Solar Energy 79 (2005) 332339 www.elsevier.

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Screening of high melting point phase change materials (PCM) in solar thermal concentrating technology based on CLFR
Akira Hoshi
a

a,*

, David R. Mills b, Antoine Bittar b, Takeo S. Saitoh

Department of Mechanical Engineering, Ichinoseki National College of Technology, Takanashi, Hagisho, Ichinoseki 021-8511, Japan b School of Physics, University of Sydney, NSW 2006, Australia Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579, Japan Received 23 February 2004; accepted 19 April 2004 Available online 30 December 2004 Communicated by: Associate Editor Erich Hahne

Abstract We have investigated the suitability of high melting point phase change materials for use in new, large scale solar thermal electricity plants. Candidate materials for latent heat thermal energy storage are identied and their operating parameters modeled and analysed. The mathematical characteristics of charging and discharging these storage materials are discussed. Several high melting point, high conductivity materials are shown to be suitable and advantageous for use with solar thermal electricity plants, such as Sydney Universitys novel, low cost CLFR and MTSA collector systems, as well as existing parabolic trough and tower technologies. 2004 Elsevier Ltd. All rights reserved.
Keywords: Solar thermal electricity; High-melting point; Phase change material; Compact linear Fresnel reector; Multi tower solar array; Latent heat thermal energy storage

1. Introduction Global warming due to carbon dioxide (CO2) emissions is an important environmental issue. The rapid implementation of advanced energy technologies for utilizing energy more eciently and the use of clean and safe renewable energy (e.g. solar energy, wind energy, sky radiation cooling, etc.) will be required (Saitoh

Corresponding author. Fax: +81 191 24 4729. E-mail address: hoshi@ichinoseki.ac.jp (A. Hoshi).

and Ono, 1984; Saitoh et al., 1985; Saitoh and Fujino, 1998) to reduce climate impacts. Since fossil fuels such as petroleum, coal, and natural gas are limited resources, renewable energy such as solar, wind, and biomass will be needed as substitute fuels. Recent advances in low cost solar thermal electricity, such as the Sydney university Compact Linear Fresnel Reector technology (Mills and Morrison, 2000), and the more recent, two axis tracking, multi tower solar array (Mills and Schramek, 1999), hold the promise for low cost, large scale solar energy implementation. These plants, as well as existing tower and trough

0038-092X/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.solener.2004.04.023

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technologies, would gain substantially from cost eective high temperature storage systems to enable near continuous operation at high temperatures and high eciencies. Among several thermal energy storage technologies, the latent heat thermal energy storage (LHTES) system using phase change material (PCM) is useful because of its ability to charge and discharge a large amount of heat at constant temperature during melting and solidication (Hoshi and Saitoh, 2001a,b). In these applications, where melting and solidication of the PCM are the main storage mechanisms, the melting process is limited by thermal conductivity and natural convection, and the solidication process is mainly limited by thermal conductivity. This paper describes high melting point PCMs suitable for low cost CLFR and MTSA technologies. In addition, the charging and discharging characteristics of high melting point PCMs are modeled and analysed numerically. The implementation of such systems in a CLFR or MTSA plant is outlined. From this, high-temperature LHTES systems suitable for use with solar thermal electricity systems using CLFR and MTSA technology are identied, and shown to be also applicable to line focus trough and parabolic dish power plants. In the following sections we present the relevant operating details of Sydney Universitys CLFR and MTSA technologies, the properties of several LHTES materials, the modeling of their properties and their implementation, and draw conclusions on their applications to these, and to similar solar thermal electricity plant. 1.1. Compact linear Fresnel reector (CLFR) and multi tower solar array (MTSA) technologies A low cost solar thermal concentrating technology based on a compact linear Fresnel reector (CLFR) arrangement is now under commercial development by the company solar heat and power (SHP) (Mills et al., 2003). The CLFR eld is based on the University of Sydney design, developed in 1993 and patented in 1995. Linear Fresnel reector (LFR) concentrators use a eld of linear reectors close to the ground which reect solar radiation upon a downward facing linear absorber. The CLFR is not a classical LFR because it employs a strategy based upon multiple towers which allows area coverage to be signicantly reduced by partially intermeshing adjacent single tower arrays. The current design also makes signicant optical eciency advances around the tower mounted receiver, which is a at cavity receiver containing boiling tubes (Mills et al., 2003). No secondary reector is used in order to maintain high optical eciency and avoid the use of hot reectors. Fluid temperatures of between 450 K and 630 K are currently envisaged using direct steam generation in the absorber tubes. Nuclear type

