IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage

2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
A Study of Erythritol as Phase Change Material
H.Kakiuchi, M.Yamazaki, M.Yabe, S.Chihara
Y.Terunuma, Y.Sakata and T.Usami
Tsukuba Research Center, Mitsubishi Chemical Corporation
8-3-1,Chuo, Ami, Inashiki, Ibaraki 300-0332, Japan
3803594@cc.m-kagaku.co.jp
Abstract
Erythritol has melting point 119 C and heat of fusion 339.8KJ/Kg. The possibility of Erythritol as heat
storage material was examined according to the standard such as thermodynamic criteria, kinetic criteria
and chemical criteria. The heat exchange performance of Erythritol was investigated with ice-on-coil type
heat exchanger vessel.
Introduction
Recently, heat storage technology, especially latent heat storage technology , are paid attention from a
viewpoint of the global environmental problems and the advanced utilization of energy in the world. In
Japan, ice storage system is becoming popular due to peak sift of electrical demand. This system stores
cold heat in night time using surplus electricity, then uses stored cold heat for air-conditioning in day
time. These are many types of ice storage system such as ice-on-coil type, dynamic type and capsule type.
Sagara (1998) reported that floor heating system came into wide use in Japan for public buildings, such as
facilities of the aged and residential buildings [1]. PCM provided by Japanese manufactures for floor
heating are Sodium Sulphate Decahydrate, having melting point of about 30C, and Paraffin having
melting point of 50C. Every manufactures use plate or tube capsules and install its into under floor.
For space heating of office building, Sodium acetate trihydrate having melting point of 58C, Sodium
Acetate Trihydrate salt mixture having melting point of 47C and Calcium Chloride Hexahydrate having
melting point of 27C have been used by capsule type heat storage system [2]. For air-conditioning system
, Sodium Sulphate Decahydrate salt mixture having melting point of about 10C has been developed
(Telkes,1974) (Kakiuchi,1994) [3, 4].
However, these temperature of phase change of these latent heat storage materials are inappropriate for
storing solar energy or waste heat given in hot water supply or in a boiler. These are required to have a
relatively high temperature of phase change of from 90 to 200C. Typical phase change material having
melting point of from 90 to 200C are Polyethylene and Pentaerythritol. Polyethylene’s melting point is
about 120 to 140C and its heat of fusion is 214KJ/Kg. Polyethylene have been used for small size
electrical stove as PCM in Japan. Pentaerythritol can store heat on going through phase transformations,
but here the transformation is solid-solid phase transition. Takahashi et al (1988) reported that
Pentaerythritol ‘s thermal conductivity was relatively low [5]. So, they tested the pentaerythritol slurry for
raising thermal conductivity.
Hoermansdoerfer (1989) proposed that sugar alcohol such as Erythritol, Mannitol and Galactitol were
able to use as a heat storage material which had a high temperature of phase change in his Patent [6].
Besides his patent, Xylitol was also proposed as phase change material (Guex,1981) [7]. In this report, we
investigated the possibility of Erythritol as phase change material, concerning with thermodynamic
properties, kinetic behaviour, thermal stability and heat exchanger experiment.
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
Sugar Alcohol Phase Change Material
Sugar alcohol is extremely safe material used as sweetening agents. Erythritol, Xylitol, Sorbitol and
other things originally exist in nature. Erythritol is used for drinks in order to sweeten without calorie.
Xylitol is very famous sweetening agents to prevent tooth decay. A gum using Xylitol is very popular in
Japan, too. Melting point, heat of fusion and cost of typical sugar alcohol are shown in Table 1. Latent
heat of fusion were measured by using differential scanning calorimeter (DSC220C) of Seiko Instruments
Inc.. Reagent grade of sugar alcohol were used without purifying. The price of sugar alcohol in Japan
depends on individual surveys of Mitsubishi Chemical Co., Ltd.
Every sugar alcohol showed in Table 1 has comparatively large heat of fusion except D-Sorbitol. It
is found that these sugar alcohol have possibility of good phase change material. These sugar alcohol’s
structural formulas are shown in Table 2. It is found that configuration of Erythritol and Galactitol is
mirror symmetric, configuration of Mannitol is axis symmetric, configuration of Xylitol and Sorbitol isn’t
divided into before mentioned both groups. Hoermansdoerfer (1989) proposed in his patent that if their
chain length was an even number and at the same time their configuration in reference to the chain centre
was symmetric, they not only showed a significant higher heat of fusion, and also possessed a noticeable
less supercooling of the melt [6]. But we think that it needs to investigate relation between symmetric
configuration and thermodynamic behaviour and between chain length and thermodynamic behaviour.
