Salt systems

Electrolysis. Electro winning of hafnium, zirconium, and titanium has been proposed as an alternative to the KroU process. Electrolysis of an all chloride hafnium salt system is inefficient because of the stabiHty of lower chlorides in these melts. The presence of fluoride salts in the melt increases the StabiHty of in solution and results in much better current efficiencies. Hafnium is produced by this procedure in Erance (17). 

Sohd salt, ground and packaged in several particle size grades, can be used in saturated salt brines to increase the fluid density (28). However, sized salt is most often used as a water-soluble material for bridging or sealing porous formations. At one time the sized salt systems were used primarily for completion or workover operations, but use has increased as ddU-in fluids for horizontal wells (29). 

Fig. 4. In the Solar Two Project a molten salt system shown in the scheme replaces Solar One s water/steam system. In operation, "cold" molten salt is pumped from a storage tank to a receiver on a tower. Sunlight reflected from a field of sun-tracking mirrors heats the salt in the receiver to 1050°C. The heated salt then flows down into a hot storage tank where it is pumped to a heat exchanger to produce the steam that drives a turbine. Some of the hot molten salt can also be stored to produce steam on demand at a later time. Salt cooled to 550°C in the steam generator recirculates through the system and...

Based on the results of the Solar One plant. Southern California Edison formed a consortium that included DOE and EPRI to constmct a Solar Two Project. Solar Two will convert the idle Solar One central receiver plant from a water/steam system to a molten salt system, thereby improving efficiency and operating performance. With the molten salt technology, solar energy can be collected during the day and stored in the salt to produce electricity when needed. The three-year demonstration is scheduled to begin in late 1996. 

G. J. Janz, C. B. AHen, N. P. Bansal, R. M. Murphy, and R. P. T. Tomkins, PhjsicalProperties Data Compilations Kelevantto Energy Storage. II Molten Salts Data on Single and Multi-Component Salt Systems, U.S. Department of Commerce, National Bureau of Standards, Washington, D.C., Apr. 1979, pp. 142-154. 

Alternatively, the TiCl may be reduced using hydrogen, sodium, or magnesium. It follows that TiCl2 is the first stage in the KroU process for the production of titanium metal from titanium tetrachloride. A process for recovery of scrap titanium involving the reaction of scrap metal with titanium tetrachloride at >800° C to form titanium dichloride, collected in a molten salt system, and followed by reaction of the dichloride with magnesium to produce pure titanium metal, has been patented (122,123). 

BeryUium reacts with fused alkaU haUdes releasing the alkaU metal until an equUibrium is estabUshed. It does not react with fused haUdes of the alkaline-earth metals to release the alkaline-earth metal. Water-insoluble fluoroberyUates, however, are formed in a fused-salt system whenever barium or calcium fluoride is present. BeryUium reduces haUdes of aluminum and heavier elements. Alkaline-earth metals can be used effectively to reduce beryUium from its haUdes, but the use of alkaline-earths other than magnesium [7439-95-4] is economically unattractive because of the formation of water-insoluble fluoroberyUates. Formation of these fluorides precludes efficient recovery of the unreduced beryUium from the reaction products in subsequent processing operations. 

In the preeipitation of salt systems, the erystallizing speeies normally exist as free ions in solution and in this ease the solubility of eaeh ion has to be taken into aeeount. Thus for a sparingly soluble substanee the solubility... 

Berry, D.A. and Ng, K.M., 1996. Separation of quaternary conjugate salt systems by fractional crystallization. American Institute of Chemical Engineers Journal, 42, 2162. 

Typical values of self-diffusion coefficients and mutual diffusion coefficients in aqueous solutions and in molten salt systems such as (K,Ag)N03 are of the order... 

Electrochemically, the system metal/molten salt is somewhat similar to the system metal/aqueous solution, although there are important differences, arising largely from differences in temperature and in electrical conductivity. Most fused salts are predominantly ionic, but contain a proportion of molecular constituents, while pure water is predominantly molecular, containing very low activities of hydrogen and hydroxyl ions. Since the aqueous system has been extensively studied, it may be instructive to point out some analogues in fused-salt systems. 

Other Pyrochemical Processes. The chemistry of pyrochemi-cal separation processes is another fertile area of research e.g., new molten salt systems, scrub alloys, etc. and the behavior of plutonium in these systems. Studies of liquid plutonium metal processes should also be explored, such as filtration methods to remove impurities. Since Rocky Flats uses plutonium in the metal form, methods to convert plutonium compounds to metal and purify the metal directly are high-priority research projects. 

Recent development work has been done defining the above operating parameters and evaluating a CaCl2-CaF2 salt system. 

Plutonium Extraction vs MgC12 Concentration in the NaCl-KCl-MgCl2 Salt System. 

Figure 7. Distribution Coefficient for Americium Extraction vs MgC12 Concentration in the NaCl-KCl-MgCl2 and NaCl-CaCI2 MgC12 Salt Systems.

The extent of these reactions will be determined by the reaction free energy and concentration for each of the impurities in the molten anode/electrolyte salt system. Americium can be used as an example of a very electropositive impurity ... 

The classical example of a soUd organic polymer electrolyte and the first one found is the poly(ethylene oxide) (PEO)/salt system [593]. It has been studied extensively as an ionically conducting material and the PEO/hthium salt complexes are considered as reference polymer electrolytes. However, their ambient temperature ionic conductivity is poor, on the order of 10 S cm, due to the presence of crystalUne domains in the polymer which, by restricting polymer chain motions, inhibit the transport of ions. Consequently, they must be heated above about 80 °C to obtain isotropic molten polymers and a significant increase in ionic conductivity. 

The ionic conductivity of the MEEP/metal salt systems was improved by adding a-Al203 particles into the complexes. Chen-Yang [603] obtained a conductivity 0=9.7x10" S cm" for the composite polymer complex MEEP/Li-CIO4/2.5 wt% AI2O3. The cation transport number was in this case 0.77. 

Table 16 Maximum conductivity of polynorbornenes bearing cyclotriphosphazenes/lithium salt systems at 30 °C...

Wave-front shearing interferometry has been applied to transparent molten salt systems by Gustafsson et al. " The optical path of a light beam traversing the cell at an arbitrary level x is expressed by... 

Sindzinger and Gillan have calculated the thermal conductivity for NaCl and KCl melts as well as for sohds on the basis of MD simulations in Ml thermal equilibrium using the Green-Kubo relations (Table 17). In a single molten salt system, the local fluxes jz and of charge and energy... 

Because of the inherent technical difficulties, investigations of transport properties in molten salts are much less common than those of aqueous solutions. However, interpretation of the phenomena seems to be even simpler in molten salts where water is not involved. Molten salt systems are considered to be the simplest liquid electrolytes. Data have been compiled largely due to the great efforts of the Janz group." "... 

The electrolysis temperature affects the electrolyte conductivity, the overpotential, and the solubility of the electrodeposit in aqueous as well as in molten salt systems. The effect of temperature is particularly important in the latter case. The lower limit of the temperature of operation is set by the liquidus temperature of the bath and the solubility of the solute. Generally, the temperature chosen is at least 50 °C above the melting temperature of... 

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