unsuperheated medium temperature Rankine cycle turbines are proposed for stand alone plants. Conventional trough systems use oil heat transfer and conventional superheated turbines. In conventional Fresnel or parabolic trough systems, a large reector separation interval is required in order to avoid the mutual shading eect between mirror rows. The newer, compact linear Fresnel reector (CLFR) conguration was developed in order to overcome the limited ground coverage of these line focus systems. The advantages of interleaving become stronger as the reector density in the eld increases. Avoidance of large reector spacing and high towers reduces the cost of ground preparation, array substructure, tower structure, and steam line cost. In addition, a second technology, called the multi tower solar array (MTSA), is being developed by the University of Sydney and SHP (Mills and Schramek, 1999; Mills et al., 2002) for large urban power plant applications for delivery of combined heat and power. This uses two-axis tracking heliostats and multiple point focus receivers on many small towers. This is suitable for temperatures of operation between 600 K and 1300 K, with temperatures between 1000 K and 1250 K being appropriate for small Stirling and Brayton Cycle turbines. In Australia, 240 MW CLFR systems with storage are being contemplated for construction beginning in 2005, and 110 MW MTSA systems are planned for later in the decade. These systems can be made less expensive if storage allows a smaller and less expensive heat engine to operate for a much longer time during the day/night cycle, with operation near the turbine design point rather than at part load. Daily storage also removes hourly uctuations from the output pattern of such plants, making them grid-friendly, and possibly providing some peaking potential for high demand periods. The advantages of low cost, eective thermal storage are, therefore, several and substantial. 1.2. High melting point phase change materials Numerous investigations of LHTES systems have been reported in recent years. Almost all of these may be classied into the low temperature category below 500 K. However, because of the development of low cost concentrator technologies, a complementary development of high-density heat storage systems of medium (500 K700 K) temperature for line focus systems and high (>700 K) temperature for point focus systems is now assuming much greater importance as solar electricity begins to replace conventional power on a large scale. The high melting point LHTES approach can reduce the energy storage equipment and containment cost, since the energy density is large. Importantly, energy with constant temperature and pressure can be supplied

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to turbines running at optimal eciency, unlike the case with sensible heat storage systems, where the temperature drops as the storage is discharged. In the high melting point LHTES system, it is important to choose the optimum PCM. The input and output temperature in the energy storage equipment is determined by the melting point of the PCM. The heat capacity is determined by latent heat and sensible heat of the PCM. In order to elucidate the applicability of the various candidate materials, we screened the relationship between melting point and heat capacity of PCMs including molten single salts (Janz, 1967; Janz et al., 1979; Seki, 1995). The results for materials with melting points in the range 300 K to 1200 K (in consideration of possible use with CLFR and MTSA arrays), are shown in Fig. 1, which is a plot of heat capacity and melting point for sugar alcohol, organic materials, molten single salts and metals. It is clear that, over the temperature range to 700 K, metals such as Sn and Zn can be used as PCMs, being Zn being interesting at the upper part of the temperature range currently used by trough collectors. For CLFR systems using low pressure turbines at or below 600 K, the salts NaNO2, NaNO3 and KNO3 are interesting candidates one. In the higher-temperature region above 500 K, mainly molten single salts are eective as PCMs, with Na2CO3 and KCO3, of interest for high temperature Brayton Cycle turbines. In this latter range, the salts themselves can be divided into sub categories. The relationship between heat capacity and melting point for the uorides, chlorides, carbonates, sulfates, bromides, nitrates and eutectic salts is shown in Fig. 2. Generally, melting point and heat capacity tend to increase in the order of nitrates, chlorides, carbonates and uorides. Finally, and as an indication of economic viability, we show in Fig. 3 the relationship between melting point