Latent heat of fusion per unit volume of these sugar alcohol and selected phase change materials are
shown in Figure 1. It is found that Erythritol, Mannitol and Galactitol are able to store high energy par
volume than other materials. We investigate Erythritol’ thermal properties and examine the behaviour in
heat exchanger in this report. Heat of fusion of Barium Hydroxide Octahydrate is very large and the
temperature of phase change is suitable for supplying hot water. But, Barium Hydroxide Octahydrate is
classified in highly toxic material in Japan and has corrosiveness. So, we think Barium Hydroxide
Octahydrate is not suitable for PCM.
Table 1 Melting point, Heat of Fusion and Cost of typical sugar alcohol
Melting Point
(C)
Heat of Fusion
(KJ/Kg)
Density
(at 20C)
Cost
(US$/Kg)
Erythritol
D-Mannitol
Galactitol
Xylitol
D-Sorbitol
120
[8]
166-168
[9]
188-189
[9]
93.0-94.5
[9]
96.7-97.7
[8]
339.8
316.4
351.8
263.3
185.0
1.45
[8]
1.52
[9]
1.47
[9]
1.52
[9]
1.5
[8]
5.0
6.7-7.5
-
6.7-8.3
1.1
*1US$ = 120YEN
C
C
C
C
CH
2
OH
CH
2
OH
HO
HO
H
H
OH
C
C
C
C
CH
2
OH
CH
2
OH
H
HO H
OH
OH
C
C
CH
2
OH
CH
2
OH
H OH
H
Mannitol
Garactitol
Erythritol
Table.2
H
H
H
OH
C
C
C
CH
2
OH
CH
2
OH
HO
H
H
C
C
C
C
CH
2
OH
CH
2
OH
HO H
OH
OH
OH
Xylitol Sorbitol
H
OH
H OH
H
OH H
HO
H
Table 2 Representative sugar alcohol’s structural formulas [8]
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
Figure 1 Latent heat of fusion per unit volume of selected phase change materials [8][9][10]
*Both data of Pentaerythritol and Pentaglycerol are solid-solid phase transition point .
*Density value is used of solid except H2O. H2O value is liquid density.
Figure 2 Enthalpy Curve of Erythritol
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
Material Investigation of Erythritol
Thermodynamic Investigation
Thermal properties of Erythritol (food additive grade ; Mitsubishi Kagaku Foods Co. Ltd. ) are shown
in Table 3. Specific heat of Erythritol were measured by using heat insulation type specific heat
measurement apparatus (SH-3000) of Vacuum Science and Engineering Company. Specific heat curve is
shown in Figure. 2. It is found that Erythritol melts at 119C from this curve. Erythritol is a single element
like ice, because it melts congruently. It has huge heat of fusion 320KJ/Kg almost equal ice’s. Erythritol
is able to store 1.4 times thermal energy than ice in a heat storage system, because Erythritol’s liquid
density is larger than Ice’s solid density. Thermal conductivity is higher than Polythene. On the other
hand, specific heat is less than inorganic salt hydrate, because Erythritol doesn’t have water molecule. In
Erythritol, the biggest problem is volume change in phase change of solid to liquid. Volume of Erythritol
changes about 10% during solid to liquid phase transition. So, heat exchanger is required tough structure
or special method reducing volume change.
Table 3 Thermal Properties of Erythritol (Food additive grade ; Mitsubishi Kagaku Foods Co. Ltd.)
Chemical Structure C
4
H
10
O
4
Molecular Weight 122.2
Melting Point (C) 118.0
Heat of Fusion (KJ/Kg) 339.8
Specific Heat (KJ/Kg]C) at 20C
at 140C
1.383
2.765
Density (Kg/dm
3
) at
20C
at 140C
1.48
1.30
Heat Conductivity (KJ/m]h]C) at 20C
at 140C
2.640
1.173
• Melting point and Heat of fusion were mesured by DSC (Seiko Instruments Inc. )
• Specific heat were measured by heat insulation type specific heat measurement apparatus
(Vacuum Science and Engineering Company)
• Density were measured by Archimedes method.
• Heat conductivity were measured by hot wire method.
Kinetic Investigation
A cylinder container made of stainless steel of volume 6.0*10
-5
m
3
was produced, to evaluate
solidification and fusion behavior of Erythritol. We poured Erythritol ( Mitsubishi Kagaku Foods Co. Ltd.
) 0.05Kg into the container and measured temperature change of it at the height of 0.01m from the bottom
of container and recorded it in a recorder. Thermocouple of copper-constantan were used for measurment.
The container containing Erythritol was sunk to the temperature controled oil bath and heated to melt
Erythritol from 30 to 140 in 3 hours. After that, holding 140 for 6 hours, erythritol was completely
melted. Then, heating was quitted to solidify Erythritol, the container in the oil bath was cooled by
natural. A temperature change of the Erythritol in this time is shown in Fig. 3.
