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Solar Energy Materials

Solar Energy Materials and Solar Cells 27 (1992) 181-187 and Solar Cells
North-Holland

Thermophysical properties of some paraffins


applicable to thermal energy storage
M. Hadjieva, St. Kanev and J. Argirov
Central Laboratory of Solar Energy and New Energy Sources, Bulgarian Academy of Sciences,
72 Boulevard Trakia, 1784 Sofia, Bulgaria

Received 11 November 1991

An experimental study has been conducted with the aim to investigate and evaluate thermo-
physical properties of technical grade paraffins appropriate for solar energy storage applications.
The results obtained involve the kinetics of phase transition and latent heat of phase change,
the thermal cycling stability at heating and cooling and specific heat for the temperature range
of application.
A method for the automatic computer controlled thermal cycling has been developed. The
dynamic mode of precise uniform rising and lowering of the temperature at various rates has
been accomplished. Nine hundred thermal cycles have been carried out on two different
mixtures of technical grade paraffins, varied by their composition.
The change of the DSC kinetics measured by Mettler TA 3000 and the relative thermody-
namic values of the phase transitions were not registered after cycling. The calculated enthalpies
of three paraffin mixtures were found to depend on their oil content and the distribution of
a t o m s defined by chemical and gas chromatographic analyses.

1. Introduction

The increasing industrial interest in finding heat storage materials for efficient
use of thermal energy in corresponding applications stimulates the investigation of
phase change materials. Paraffin mixtures have been evaluated as suitable thermal
storage materials (TSM) with melting points in the temperature range of 25-100°C.
Homogeneous mixtures formed by some substances of homologous series of
saturated hydrocarbons (CnH2n+2) and unsaturated hydrocarbons in different
volume ratios, may cover a wide range of phase transition temperatures. The
advantages such as a sufficiently high enthalpy of phase change, small segregation
of components, small changes in structure during repeated phase transitions, as
well as low price, provoke their investigation [1-5]. The results presented in the
publications pointed out a comparatively small number of thermal cycles. They
cannot serve the evident proof of practical applicability. Abhat [1], for example,
referred to 150 thermal cycles without established changes in the thermodynamic

Correspondence to: St. Kanev, Central Laboratory of Solar Energy and New Energy Sources, Bulgarian
Academy of Sciences, 72 Boulevard Trakia, 1784 Sofia, Bulgaria.

0927-0248/92/$05.00 © 1992 - Elsevier Science Publishers B.V. All rights reserved


182 M. Hadjieua et al. / Thermophysical properties of some paraffins

characteristics of the paraffins investigated. Moreover, the previous publications


do not offer complete analyses of paraffins including their composition and
structure. That makes it difficult for the correct comparison and understanding of
the thermal storage results.
The aim of the present investigation was to study three different mixtures of
technical grade paraffins, which are by-products of lubrication oil production: to
find the temperature of phase change, to calculate the latent heat, to determine
the influence of a sufficiently large number of thermal cycles on the value of the
enthalpy of melting, to study the dependence of the enthalpy on the hydrocarbon
composition and oil content.

2. Measurement technics
Testing the thermal performance and reliability upon repeated cycling allows
the experimental evaluation of the storage performance of technical grade paraf-
fins.
The investigation method is based on the evaluation of the melting and freezing
curves as a plot of temperature versus time during repeated thermal cycling. The
response upon heating and cooling gives information about the storage capacity of
phase change materials (PCM). It depends on the rate of heating and cooling, the
thermal conductivity and density of PCM and on the degree of impurity as well.
Taking into account the considerations above, the computer controlled measur-
ing system for thermal cycling has been accomplished (fig. 1) to study the thermal

Fig. 1. Technical scheme of computer controlled measuring system for thermal cycling of TCM: (1)
vessel for cooling fluid, (2) electromagnetic valve, (3) circulation pump, (4) cold end of thermocouple
sunk in ice, (5) measuring unit, (6) control unit, (7) Apple II computer, (8) monitor, (9) heater, (10)
water in the glass capsule, (11) thermostat, (12) reference thermocouple, (13, 14) TS material under
investigation.
M. Hadjieva et al. / Thermophysical properties of some paraffins 183

TEMPERATURE vs TIME IMINI


60
SEiYO
rY_
0 34
1 32 . 9
2 33
3 32.6 60 -
4 32.7
5 33.3
6 33.1
7 33.1
a
9
Ii- >o
c - >OFF
dT=O 304 0 . 301 , 60
. 1 40 ’ tie ’
.
mrasurem~ It ,‘: f 33 7 CYCLE Yf
ttmc 0 cc. 43 33.-O FREE 362

