A novel method proposed to choose the optimal working fluid—solely from the point of view of expansion route—for a given heat source and heat sink (characterized by a maximum and minimum temperature). The basis of this method is the novel classification of working fluids using the sequences of their characteristic points on temperature-entropy space. The most suitable existing working fluid can be selected, where an ideal adiabatic (isentropic) expansion step between a given upper and lower temperature is possible in a way, that the initial and final states are both saturated vapour states and the ideal (isentropic) expansion line runs in the superheated (dry) vapour region all along the expansion. Problems related to the presence of droplets or superheated dry steam in the final expansion state can be avoided or minimized by using the working fluid chosen with this method. Results obtained with real materials are compared with those gained with model (van der Waals) fluids; based on the results obtained with model fluids, erroneous experimental data-sets can be pinpointed. Since most of the known working fluids have optimal expansion routes at low temperatures, presently the method is most suitable to choose working fluids for cryogenic cycles, applied for example for heat recovery during LNG-regasification. Some of the materials, however, can be applied in ranges located at relatively higher temperatures, therefore the method can also be applied in some limited manner for the utilization of other low temperature heat sources (like geothermal or waste heat) as well.
One of the most crucial challenges of sustainable development is the use of low-temperature heat sources (60–200 °C), such as thermal solar, geothermal, biomass, or waste heat, for electricity production. Since conventional water-based thermodynamic cycles are not suitable in this temperature range or at least operate with very low efficiency, other working fluids need to be applied. Organic Rankine Cycle (ORC) uses organic working fluids, which results in higher thermal efficiency for low-temperature heat sources. Traditionally, new working fluids are found using a trial-and-error procedure through experience among chemically similar materials. This approach, however, carries a high risk of excluding the ideal working fluid. Therefore, a new method and a simple rule of thumb—based on a correlation related to molar isochoric specific heat capacity of saturated vapor states—were developed. With the application of this thumb rule, novel isentropic and dry working fluids can be found applicable for given low-temperature heat sources. Additionally, the importance of molar quantities—usually ignored by energy engineers—was demonstrated.
Recent results are shown about the peculiarities of the pseudo-critical region, with special emphasis on properties important for energy production and conversion. The property-map of some materials, which are relevant as model fluids or as working / cooling fluids in energy engineering (argon, methane, water and carbon dioxide) and their relative positions to various adiabats – influencing their stability through the anomalous properties – are presented. Some potential technological problems related to the existence of these anomalies are discussed.
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