and the media costs per kWh. The costs, calculated from the price of the reagent, appear to indicate the cost eectiveness of high temperature LHTES for the applications envisaged above. With this additional information, NaNO2 seems preferred for low temperature CLFR turbines, Zn for a high temperature trough, and Na2CO3 for a high temperature turbine for the MTSA. These media are all the same cost, but containment issues would be dierent for metals and salts. In a recent presentation (Tamme, 2003), studies PCMs as storage elements in a trough system using oil heat transfer. He shows that some salt mixtures, notably NaOH/Na2CO3 have a superior heat capacity to single salts of similar melting point such as NaNO2, with the former having a heat capacity of 370 kJ/kg compared to the 212 kJ/kg of the latter. However, the medium cost will be signicantly higher for the mixture. He also describes the case of NaCl (42.5%)/KCl(20.5%)/MgCl2 which attains 410 kJ/kg at a melting point of approximately 660 K. In this case the medium cost is about the same as Pb but the thermal conductivity will be much lower. 1.3. Numerical analysis of charging and discharging Over and above the heat capacity, melting point and cost of high temperature PCM, their thermal performance during charging and discharging is of importance in the STE applications. For this, we have developed a model for, and an analysis of, the charging and discharging performance of two dierent candidate materialsa metal and a salthaving otherwise similar characteristics. From Figs. 13, the melting point, heat capacity and costs per kWh for KNO3 and Pb are almost the same. However, the metal specic heat is smaller and its thermal conductivity is larger than the

600 Sugar alcohol 500 Organic materials Molten single salts Metal LiOH 300 Zn 200 100 LiNO3 NaNO3 Erythritol Sn NaNO2 Mannitol KOH NaOH KNO 3 Pb Polyethylene 400 500 600 800 900 700 Melting point Tm, K LiCl Li2CO3 MgCl2 NaCl Na2CO3 KCl CaCl2 K2CO3 1200 KF LiF

Heat capacity, kWh/m3

400

0 300

1000

1100

Fig. 1. Heat capacity of high melting point phase change materials.

A. Hoshi et al. / Solar Energy 79 (2005) 332339

800 Fluorides Chlorides Carbonates Sulfates Bromides Nitrates Hydroxides Eutectics LiOH 200 LiNO3 NaNO3 NaOH 0 500 600 Li2CO3Na2CO3 KNO3 KOH LiBr LiCl

335

Heat capacity , kWh/m3

600

LiF NaF LiF-CaF2 Li2CO3 MgCl2 NaCl KCl CaCl2 Li2SO4 900 1000 1100 Na2CO3 K2CO3 Na2SO4 1200 1300 KF

400

NaCl-CaCl2 800 Melting point Tm, K

700

Fig. 2. Heat capacity of molten salts.

1200

1000
Costs per kWh, US$/kWh

LiOH

Sugar alcohol Organic materials Molten single salts

800

LiNO3 NaNO3 Sn Pb KNO3 KOH Zn

Metal

600

400

LiCl Li2CO3

NaOH

K2CO3

200

0 300

Mannitol NaNO2 Erythritol Polyethylene 400 500 600

MgCl2

CaCl2 LiF KF KCl NaCl Na2CO3 1100 1200

800 900 700 Melting point Tm, K

1000

Fig. 3. Media costs of high melting point phase change materials.

salt. We compare their charging and discharging performances in a double tube LHTES model system shown in Fig. 4. The primary assumptions of the model are as follows: (1) The physical properties are constant. (2) Volumetric expansion during melting is negligible. (3) Natural convection is negligible in the liquid region. The governing energy equations for the liquid and the solid regions may then be written as:

Liquid:  2  oT l o T l 1 oT l al ot or2 r or (Charging) r0(t) < r < r m(t) (Discharging) rm(t) < r < r1 Solid:  2  oT s o T s 1 oT s as r or ot or2 0 < r < Rm t1 2 1

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Fig. 4. Schematic model for high-temperature LHTES.

