Alternate working fluids and their properties

for high temperature plants

Jyoti Swaroop Repaka Praveen Jain
07010042 07d10002
April 10, 2010

Department of Mechanical Engineering,

Indian Institute of Technology Bombay.

Abstract
This is a part of the course ME 306 - Applied Thermodynamics
taught by Prof. Uday N. Gaitonde. The topic is Alternate working
fluids and their properties for high temperature plants. (Topic ID-268).
Water has long been used as the working fluid for high-temperature
plants. But the increasing need for efficiency, higher power output and
wider range of applications of working fluids have created a need for
alternate working fluids. This report investigates the various alterna-
tives available. 1

1
Typeset in LATEX.

i
Contents
1 Introduction 1

2 Water as a working fluid 1

3 Various other choices of working fluids 2

4 General constraints in the selection of working fluids 3

5 Carbon Dioxide 3

6 Organic and Titanium Based working fluids 4

7 BZT Fluids Siloxanes 5

8 Alkali Metals 6

9 Mercury 6
9.1 Schiller power station . . . . . . . . . . . . . . . . . . . . . . . 6
9.2 Nuclear-heated mercury power plant . . . . . . . . . . . . . . 7

10 Organic Rankine Cycle working fluids 7

List of Figures
1 A mercury-steam power plant. . . . . . . . . . . . . . . . . . . 6
2 The NASA nuclear mercury turbine system. Note the extra
cooling and lubricating loop using polyphenyl ether. . . . . . . 7
3 Plant layout for organic rankine cycles. . . . . . . . . . . . . . 8

ii
1 Introduction
The working fluid in a machine is the pressurized gas or liquid which actuates
the machine.[6] Examples include steam in a steam engine, air in a hot air
engine and hydraulic fluid in a hydraulic motor or hydraulic cylinder.
It absorbs thermal energy and converts and provide work output in a
turbine. For a specified power output, the required size and obtained per-
formance of a thermodynamic power system releasing mechanical work are
very dependent upon the properties of the working fluid.

2 Water as a working fluid

Water is an excellent working fluid for high-temperature industrial heat
pumps due to its favourable thermodynamic properties and the fact that
it is plentiful, low in cost, nontoxic, chemically stable, and relatively noncor-
rosive. Water has mainly been used as a working fluid in open and semi-open
MVR systems, but there are also a few closed-cycle compression heat pumps
with water as working fluid. Typical operating temperatures are in the range
from 80◦ C to 150◦ C. 300◦ C has been achieved in a test plant in Japan, and
there is a growing interest in utilising water as a working fluid, especially
for high- temperature applications. The major disadvantage with water as
a working fluid is that the low volumetric heat capacity (kJ/m3 ) of water.
This requires large and expensive compressors, especially at low tempera-
tures. In addition, water has a relatively large change in specific enthalpy
when it vaporizes at ordinary steam generator pressures, which tends to limit
the mass flow rate for a desired power plant output. The properties of liq-
uid water and water vapor are also such that the back work ratios achieved
are characteristically quite low, and the techniques of superheat, reheat, and
regeneration can be effective for increasing power plant efficiencies.[7]
Water is less satisfactory insofar as some other desirable working fluid
characteristics are concerned. For example, the critical temperature of water
is only 374.14◦ C, which is about 225◦ C below the maximum allowable tur-
bine inlet temperatures. Accordingly, to achieve a high average temperature
of heat addition and realize the attendant higher thermal efficiency, it may
be necessary for the steam generator to operate at supercritical pressures.
This requires costly piping and heat exchanger tubes capable of withstand-
ing great stresses. Another undesirable characteristic of water is that its
saturation pressure at ordinary condenser temperatures is well below atmo-
spheric pressure. As a result, air can leak into the system, necessitating the
use of special ejector pumps attached to the condenser or de-aerating feed

1
water heaters to remove the air.
Although water has some shortcomings as a working fluid, no other single
working fluid has been found that is more satisfactory overall for large electri-
cal generating plants. Still, vapor power cycles intended for special uses may
employ working fluids that are better matched to the application at hand
than water. Cycles that operate at relatively low temperatures may perform
best with a refrigerant such as ammonia as the working fluid. Power systems
for high-temperature applications may employ substances having desirable
performance characteristics at these temperatures. Moreover, water may be
used together with some other substance in a binary vapor cycle to achieve
better overall performance than could be realized with water alone.

3 Various other choices of working fluids

• Carbonic acid / CO2 [9]

• Organic and Titanium Based

• BZT fluids eg. Siloxanes [3]

• FC-72 [13]

• Ethanol [13]

• Zeotropic working fluids

• Ammonia Maximum temperatures attainable are 58◦ C-78◦ C

• HCFCs and HFCs

• Petrol and alcohol

• Mercury

• Compressed air

• Alkali Metals[8]

• Other organic working fluids

• Ether and Chloroform Low boiling points and hence are not used in
high temperature plants.

