 1) 1)
(Experiment
candidate as HTF due to its wide operation range. 0.035
500°C
500 °C100 min-1 -1(Experiment
100mlml·min (Experiment
1) 1)
500°C
°C100
100mlml·min -1 (Experiment
500 min-1 (Experiment 2) 2)
450°C
°C100
100mlml·min -1
0.030 450 min-1

0.025
101
0.020
100
0.015
Mass loss - TG signal [%]

99 0.010
KNO3
NaNO3 0.005
98 Ca(NO3)2
LiNO3 0.000
97 NaNO2 0 100 200 300 400 500 600 700 800 900 1000
KNO2 Time t in hours
96 K,Li,Na // NO2,NO3 (Tm=75°C)
Ca,K,Na // NO3 (Hitec XL) Fig. 7: Kinetics of nitrite formation in NaNO3 in synthetic
95 K,Na // NO3 (Eutectic)
K,Na // NO2,NO3 (Hitec)
air atmosphere in an open type system
94
0 100 200 300 400 500 600 700
Temperature [°C]
For Solar Salt, we examined not only the kinetics of nitrite
Fig. 6: Thermogravimetric measurement results of single formation but also the kinetics of oxide formation in the
alkali nitrate salts (filled symbols) and alkali metal nitrite melt by an indirect method. The examined oxides form an
salts (asterisk symbols) and salt mixtures (open symbols) alkaline solution if dissolved in water. Subsequently, an
acid-base titration with HCl solution was performed [14].
As discussed in the previous paragraph, the primary
More detailed stability examination focused on NaNO 3 and decomposition reaction with nitrite formation in the melt
Solar Salt. The thermal stability of these nitrate salts was and oxygen release is well examined. The secondary
examined by two methods. These were dynamic and static decomposition reaction with alkali metal oxide formation

5
and nitrogen/nitrogen oxide is less understood and oxides oxygen pressure leads to a high decomposition temperature.
within the melt could be corrosive. The chemistry of these In other word, the stability of NaNO 3 and Solar Salt
oxygen species is complex and some of the evidence is in improve with increased partial oxygen pressures. Results
conflict. In literature the formation of oxide, superoxide and were extrapolated to equilibrium conditions (0 K min-1
peroxide is discussed [18,19]. Results in Figure 8 refer to heating rate). For NaNO 3 and equilibrium conditions,
measurements of Solar Salt at 550 °C in synthetic air results show a decomposition temperature of 525 °C in
atmosphere. The figure plots not only the NO 2 -/NO 3 - ratio synthetic air and 542 °C in oxygen at atmospheric pressures.
(left hand axis) but also the equivalence point of the titration For Solar Salt and equilibrium conditions, the values are
(right hand axis). It can be seen that the NO 2 -/NO 3 - ratio 529 °C (synthetic air) and 562 °C (oxygen). This value is
reaches equilibrium after a few ten hours as opposed to the lower compared to the previously reported value of 565 °C
volume of titration which increases steadily. It can be [8]. Own measurements refer to a mass loss of 3wt%. It
concluded that although the NO 2 -/NO 3 - ratio reaches should be considered that different mass loss definitions will
equilibrium, the alkali metal oxide level with nitrogen result in other stability limits. Also, static and dynamic test
release reaches no equilibrium within the experimental time may result in different decomposition temperatures. Our
frame. Hence, further work focuses on the long-term measurements show that the thermal stability of Solar Salt is
thermal stability limit of Solar Salt to examine the different higher compared to NaNO 3 . It can be also seen that the
decomposition mechanisms. stability of Solar Salt (Figure 10) depends more strongly on
the partial oxygen pressure than NaNO 3 (Figure 9). For
NaNO 3 the stability difference between synthetic air and
oxygen is 17 K (542 °C minus 525 °C), whereas the Solar
Salt value is 33 K.