(Charging) rm(t) < r < r1 (Discharging) r0 < r < rm(t) where the variables used follow the nomenclature given in Table 1. The initial conditions are given by T l r; 0 T s r; 0 T m 0<r<R 3

Discharging T s r0 ; t T 0 oT l r1 ; t 0 t>0 or

t>0

The heat balance equation at the solidliquid interface of the system may be written as: qL drm t qLrm t dt oT s rm t; t oT l rm t; t ks kl or or

and the boundary conditions during charging and discharging are respectively Charging T l r0 ; t T 0 oT s r1 ; t 0 t>0 or t>0 4

t>0

The numerical integration of these equations may then be carried out using the Successive Over-Relaxation (SOR) method proposed by Saitoh (Saitoh, 1994). The results for charging energy versus real time under the same volume are shown in Fig. 5. The charging energy

Table 1 Nomenclature for charging and discharging model a k L r r1, r2 rm T t Greek symbols q Subscripts and superscripts l s thermal diusivity thermal conductivity latent heat coordinates cylinder radius melting front temperature time density liquid latent heat

200

r0 = 0.01 m
Charged energy Echarge, MJ/m3

150

r1 = 0.1 m T0 = ( Tm + 10 ) K Pb

100

KNO3
50

0 0 500 1000 1500 2000 Time t, min

2500

Fig. 5. Comparison of KNO3 and Pb charging speeds in model LHTES.

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time for lead is very much shorter than for potassium nitrate, as expected. Fig. 6 shows the discharging energy versus real time under the same volume. The discharging speed for potassium nitrate is very much slower than for lead, and discharging time is substantially longer under the same volume. These large dierences are essentially a consequence of dierences in the thermal conductivity of the two media. In the high melting point LHTES system, the thermal conductivity therefore becomes a very important parameter in the choice of materials. We show in Fig. 7 the relationship between thermal conductivity and melting point for the uorides, chlorides, carbonates, hydroxides, bromides, nitrates and eutectics identied above. Some of the materials having high melting point also exhibit a high thermal conductivity. These are likely to be most important for the

design of high melting point LHTES systems suitable for the MTSA especially. This is particularly true of NaCO3. 1.4. Application to a high-temperature latent heat thermal energy storage (LHTES) system Solar thermal concentrating technology based on the CLFR is undergoing commercial development at Liddell Power Station (Mills et al., 2003). The solar radiation will be collected by more than 132,000 m2 of mirrors focusing onto ten absorber lines. This CLFR plant will produce a peak of 95 MW of thermal energy and will be used for preheating feed water with design steam delivery conditions as 265 C and 5 MPa wet steam. As an application, one could introduce the high-temperature LHTES system into the solar thermal electricity system based on such a CLFR. Fig. 8 shows a schematic diagram of the solar thermal power plant with LHTES storage included. Such a system could operate with a low cost single salt option such as NaNO2, which has a suitable melting point, low cost, and acceptable heat capacity. The feasibility of applying this type of LHTES system to a further, 240 MW CLFR project in NSW, (Australia) is also being investigated. The 240 MW project is expected to operate at these temperatures and employ inexpensive, low pressure turbines similar to those employed in nuclear power plants. Although the CLFR array can be designed to supply solar steam at 360 C to the main boiler steam drum, it is currently unclear whether this would oer cost advantages over the lower temperature approach envisaged above. Application of LHTES to an MTSA system would follow a similar design approach shown schematically

300
Discharged energy Edischarge, MJ/m3

r0 = 0.01 m
200

r1 = 0.1 m T0 = ( Tm - 10 ) K Pb

100

KNO3
0 0 10 20 Time t, min 30 40 50

Fig. 6. Comparison of KNO3 and Pb discharging speeds in model LHTES.

3.0 Fluorides Chlorides Carbonates Bromides Nitrates Hydroxides Eutectics

Thermal conductivity , W/mK

2.0

Li2CO3 LiF Na2CO3

CaCl2 1.0 NaOH NaNO3 LiNO3 0 500 KNO3 LiBr 600 700 800 900 1000 1100 Li2CO3Na2CO3 LiCl MgCl2 KCl NaCl

NaF

1200

1300

Melting point Tm, K

Fig. 7. Thermal conductivity of molten salts.