• Carbon Disulphide Low boiling point, 46.3◦ C and hence cannot be

used in high temperature plants

2
4 General constraints in the selection of work-
ing fluids
The following parameters are considered, while selecting working fluid for a
plant.[10]
1. Molecular weight.
2. Critical temperature.
3. Critical pressure.
4. Acentric factor.
5. Boiling point.
6. Auto-ignition temperature.
7. Vapor pressure of the liquid.
8. Heat of vaporization.
9. Heat capacity of the liquid.
10. Heat capacity of ideal gas.
11. Cost.
12. Toxicity to humans.
13. Eco-friendly nature.
Based on the above parameters, the advantages and properties
of some of the working fluids are now discussed in detail.

5 Carbon Dioxide
Many Hot Dry Rock geothermal energy plants have started utilizing super-
critical CO2 instead of water.[9] Such plants run at approximately 200◦ C and
pressure of a few hundred bars.
Favorable properties of CO2 include the following:
1. Large expansivity, which would generate large density differences be-
tween the cold CO2 in the injection well and the hot CO2 in the pro-
duction well, and would provide buoyancy force that would reduce the
power consumption of the fluid circulation system.

3
 2. Lower viscosity, which would yield larger flow velocities for a given
pressure gradient.

3. CO2 would be much less effective as a solvent for rock minerals, which
would reduce or eliminate scaling problems, such as silica dissolution
and precipitation in water-based systems.

While the thermal and hydraulic aspects of a CO2 - EGS (Enhanced geother-
mal system) system look promising, major uncertainties remain with regard
to chemical interactions between fluids and rocks. An added advantage in
using CO2 is: Fluid losses are an unavoidable, and loss of water would be dis-
advantageous and costly, whereas fluid loss in an EGS plant running on CO2
would offer the possibility of geologically storing this greenhouse gas. CO2
may be an attractive heat transmission fluid not only for high-temperature
resources used for electricity generation, but may offer even greater benefits
for direct heat applications of lower-temperature geothermal resources.

6 Organic and Titanium Based working flu-

ids
Examples include:

1. Biphenyl

2. Biphenylmethane

3. Naphthalene

4. Isoquinoline

5. Titanium Tetrabromide

6. Titanium Tetraiodide

These working fluids which represent a promising cleaner alternative to

fossil fuel heating were assessed thermodynamically as potential working flu-
ids for high temperature mechanical heat pumps by C.Zamfirescu et al.[12]
Their results have been summarized:

4
 Biphenyl Forms saturated vapor condensate during compression.
Biphenyl Methane Not suitable in vapor compression heat pumps.
Naphthalene Forms saturated vapor condensate during compression.
Isoquinoline Not suitable in vapor compression heat pumps.
Titanium Tetrabromide High energetic and exergetic COPs.
Titanium Tetraiodide High energetic and exergetic COPs and can obtain temperatures of 6

This suggests that TiI4 is a promising working fluid for a heat pump
running at high temperatures.

7 BZT Fluids Siloxanes

It is demonstrated theoretically that fluids composed of molecules of sufficient
complexity may display isentropes that are concave in the pV thermodynamic
diagram in a limited region on the vapour side, in the vicinity of the criti-
cal point. As a consequence, it is physically possible that supersonic waves
evolving in that region behave in a counter-intuitive fashion: compressions
are smooth and isentropic while expansions are steep and non-isentropic.
These effects may be exploited in designing turbomachinery for better effi-
ciency and compactness.[3] The related phenomena and the complex fluids
that support them are known nowadays as BZT, from the names of the three
researchers who pioneered the field.[2]

V 3 δ2p
 
Γ≡ 2 (1)
2c δv 2 s
where v is the specific volume, p is the pressure and c2 = V 2 (δP/δv)s is
the zero-frequency speed of sound. A fluid to be BZT has to have a thermo-
dynamic region where Γ is negative. Various studies have been done on the
performance with various BZT working fluids for a range of parameters, and
it has been observed that Siloxanes perform greatly. 2
2
A siloxane is a chemical compound composed of units of the form R2 SiO

5
8 Alkali Metals
Alkali metals such as lithium, sodium and potassium are very efficient work-
ing fluids. They are generally used with the heat sources in a range above
800K-1250K. However, because these metals are highly corrosive, the heat
pipe envelopes have to be fabricated from high temperature refractory metals.[8]

9 Mercury
Liquid mercury has been proposed as a working fluid for a heat pipe type
of cooling device for spacecraft heat rejection systems or radiation panels.
The choice of mercury for a working fluid may seem bizzare as its both
expensive and extremely poisonous. But owing to sound thermodynamic
reasons, mercury has been used.[1] Mercury has a higher boiling point than
water, i.e. at 357◦ C.