When heating was started, temperature of Erythritol rose with oil and became with 119 degree
constant. It was understand that it was melting. In the cooling process, the change of temperature wasn’t
obserbed even if it passed 119 degree that was a melting point in a cooling process. After that, it was
crystallized at 82 degree and a temperature rose up to the melting point. It is found that Erythritol
crystalizes between 60 to 100 degree from liquid phase by our experiments. We think that a nucleating
agent becomes necessary to inhibitate supercooling if it is used in a capsule type heat storage system.
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
• Figure 3 Melting and Solidification curve of Erythritol
Chemical Investigation (Thermal stability of Erythritol)
Erythritol originally exists in nature and is extremely safe material used as sweetening agents.
Although erythritol is combustibles, we are not thinking so danger. Because, the flash point of erythritol
is very high which is 245 C in comparrison with normally used temperature. Corrosiveness to container
material is evaluating now.
The heat degradation of Erythritol becomes a problem most in the case that Erythritol is used as a
heat storage material. It was found that Erythritane was formed when Erythritol was heated. Erythritane is
formed by erythritol’s dehydration of 1,4 position. It is well known that cyclic ther is synthesized from
sugar alcohol by heating in the presence of an acid catalyst. Even this reaction is thought with the kind of
its.
We evaluated thermal stability of erythritol in the sealing container made of stainless steel. Inside
volume of the stainless steel container was about 1.4*10
-5
m
3
. Erythritol was filled up to 50vol %, 90vol %
of the container and was carried out evaluation. It was found that the degradation reaction from erythritol
to erythritane that was suggested with Table4 was comparatively restrained in a stainless steel sealing
container. Also, it was found that the degradation reaction depended on oxygen concentration, because
the degradation speed of filling quantity 50vol % was faster than the degradation speed of 90vol %. It
was suggested that a acid catalyst didn’t form sufficiently because of low oxygen concentration in the
sealing container.
Next, we carried out the degradation rate constant of erythritol in stainless steal sealing container
about each temperature (140,150,160,180 ) and Arrhenius plot. From above results, the degradation rate
of erythritol was able to suppose a first order reaction style. The result is shown to Table. 5.
A heat storage material is repeated solidification and fusion for a long time. Accordingly, the
prediction of heat of fusion quantity versus using time is very important. Lifetime prediction of erythritol
was carried out on the basis of the experiment result in the sealing container made of stainless steel. The
terminating point was determined when purity of erythritol reached to 90% of initial. The purity of
erythritol decreases to 90% about 70,000 hours later when it continuously is heated to 140 degree in the
sealing container. It is understood to have sufficient lifetime as a heat storage material, because
degradation is 10% in initial even if it is used for about 8 years with continuation heating. Although we
are doing a repetition test of solidification and fusion at present, the acceleration of the degradation by
solidification and fusion has not been observed during evaluation. We think that lifetime of erythritol
higly depends on temperature than repeat of solidification and fusion.
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
Table 5 E and A value of Erythritol in stainless steal container
E(Kcal/K) A(1/hr)
50vol% 90vol% 50vol% 90vol%
Erythritol 31.5 32.9 1.24E11 4.21E11
* E : Activation Energy ; A : Frequency Factor
O
HO
OH
O
HO
OH
O
HO
OH
Acid
+ Acid +
H2O
Erythritol
Erythritane
+ O2
C C C C
OHOH
H H H
OH
H
H
OH
H
C C C C
OHOH
H H H
OH
H
H
OH
H
Table 4 Mechanism of Erythritol Degradation
Figure 4 Lifetime of Erythritol as PCM
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
Heat Exchanger Investigation using Erythritol
Experimental
Latent heat storage material is used actually by heat exchange with heat transfer medium. Therefore, it
is very important to understand theproperties of heat exchanger. The heat exchange vessel shown in
Photo1 was produced to evaluate heat exchange characteristics of erythritol. A heat exchange method was
adopted the simplest ice-on-coil type. Inside volume of the heat storage vessel used to evaluation is
210dm
3
and erythritol is included 240 . This system consists of electricity heater unit (3kW), feed water
unit, bypass line and hot water supply line other than it.
Discharging performance were measured swinging flow rate with 3,5,8,10 dm
3
/min. in condition of
room temperature 20 22 , heat storage temperature 140 , Tin10 within 3 . Experiments enforced
8 times a total, by twice every each flow rate. Yet, bypass valve was controlled, for the purpose of doing
not discharge steam from exaust gate, while Tout had being over 100 degree.
Experiment result is shown in Figure 5 and fine reproducibility was confirmed in each flow rate.
