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Jyoti Swaroop Repaka 07010042 April 10, 2010
Department of Mechanical Engineering, Indian Institute of Technology Bombay.
Praveen Jain 07d10002
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 alternatives available. 1
1 A Typeset in L TEX.
1 Introduction 2 Water as a working ﬂuid 3 Various other choices of working ﬂuids 4 General constraints in the selection of working ﬂuids 5 Carbon Dioxide 6 Organic and Titanium Based working ﬂuids 7 BZT Fluids Siloxanes 8 Alkali Metals 9 Mercury 9.1 Schiller power station . . . . . . . . . . . . . . . . . . . . . . . 9.2 Nuclear-heated mercury power plant . . . . . . . . . . . . . . 10 Organic Rankine Cycle working ﬂuids 1 1 2 3 3 4 5 6 6 6 7 7
List of Figures
1 2 3 A mercury-steam power plant. . . . . . . . . . . . . . . . . . . The NASA nuclear mercury turbine system. Note the extra cooling and lubricating loop using polyphenyl ether. . . . . . . Plant layout for organic rankine cycles. . . . . . . . . . . . . . 6 7 8
The working ﬂuid in a machine is the pressurized gas or liquid which actuates the machine. 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 performance of a thermodynamic power system releasing mechanical work are very dependent upon the properties of the working ﬂuid.
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 noncorrosive. 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 temperatures. 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 liquid 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. 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 turbine 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 withstanding great stresses. Another undesirable characteristic of water is that its saturation pressure at ordinary condenser temperatures is well below atmospheric 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 electrical 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.
Various other choices of working ﬂuids
• Carbonic acid / CO2  • Organic and Titanium Based • BZT ﬂuids eg. Siloxanes  • FC-72  • Ethanol  • Zeotropic working ﬂuids • Ammonia Maximum temperatures attainable are 58◦ C-78◦ C • HCFCs and HFCs • Petrol and alcohol • Mercury • Compressed air • Alkali Metals • 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
General constraints in the selection of working ﬂuids
The following parameters are considered, while selecting working ﬂuid for a plant. 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.
Many Hot Dry Rock geothermal energy plants have started utilizing supercritical CO2 instead of water. 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 between the cold CO2 in the injection well and the hot CO2 in the production 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 geothermal 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 disadvantageous 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.
Organic and Titanium Based working ﬂuids
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 ﬂuids for high temperature mechanical heat pumps by C.Zamﬁrescu et al. Their results have been summarized:
Biphenyl Biphenyl Methane Naphthalene Isoquinoline Titanium Tetrabromide Titanium Tetraiodide
Forms saturated vapor condensate during compression. Not suitable in vapor compression heat pumps. Forms saturated vapor condensate during compression. Not suitable in vapor compression heat pumps. High energetic and exergetic COPs. 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.
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 critical 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 eﬃciency and compactness. 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. Γ≡ V3 2c2 δ2p δv 2 (1)
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 thermodynamic 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
A siloxane is a chemical compound composed of units of the form R2 SiO
Alkali metals such as lithium, sodium and potassium are very eﬃcient working 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.
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. Mercury has a higher boiling point than water, i.e. at 357◦ C.
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
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.
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. 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. 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. 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. Butylbenzene shows highest eﬃciency. It has the lowest maximum and minimum process 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. Butylbenzene 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.
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