Fig. 2. Linear programmed mode for temperature changes in a heat transfer medium.

stability of thermal storage materials. During the present investigation the glass
capsules with TSM hermetically sealed, were sunk in a thermostat containing
water (12 dm3) as the heat transfer medium. Cu/constantan differential thermo-
couples with the cold end sunk in melting ice were used to measure the tempera-
ture of the sample specimens. The temperature control was realized by a differen-
tial thermocouple with a hot end directly immersed in the heat transfer medium.
The thermocouples were connected to an amplifier and a 1Zbit analog-digital
converter (ADC) using a multiplexer. An electromagnetic valve controlled the
mass flow rate of the cooling water. The circulation pump helped the thermal
homogeneity of the water in the thermostat by intensive stirring to avoid thermal
stratification. A BASIC program for an Apple II microcomputer served to realize
a heating and cooling mode at a constant rate (fig. 2), to collect and store the
measured data, and to visualize and compare them. The cycling mode was
established at a temperature range of 28 to 70°C in order to include the
temperature ranges of phase transitions of several types of paraffin mixtures, and
to provide the possibility of cycling them simultaneously at the same conditions.
The optimum rate of heating and cooling for the investigated TSM was fixed at
1.2 deg/min. The duration of the heating and cooling processes was established
both at 35 min. Each thermal cycle included one hundred and thirteen measure-
ments of the temperature. The reproducibility of the temperature measurements
at the selected rate of heating and cooling was *OS”C. It was achieved by
comparing the temperature of water in the whole water volume of the thermostat
to the temperature of the water measured in one of the capsules. So, the influence
of the thermal conductivity of the glass wall was taken into account by two
reference points.
A differential scanning calorimeter with the software of the Mettler TA 3000
system was used to measure and calculate the thermodynamic (TD) parameters
before and after thermal cycling.
184 M. Hadjieva et al. / Thermophysical properties of some paraffins

Table 1
Basic characteristics of the composition of the paraffin mixtures

Type Molecular C H Density Oil


weight (%) (%) (g/cm’) content
(%o)
A (CZZHWI) 311 85.80 14.19 0.7536 2.09
B (Cz.zHd 327 85.13 14.84 0.7554 1.89
C (C24.7%3) 348 85.25 14.75 0.7593 8.67

Chemical analyses of the samples and gas chromatographic analyses were done
to identify the composition and structure of the investigated mixtures of paraffins.

3. Results and discussion

Three different paraffin mixtures indicated as type A, B, and C with hydrocar-


bon formula C22.2T-L17 C23.2H40.4, and C2J-L respectively, were investigated.
The results of the chemical analysis of the samples are presented in table 1.
The kinetics data of the nine hundred thermal cycles carried out at the
established cycling mode on TSM samples (4 g each) were registered by a
computer controlled cycling system.
The curve shown in fig. 3 illustrates the typical behavior of TSM under
investigation at the cycling mode of heating and cooling until complete melting and
solidification. A small hysteresis of a few degrees can be seen, probably due to a
comparatively low thermal conductivity of TSM. Preliminary calculations concern-

68

0 10 20 30 40 50 60 70
1 i ME lmin 1
Fig. 3. Typical thermal cycling curve of the paraffins in comparison with the temperature curve of the
water in the capsule.
h4. Hadjieva et al. / Thermophysical properties of some paraffinr 185

TEMPERATURE *C HEAT FLOW


EXOTHERMAL-- a

I 10.000 mw I

30.00

40.00

50.00

60.00
/ --”

Fig. 4. Typical DSC curve of melting of the paraffins, type A and B.