Also, discharged heat quantity of experiment is biggest 142MJ and agreed for the most part with
theoretical discharged heat quantity 147MJ. It was found that erythritol acted as heat storage material
with ice-on-coil type heat exchanger vessel from this result.
Photo. 1 Experimental Apparatus of Heat Storage Vessel using Erythritol
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
Simulation analysis
A simulation model was designed in accordance with the following principle.
1. Heat storage behavior of Erythritol is able to expresse with all specific heat at constant volume
( Melting point is 119 120 ).
2. There is no supercooling.
3. There is no convection heat transfer of a liquid phase.
4. Heat transfer tube is a straight tube.
5. Heat storage material exists only around the tube.
( Namely, heat storage material grows to radius 25 mm thickness.)
6 .Water does not boil.
7. Outside of system makes a complete heat insulation condition except for entrance of water.
8. The stream makes turbulent flow that progressed.
The comparative result between actual hot water supply experiment and caliculation in a flow rate
0.312m
3
/h., average Tin 7 by simulation are shown in Figure6. In this figure, the result of simulation
are showed thin line, experimental data with thick line. A difference is observed in the diacharging
temperature curve of hot water supply in part, but accumlation curve of discharging heat quantity fits
experimental discharging curve. A calculation experiment of erythritol with heat storage vessel of ice-on-
coil type became possible by using this simulation from this result. We think that it is needed to evaluate
heatdischarging properpies changing plumbing pitch and plumbing diameter etc. according to a purpose,
from now on.
Figure 5 Evaluation of Heat discharging property
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
Conclusion
It was found that erythritol was able to use as heat storage material from this investigation. The possibility
of erythritol as heat storage material was examined according to the standard such as thermodynamic
criteria, kinetic criteria and chemical criteria. Erythritol was investigated heat exchange performamnce
with ice-on-coil type heat exchanger vessel.
Details are shown as follows:
Thermal properties of erythritol necessary as a heat storage material was measured. It was found that
erythritol was an excellent heat storage material and heat of fusion per unit volume was 1.4 times of
ice. However, it was suggested that an attention was necessary to the design of heat storage apparatus
because volume change about 10% on going through phase transformation.
Erythritol melted congruently and phase separation was not observed. Erythritol melted sharply at the
melting point. Supercooling phenomenon was observed. It was found that erythritol crystallised
60 100 degree in a range.
It was found that Erythritane was formed by erythritol’s dehydration of 1,4 position when erythritol
was heated. Also it was found that degradation of erythritol was retarded throughout a sealing
container.
It was found that the purity of erythritol decreased to 90% about 70,000 hours later when it
continuously was heated to 140 degree in the sealing container filled up to 90% of volume.
We carried out a discharging experiment by using erythritol as a heat storage material with ice-on-coil
type heat storage vessel. It was obtained 97% of theoretical discharging heat quantity in a discharging
process. Although a discharging experiment was enforced 8 times a total changing a flow rate,
reproducibility was admitted. It was understood that erythritol was able to use with ice-on-coil heat
storage vessel.
A discharging simulation program of erythritol in ice-on-coil type heat storage vessel was prepared.
The calculated discharging heat quantity was reproducing observed data well.
Figure 6 Comparison of calculation result using Erythritol simulation model with experimental result
IEA Annex 10 – PCMs and Chemical Reactions for Thermal Energy Storage
2
nd
Workshop, November 11-13 1998, Sofia, Bulgaria
Reference
1. Sagara, K., 1998, “ Present Situation of PCM Thermal Energy Storage in Japan”, IEA Annex-10,
Phase Change Materials and Chemical Reactions for Thermal Energy Storage, First Workshop, 16-
17 April, Adana, Turky.
2. Ono, K., and Sue, N., “ STL Heat Storage System “, Air-conditioning and Refrigerator, vol.26, No.6.
(in Japanese)
3. Telkes, M., 1974, “Solar Energy Storage “, ASHRAE.J., 16, 38.
4. Kakiuchi, H., 1994, “Efficient Use of Electric Energy and Latent Heat Thermal Energy Storage”,
MIFS’94, Mie, Japan.
5. Takahashi, Y., Kamimoto, M. and Abe, Y., 1988, “ Heat Capacity, Heat of Transition and Thermal
Conductivity of Pentaerythritol and its slurry ”, Netsu Bussei, 2[1], 53-58.
6. Hoermansdoerfer, G., 1989, US Patent 4,795,580.
7. Guex, W. Riehen, K. and Fullinsdorf, P., 1981, US Patent $,295,517.
8. Monick, J. A., 1968, “Alcohols “, Reinhold Book Corp. USA, 416-417.
9. The Merck Index 11
th
Edition, 1989, Merck & Co. Inc.
10. Seki, N., 1995, “Chikunetsu Kougaku “, vol.1, Morikitasyuppan. (in Japanese)