Graduation Year

2015

Document Type

Dissertation

Degree

Ph.D.

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Chemical Engineering

Degree Granting Department

Chemical Engineering

Major Professor

Yogi Goswami, Ph.D.

Co-Major Professor

Elias Stefanakos, Ph.D.

Committee Member

Venkat Bhethanabotla, Ph.D.

Committee Member

Babu Joseph, Ph.D.

Committee Member

George Philippidis, Ph.D.

Keywords

conduction, inorganic salts, PCM, sensible heat, thermal radiation

Abstract

Inorganic salts are very promising as high-temperature heat transfer fluids and thermal storage media in solar thermal power production. The dual-tank molten salt storage system, for example, has been demonstrated to be effective for continuous operation in solar power tower plants. In this particular storage regime, however, much of the thermal storage potential of the salts is ignored. Most inorganic salts are characterized by high heats of fusion, so their use as phase-change materials (PCMs) allows for substantially higher energy storage density than their use as sensible heat storage alone. For instance, use of molten sodium-potassium eutectic salt over a temperature range of 260 to 560°C (the approximate operating parameters of a proposed utility-scale storage system) allows for a volumetric energy storage density of 212 kWhth/m3, whereas the use of pure sodium nitrate (T_m = 307°C) over the same temperature range (utilizing both sensible and latent heat) yields a storage density of 347 kWhth/m3.

The main downside to these media is their relatively low thermal conductivity (typically on the order of 1 W/m-K). While low conductivity is not as much an issue with heat transfer fluids, which, owing to convective heat transfer, are not as reliant on conduction as a heat transfer mode, it can become important for PCM storage strategies, in which transient charging behavior will necessarily involve heating the solid-phase material up to and through the process of melting. This investigation seeks to develop new methods of improving heat transfer in inorganic salt latent heat thermal energy storage (TES) media, such as sodium / potassium nitrates and chlorides. These methods include two basic strategies: first, inclusion of conductivity-enhancing additives, and second, incorporation of infrared absorptive additives in otherwise transparent media. Also, in the process, a group of chloride based salts for use as sensible storage media and/or heat transfer fluids has been developed, based on relevant cost and thermophysical properties data.

For direct conductivity enhancement, the idea is simple: a PCM with low conductivity can be enhanced by incorporation of nanoparticulate additives at low concentration (~5 wt %). This concept has been explored extensively with lower temperature heat transfer fluids such as water, ethylene glycol, etc. (e.g., nanofluids), as well as with many lower temperature PCMs, such as paraffin wax. Extension of the concept to high temperature inorganic salt thermal storage media brings new challenges—most importantly, material compatibility. Also, maintenance of the additive distribution can be more difficult. Promising results were obtained in both these regards with nitrate salt systems.

The second heat transfer enhancement strategy examined here is more novel in principle: increasing the infrared absorption of a semitransparent salt PCM (e.g., NaCl) with a suitable additive can theoretically enhance radiative heat transfer (for sufficiently high temperatures), thereby compensating for low thermal conductivity. Here again, material compatibility and maintenance of additive dispersion become the focus, but in very different ways, owing to the higher temperatures of application (>600°C) and the much lower concentration of additives required (~0.5 wt %). Promising results have been obtained in this case, as well, in terms of demonstrably greater infrared absorptance with inclusion of additives.

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