ing the absorbed and released thermal energy lead to the conclusion that the
amount of released heat corresponds to the amount of absorbed heat. The
amounts remain practically unchanged during thermal cycling.
The DSC curves of heating of type A and type B were recorded before, during
and after thermal cycling. A typical DSC curve of melting is illustrated in fig. 4 and
shows two temperature peaks corresponding to two temperature ranges of solid-
solid and solid-liquid phase transitions, respectively. They were practically un-
changed after 900 thermal cycles for type A and type B paraffin mixtures. While
Abhat [l] referred to a lowering after cycling of the secondary peak in the DSC
curve, which corresponds to a solid-solid phase transition and is connected with
polymorphic transformations.
The DSC curve of type C paraffins shows only one ill defined peak at the
temperature of melting, probably due to overlapping of the solid-solid and
solid-liquid phase transition ranges.
The obtained DSC results for thermodynamic characteristics of the three types
of paraffins are summarized in table 2. The TD values for average peak tempera-
tures of phase transitions remain unchanged before, during and after testing on
thermal cycling. The calculated values of the specific heat CC,> depending on the
phase state are included within the range of the published data [l-3,5]. The
calculated enthalpy of melting is a total value summing up the heat of solid-solid
and solid-liquid phase transitions. The enthalpies before thermal cycling do not
differ substantially from the enthalpies after cycling for both type A and B. It
could be concluded, that there is no evident segregation and degradation of the
investigated paraffins. The evidently low enthalpy of type C and its broad phase
transition range determined its elimination from the tests of cycling.
The previous publications [1,2,4] do not report detailed data about the composi-
tion and structure of the paraffins investigated to facilitate the exact comparison of
the obtained results and to understand the matter of the properties shown. Our
186 M. Hadjieva et al. / Thermophysical properties of some paraffins

Table 2
Thermophysical characteristics of three types of paraffin mixtures

Type Tsolid-solid Tsolid-liquid AH Cp (J g - 1 °C - 1)


(°C) (°C) (kJ/kg) solid liquid
Type A
before cycling 30.5 47.1 166 2.51 1.98
after cycling 30.8 46.6 163 2.00 1.39

Type B
before cycling 41.8 57.1 220 2.80 2.20
after cycling 43.0 57.8 224 2.60 2.00

Type C
before cycling 62.6 155 2.6 1.8

Tsolid_solid, Tsolid_liquid = average peak temperature

results from chemical analysis, gas chromatographic analysis (table 3) and DSC
analysis allow the comparison and suggest a relation between the oil content and
the value of latent heat. If we would only considered the influence of the oil
content, our results would be in contradiction to the conclusion of Abhat [1]: The
total enthalpy of phase transition of type C (8.67% of the oil content) is lower than
the enthalpy of type A and B, which could be related to its higher oil content. The
TD parameters of type B in comparison with type A and C confirm the same
relation showing the highest enthalpy at its lowest value of the oil component.
On the other hand, the presence of a higher concentration of monocyclic
naphtene (3.2%) and bicyclic naphtene (2.9%) in type B could contribute to the
value of its phase transition enthalpy by their rich energy, spatial conformation
forms of molecules. The matter continues to be under forthcoming investigations.

Table 3
Distribution of C atoms for two fractions of paraffins (type A and B)
Distribution among a type of Distribution of saturated hydrocarbons
CH groups (alkanes) among a number of CH groups
Hydrocarbons Content (%) Alkanes Content (%)
type Type A Type B type Type A Type B
Alkanes
(CHH2H+2) 99.6 93.9 C18H38 1.3 -
Monocyclic naphthene 1.8 3.2 C19H40 4.4 1.1
Bicyclic uaphthene 1.6 2.9 C20H42 14.7 6.1
C21H44 18.8 16.6
C 22H 46 20.3 26.8
Cz3H48 18.2 23.8
C24H50 14.3 15.2
C25H52 8.0 6.6
C26H54 - 3.8
M. Hadjieva et al. / Thermophysical properties of some paraffins 187

4. Conclusions

(1) The investigation of mixtures of technical grade paraffins has proved the
presence of two peaks of phase transitions at a comparatively low value of the oil
component (type A and B). They remain practically unchanged after a sufficiently
large number of thermal cycles.
(2) From the obtained values, no significant difference in the total latent heat
before, during and after repeated thermal cycling can be seen. The results draw
the conclusion that there is no noticeable degradation in the structure of the
paraffins tested on thermal cycling.
(3) The dependence of the amount of latent heat on the oil content and the
presence of the cyclic naphtene should be discussed further.
(4) The paraffins of type B are proposed as an efficient material in thermal
energy storage. Their relatively high enthalpy of phase transition and stability of
structure at thermal cycling, also their advantage as a cheap by-product, are clear
evidence of their practical applicability.

References

[1] A. Abhat, Thermal Energy Storage (Reidel, Dordrecht, 1982) p. 33.


[2] E. van Galen and G.J. van den Brink, Int. J. Ambient Energy 7, 1 (1986).
[3] A.G. de Jong and G.J. Hoogenforn, Thermal Storage of Solar Energy, The Hague, 1989, p. 123.
[4] S. Hasnain, B.N. Gibbs, ISES Solar World Congress, Hamburg, Germany, 1987.
[5] N. Mancini, Thermal Storage of Solar Energy, Amsterdam, 1980, p. 99.