680
Thermal decomposition temperature Tz

TZ = 612.5 + 3.474 ⋅ pO 2
0.5

660
TZ = 595.8 + 4.084 ⋅ pO 2
0.5

10 K∙min-1
640
of NaNO3 3wt% in °C

620 5 K∙min-1
TZ = 569.1 + 2.700 ⋅ pO 2
0.5
600 2 K∙min-1
580
TZ = 525.3 + 3.069 ⋅ pO 2
0.5
560 0.5 K∙min-1
540
0 K∙min-1 (extrapolated
Fig. 8: Kinetics of oxide formation in Solar Salt in synthetic 520 from 0.5 and 2 K∙min-1)
air atmosphere in an open type system at 550 °C 500
0 10 20 30 40 50 60 70 80 90 100
Relative partial oxygen pressure po2 in % (21 % = air)
In addition to static measurements, dynamic measurements Fig. 9: Experimental thermogravimetry results of the
with a heating ramp were performed by thermogravimetry thermal stability of NaNO 3 depending on the partial oxygen
(TG) [14]. The major parameters were the salt composition, pressure and the heating rate (0.5 K min-1 to 10 K min-1).
partial oxygen pressure and the heating rate. This approach
led to a large number of TG measurements. For all 680
Thermal decomposition temperature Tz

measurements, the thermal decomposition temperature TZ = 603.2 + 6.635 ⋅ pO 2


0.5 5 K∙min-1
660
refers to the temperature with a mass loss of 3 wt%
of Solar Salt 3wt% in °C

640
compared to the base line. The atmospheres were pure 2 K∙min-1
620
nitrogen or an oxygen-nitrogen mixture with a total flow of
TZ = 576.7 + 7.490 ⋅ pO 2
0.5

100 ml min-1. The heating rates ranged from 0.5 K min-1 to 600
0.5 K∙min-1
10 K min-1. 580 TZ = 520.9 + 6.439 ⋅ pO 2
0.5

Work at Sandia aims for oxygen-stabilized Solar Salt up to 560


650°C [20]. Own work focused on the impact of the partial 540 0 K∙min-1 (extrapolated
pressure of oxygen on the thermal stability. Figure 9 and 10 from 0.5 and 2 K∙min-1)
520
plot results of dynamic TG-measurements of NaNO 3 and
500
Solar Salt depending on the partial oxygen pressure. It can 0 10 20 30 40 50 60 70 80 90 100
be seen that the measured decomposition temperature Relative partial oxygen pressure po2 in % (21 % = air)
depends on the heating rate. Higher heating rates result in Fig. 10: Experimental thermogravimetry results of the
higher decomposition temperatures due to the measurement thermal stability of Solar Salt depending on the partial
principle. All measurement series show that a higher partial oxygen pressure and heating rate (0.5 K min-1 to 5 K min-1)

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4. DESIGN OF A MOLTEN SALT LOOP AT DLR sink for operating thermal cycles. For the testing and
examination of components and storage tanks, the test loop
Research on molten salt as heat transfer or storage medium is anticipated to have a scale which can provide real
focuses currently on mainly two aspects: operation conditions of a solar thermal power plant in terms
of mass flow rates and receiver diameters. For the first test
• Development of innovative salt mixtures with lower phase, Solar Salt will be used as the HTF and storage
melting temperature and/or higher thermal stability
medium.
• Demonstration and optimization of molten salt
processes e.g. as heat transfer medium in parabolic
troughs or in innovative storage systems.
Cooler
Especially the second focus has gained more importance.
The main advantage of using molten salt in parabolic trough
plants are the potential reduction of investment costs for the
heat transfer fluid, since nitrate salt is less expensive than
thermal oil and the simplification of the process technology Measurement
because the molten salt heat transfer fluid also acts as the Section
storage medium. Another advantage is the higher operation Heater
temperature of the solar field. This enables a higher
conversion efficiency of the power block and a larger
temperature difference in the storage system and thus a
significantly increased specific storage capacity (Table 1).
However, to-date no commercial large-scale parabolic
trough plants applying this technology has been realized. Hot Tank /
Converting the design of parabolic trough collector is not a Cold Thermocline
straightforward issue. The operation temperature is more Tank
than 150 °C above state of the art collectors and components
such as receivers, flexible tube connections and control
valves, have to be qualified and have to prove reliability
under realistic operating conditions. The challenging Fig. 11: Schematic of the molten salt test loop in a design
chemical behavior, creepage and corrosion of molten salts stage at DLR
introduce new requirements on components that are in
contact with the salt.
Even though molten salt storage systems are commercially
5. SUMMARY AND CONCLUSION
available for indirect and direct storage systems and realized
in ANDASOL-like power plants [3] as well as in the
This paper gave an overview of commercial molten salt TES
Gemasolar power plant [6], storage costs are a major issue in
systems for CSP plants. These systems are the two-tank
the economic evaluation of concentrated solar power (CSP)
direct storage system for power towers and two-tank
plants. Therefore, the development of new storage concepts
indirect storage systems for parabolic troughs. The
with reduced costs for the storage material, such as the
following research and development aspects were identified:
thermocline concept [8] or the floating barrier concept [7] is
crucial for improving the profitability of CSP. Additionally, • Identification and characterization of salt
components such as pumps, valves and other instruments are formulations with a low liquidus temperature and
a major engineering issue in a molten salt system with suitable thermal stability
parabolic trough collectors or a central receiver and a molten • Examination of nitrate salts at their thermal
salt storage. Up to now, only a few suppliers are available stability limit under different atmospheric
and thus experience with molten nitrate salt operation over conditions including corrosion aspects
500 °C is limited. • Component tests under realistic operation
In order to face the mentioned challenges a molten salt test conditions (e.g. valves, pumps, solar collectors)
loop as shown in Figure 11 will be erected at DLR. The test • Development of new storage concepts with
loop will be designed to be able to store the complete salt improved economics compared to the two-tank
inventory in the cold tank. By using the cold tank as a drain, design (e.g. floating barrier, thermocline concept)
different components can be installed in the measurement
section. In addition, the hot tank can be drained in order to Phase diagram measurements demonstrated that novel salt
test various thermocline setups. The system will have a mixtures with a low melting temperature are feasible.
heater to achieve salt temperatures over 500 °C and a heat However, the identification of further suitable multi-