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Fig. 8. Power plant design incorporating high-temperature LHTES storage.

in Fig. 8. The storage unit and turbine would be situated on the ground, and air would probably be used as the primary circulating uid in the tower receivers. Use of a single storage and turbine unit for multiple towers will allow increased eciency, not only through a reduction in part-load turbine operation, but because the eciency of Brayton cycle turbines increases quite rapidly with turbine size in the hundred kW region. In this case, suitable salts would include NaCl or Na2CO3, the latter having a melting point suitable for advanced Brayton turbines, low medium cost, and high thermal conductivity. This paper has not addressed the design aspects of PCM systems at medium and high temperature. Tamme (2003) proposes a cascaded PCM system for trough collectors using oil heat transfer uid, but this would be unnecessary in a direct steam generation CLFR, which would need only one steam generation temperature. He outlines some design problems associated with the low thermal conductivity of salts and salt mixtures used as PCMs in the medium temperature range. The low conductivity of salt mixtures, vessel corrosion, and the avoidance of freezing stresses in the containment vessels of metal PCMs are serious design problems in medium and nigh temperature PCM systems. Thermal conductivity may be able to be overcome using direct heating of the PCM without a heat exchanger wall, or by micro encapsulation. The latter method has the disadvantage of use of a non-PCM matrix. Dynamic thermal modeling of various design options is required and will form part of on-going investigations aimed at integrating LHTES storage into STE power plants based on low cost CLFR and MTSA. Sensible heat molten salt storage systems and exist in the medium temperature range, and their corrosion problems are

under control. However, the very low volume of PCM salts required compared to sensible heat molten salt storage, and the advantage of more constant temperature output, suggests that PCMs must be more cost eective once thermal conductivity issues are resolved.

2. Conclusion High-melting point PCMs in solar thermal electricity based CLFR are described and the charging and discharging characteristics of high melting point PCMs are discussed theoretically and numerically. From the present study, the following conclusions may be drawn: 1. In selecting high melting point phase change materials for use with the CLFR and MTSA solar array technologies, molten salts with melting point in the 5001300 K appear promising. Generally, melting point and heat capacity tend to increase in the order of nitrates, chlorides, carbonates and uorides, making very high temperature PCMs potentially attractive for the MTSA. Some metal PCMs may also be considered. 2. In high melting point LHTES systems, the thermal conductivity of the PCM becomes an important factor. Materials which exhibit appropriate high melting points can also exhibit large thermal conductivity. In particular, Na2CO3 has been identied as a useful low cost high conductivity storage option for MTSA operating with Brayton Cycle turbines. 3. Large CLFR plants using low pressure turbines could successfully incorporate LHTES storage based on a PCM salt such as NaNO2, which is low cost and

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has a suitable melting point. Zn may be a cost eective option for trough systems using higher boiler temperatures. Implementation of high temperature LHTES storage in solar thermal electricity systems based on CLFR and MTSA systems will require numerous design issues to be resolved associated with thermal conductivity, vessel corrosion, and vessel integrity under PCM freezing. However, such PCMs are potentially both technically and economically feasible and will be the subject of further investigations.

References
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to energy storage. vol. 2. U.S. Dept of Commerce, National Bureau of Standards. Mills, D.R., Morrison, G.L., 2000. Compact linear Fresnel reector solar thermal power plants. Solar Energ. 68 (3), 263283. Mills, D.R., Schramek, P., 1999. Multi tower solar array (MTSA) with ganged heliostats solar paces, Font-Romeu France, Journal de Physique IV, 9, Pr3.8388. Mills, D.R., Schramek, P., Dey, C., Buie, D., Imenes, A.G., Haynes, B.S., Morrison, G.L., 2002. Multi Tower Solar Array Project, Proceedings of the 40th annual ANZSES conferenceSolar Harvest, Newcastle, Australia, November 2730. Mills, D.R., Le Lievre, P., Morrison, G.L., 2003. Solar preheating of the liddell coal red power plant, Proceedings of ANZSES 2003 Conference, Melbourne, December. Saitoh, T.S., 1994. Moving Boundary Heat Transfer. Yokendo, Ltd., Bunkyo-ku, Tokyo, Japan. Saitoh, T.S., Fujino, T., 1998. J. JSES 24 (6), 3542. Saitoh, T.S., Ono, T., 1984. Trans. ASME J. Sol. Energ. Eng. 106, 403407. Saitoh, T.S., Matsuhashi, H., Ono, T., 1985. Solar Energ. 135 (6), 541547. Seki, N., 1995. Thermal Storage Engineering. Morikita Publ. Co., Ltd., Chiyoda-ku, Tokyo, Japan. Tamme, R., 2003. NREL Workshop on Thermal Storage for Trough Power Systems, Golden, Colorado, February 2123. Available at http://www.eere.energy.gov/troughnet/documents/thermal_energy_storage.html.