9.1 Schiller power station

The Schiller power station at Portsmouth, New Hampshire, USA was the
last binary mercury/steam plant built. The site has two decommissioned
GE Mercury Turbines and two B&W Mercury/Steam boilers. It currently
uses three 50 MW coal-fired steam boilers built in 1950s. One of these is
being replaced with a fluidized-bed boiler to burn whole-tree wood chips and
other clean low-grade wood materials. The Schiller station consisted of two
7.5MW mercury units and one 25MW steam turbine. The rated capacity was
40MW. It was equipped to run on either Bunker-C fuel oil or bituminous coal.

Figure 1: A mercury-steam power plant.

6
9.2 Nuclear-heated mercury power plant
NASA designed a nuclear-heated mercury power plant intended to generate
large amounts of electricity in space. The reactor is cooled with a mixture of
sodium and potassium, (NaK) which heats a mercury boiler. The mercury
vapour drives a turbo-alternator and is then condensed and subcooled by
a secondary NaK heat rejection loop which transfers the waste heat to a
radiator for rejection to space. The design has an exotic potassium/mercury
boiler. It is a spiral stucture designed to fit in a small toroidal space in
a cylindrical spacecraft. The heat exchanger tubes are made of tantalum,
which is readily wetted by mercury, making for good heat transfer. The net
power output was 37 kW.

Figure 2: The NASA nuclear mercury turbine system. Note the extra cooling
and lubricating loop using polyphenyl ether.

10 Organic Rankine Cycle working fluids

In the last years, large endeavors have been made to extend the market share
of renewable energies. Power and heat cogeneration by solid biomass is one of
the most interesting options for a sustainable and reliable energy supply due
to its high availability.[4] Electrical power is usually generated in processes
based on the Rankine with water as a working fluid. The ORC process
uses an organic working fluid instead of water.[5] In contrast to water, the
expansion in the turbine ends for most organic fluids not in the wet steam
regime but in the gas phase above condenser temperature. Thus, often an
internal heat exchanger is used to improve efficiency.[11]

7
 Figure 3: Plant layout for organic rankine cycles.

Toluene has the highest vaporization enthalpy, but at a low temperature

level. Thus, toluene shows worst efficiency of the alkylbenzenes. Butylben-
zene shows highest efficiency. It has the lowest maximum and minimum pro-
cess pressure, vaporizes at maximum process temperature and its condenser
temperature is only slightly lifted. OMTS vaporizes at higher temperature
as toluene, but its vaporization enthalpy is significantly lower. It has the
lowest efficiency of the selected fluids.
As expected, efficiency rises with maximum process temperature. Butyl-
benzene gains 6.5% points and OMTS 4.7 % points from 523K to 623K. In
general, efficiency difference between the fluids rises with higher maximum
process temperature.

8
References
[1] Unusual working fluids, 2008.
[2] Bethe, H. A., and Teller, E. Deviations from thermal equilibrium
in shock waves.
[3] Colonna, P., Guardone, A., and Nannan, N. R. Siloxanes:
A new class of candidate bethe-zel’dovich-thompson fluids. Physics of
Fluids 19, 8 (2007), 086102.
[4] Curran, H. M. Use of organic working fluids in Rankine engines.
NASA STI/Recon Technical Report N 80 (Sept. 1979), 30917–+.
[5] Drescher, U., and Brggemann, D. Fluid selection for the organic
rankine cycle (orc) in biomass power and heat plants. Applied Thermal
Engineering 27, 1 (2007), 223 – 228.
[6] Eastop, and McConkey. Applied Thermodynamics for Engineering
Technologists, 5th ed. Prentice Hall, Singapore, 1993.
[7] Moran, M. J., and Shapiro, H. N. Fundamentals of Engineering
Thermodynamics, 5th ed. John Wiley & Sons Ltd, England, 2006.
[8] Morris, James F. (Fairview Park, O. Heat pipes containing alkali
metal working fluid.
[9] Pruess, K. Enhanced geothermal systems (egs) using co2 as working
fluid–a novel approach for generating renewable energy with simultane-
ous sequestration of carbon. Geothermics 35, 4 (2006), 351 – 367.
[10] S., G. Selection of working fluids for high-temperature heat pumps.
Fuel and Energy Abstracts 36 (September 1995), 367–367(1).
[11] Saleh, B., Koglbauer, G., Wendland, M., and Fischer, J.
Working fluids for low-temperature organic rankine cycles. Energy 32,
7 (2007), 1210 – 1221.
[12] Zamfirescu, C., Dincer, I., and Naterer, G. Performance evalu-
ation of organic and titanium based working fluids for high-temperature
heat pumps. Thermochimica Acta 496, 1-2 (2009), 18 – 25.
[13] Zhang, X. M. Experimental study of a pulsating heat pipe using fc-72,
ethanol, and water as working fluids. Experimental Heat Transfer 17, 1
(2004), 47 – 67.