7
component mixtures requires a large number of Design for Solar Thermal Power Plants, Solar Paces,
measurements due to their degrees of freedom. Thus, Perpignan, France, 2010
advanced techniques to determine phase diagrams will be (8) Pacheco, J. E., Showalter, S. K. and Kolb, W. J.,
required. They include phase diagram prediction by Development of a Molten-Salt Thermocline Thermal
modeling and high-throughput experimental methods. Storage System for Parabolic Trough Plants, Journal of
The thermal stability of nitrate salts depends on several Solar Energy Engineering 124, pp. 153, 2002
aspects. They include the salt composition, the gas (9) Brosseau, D. A., Hlava, P. F. and Kelly, M. J., Testing
composition with partial pressures and the release of Thermocline Filler Materials and Molten-Salt Heat Transfer
decomposition products (open and closed type system). The Fluids for Thermal Energy Storage Systems Used in
paper described results on the primary decomposition Parabolic Trough Solar Power Plants, SAND2004-3207,
reaction with nitrite formation in the melt and oxygen 2004
release and a secondary decomposition reaction with alkali (10) Yang, Z. and Garimella, S. V., Thermal analysis of
metal oxide formation in the melt and nitrogen/nitrogen solar thermal energy storage in a molten-salt thermocline,
oxide release. Measurements indicate that the kinetic time Solar Energy 84, pp. 974-985, 2010
constants of these two decompositions are not the same (11) Yang, Z. and Garimella, S. V., Molten-salt thermal
under the examined experimental conditions. Hence, further energy storage in thermoclines under different
work on the nitrate salt chemistry near the stability limit is environmental boundary conditions, Applied Energy 87, pp.
required. 3322-3329, 2010
In order to assess operational challenges on a system level, a (12) Breidenbach, N., Bauer, T., Laing, D. and Tamme, R.,
flexible molten salt test loop is in a design stage at DLR. Assessment and development of molten salt storage and
This test loop should allow for component tests with typical heat transfer fluids for solar thermal power plants and
mass flow rates and tube diameters in CSP plants. In addition, industrial processes, World Engineers' Convention, Geneva,
thermal cycling operation and full drainage procedures are Italy, 2011
anticipated. This should allow for the research and (13) Bauer, T., Laing, D. and Tamme, R., Characterization
development of new single-tank concepts in a sufficient of Sodium Nitrate as Phase Change Material, International
scale. Journal of Thermophysics 33, pp. 91-104, 2012
(14) Bauer, T., Pfleger, N., Breidenbach, N., Eck, M.,
6. ACKNOWLEDGMENTS Laing, D. and Kaesche, S., Material Aspects of Solar Salt
for Sensible Heat Storage, Innostock 2012, The 12th
We express our thanks especially to Ulrike Kröner and International Conference on Energy Storage, Lleida, Spain,
Markus Braun for the experimental part and data analysis. 2012 (submitted for publication)
(15) Bauer, T., Laing, D. and Tamme, R., Recent Progress
in Alkali Nitrate/Nitrite Developments for Solar Thermal
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