IEA/ECES Annex 18, The Fifth Workshop and Expert Meeting

Freiburg/Germany, November 3 – 5, 2008

Paraffin/Water Emulsion for Cold Storage

and Distribution Applications

Li Huang, Christian Dötsch

Fraunhofer Institute of Environmental, Safety, and
Energy Technology UMSICHT, Germany
 Introduction

Phase Change Slurry (PCS)

§ binary fluid composed of a Phase Change Material (PCM) and a carrier fluid
§ high energy density, pumpable

Ice slurry Hydrate slurry (TBAB)

Source: Fraunhofer UMSICHT Source: JFE Engineering Corporation

2
 Introduction

PCS based on paraffins

Shape-stabilized Microencapsulated paraffin Paraffin/Water-Emulsion

paraffin suspension suspension

Water

Paraffin

Surfactant
Source: H.Inaba, 1997

§ Suspension where § Suspension of § Dispersion of paraffin

paraffin is embedded into a microencapsulated paraffin in droplets in water with
support material water the help of surfactants

3
 Emulsion Components and Properties

Paraffin/water-emulsion components
Nucleating agent
PCM
prevent the
alkanes CnH2n+2 with supercooling effect of
n=14-16 or the emulsions induced
blends with a melting by the small droplet size
point of 0-20 °C (1-10 µm)

Surfactant
prevent the phase
separation and to 50 um

stabilize emulsions

4
 Emulsion Components and Properties

Paraffin and heat transfer capacity of emulsions

§ Paraffin: Rubitherm RT10 with a
120
melting point of 10 °C and a heat 110 Emulsion RT10-30%
100 Water
of fusion of 120 kJ/kg 90

Heat capacity [kJ/kg]

80
70
§ Total heat capacity 60
50
- sensible heat capacity of water
40 58 kJ/kg
- heat of fusion of the paraffin 30
20
10 29 kJ/kg
§ In the temperature range of 5-12 °C 0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
- Water: 29 kJ/kg Temperature [°C]

- Emulsion RT10-30 %: 58 kJ/kg

5
 Emulsion Components and Properties

Paraffin and heat transfer capacity of emulsions

§ The heat capacity of the
5
emulsion increases proportionally
with the paraffin fraction.

RT10 emulsions to water

4

Ratio heat capacity

§ Emulsion RT10-30 %: 2 times
3
Emulsion RT10-50 %: 2.8 times
§ Heat capacity of a PCS à
2
RT10 fraction >= 30 wt.%
1

0 10 20 30 40 50 60 70 80 90 100
RT10 concentration [wt.%]

6
 Emulsion Components and Properties

Paraffin and rheological behaviors of emulsions

§ Non-Newtonian fluid,
1000
shear-thinning behavior RT10-20 % RT10-30 %
RT10-40 % RT10-50 %
§ Viscosity of the emulsion increases 100 RT10-60 % RT10-70 %

sharply when the paraffin fraction

Viscosity [Pas]
10
exceeds 50 %.
1
§ The optimal RT10 fraction is 30-50 %,
when considering both the heat 0.1

capacity and the viscosity. 0.01

0 50 100 150 200
Shear rate [1/s]

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 Emulsion Components and Properties

Surfactant and stability of emulsions

§ Surfactants: amphipathic molecules
consisting of a non-polar
hydrophobic portion and a polar or water
surfactant hydrophilic
ionic portion (hydrophilic)
portion
§ Requirements on the emulsion for
hydrophobic
cold applications portion

- over long term storage and oil droplet

- under thermal-mechanical loads in

the pump systems
§ Stability: change in the droplet size

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 Emulsion Components and Properties

Surfactant and stability of emulsions

16
§ Sample: RT10-30 % th
measured on Februar 8 , 2007
th
14 measured on June 25 , 2008
§ No dramatic change in the drop

Density distribution [%]

12
size distribution was detected
10
over one year of storage.
8

0
0.01 0.1 1 10 100 1000
Droplet size [µm]

9
 Emulsion Components and Properties

Surfactant and stability of emulsions

§ Sample: RT10-30 %
§ Temperature: 5-18 °C, 50 cycles

10
 Emulsion Components and Properties

Surfactant and stability of emulsions

§ Sample: RT10-30 % st
16 Sample before the test, on August 8 , 2008
st
§ slight coalescence after a week Sample on August 11 , 2008
14 nd
Sample on August 12 , 2008
rd
Sample on August 13 , 2008
§ Sample RT20-30 % (melting point

Density distribution [%]

12 th
Sample after the test, on August14 , 2008
20 °C) was tested at Fraunhofer ISE 10

§ The emulsion withstood about 8400 8

6
cooling/heating cycles.
4

0
0.01 0.1 1 10 100 1000
Droplet size [µm]

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 Emulsion Components and Properties

Nucleating agent and supercooling effect of emulsions

1.0
§ Supercooling effect induced
0.8
by the small droplet size 0.6
0.4

Heat flow [mW/mg]

§ The nucleating agent offers
0.2
the necessary embryo surface 0.0
to start the nucleation in the -0.2
Emulsion RT10-30%+nucl., fr.
paraffin droplets and thus is -0.4 Emulsion RT10-30%+nucl., mel.
Emulsion RT10-30%, freezing
-0.6 Emulsion RT10-30%, melting
acting as a nucleating
-0.8 Paraffin, freezing
catalyst. Paraffin, melting
-1.0
-5 0 5 10 15 20 25
Temperature [°C]

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 Emulsion Components and Properties

little supercooling Nucleating

effect agent

high energy density

(min. 2 times water)
Paraffin O/W Paraffin
Emulsion (30-50 %)

relatively low viscosity

(max. 40 mPas)

good stability Surfactant

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 Application Study

§ Application in cold supply networks or cold storage systems

Source: Fraunhofer UMSICHT

14
 Application Study

§ Application in building cooling

capillary tube systems with the paraffin emulsion having a melting temperature of 20 °C for
cooling ceilings or walls

Source: Clina Heiz- und Kuehlelemente GmbH

15
Thank you very much for your attention!

L. Huang
Fraunhofer Institute for Environmental,
Safety and Energy Technology UMSICHT
Osterfelder Strasse 3
46047 Oberhausen, Germany
Tel.: +49 (0) 208/85 98-1149
Fax: +49 (0) 208/85 98-12 90
E-mail: li.huang@umsicht.fraunhofer.de