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Study on the Properties and Applications of Molten Salts

Conference Paper · December 2010

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 Study on the properties and applications of
molten salts
Xiang-yang ZHAO, Zhi-tong YAO, Jin-hui LI*
Department of Environmental Science & Engineering, Tsinghua University, Beijing, China
Email: better.001@163.com, jinhui@tsinghua.edu.cn

Abstract: The general properties of molten salt were reviewed. It had wide applications in the
fileds or using as catalyzers, solvents, heat transfer medium, pyroprocessings, electrolytes,
and molten salt oxidation. The development of molten salt oxidation was emphasized
especially.
Key words: molten salt; catalyzers; heat transfer medium; pyroprocessings; electrolytes;
molten salt oxidation

1. Introduction solvents: thermal and chemical stability

especially toward moisture, negligible pressure
Molten salt refers to a salt that is in the
vapors, non-flammable, stability at high
liquid phase that is normally a solid at standard [3, 4]
potential, and high conductivity .
temperature and pressure (STP). A salt that is
As a non-flame, thermal process that
normally a liquid at STP is usually called a room
destroys all organic materials while retaining
temperature ionic liquid, although technically
inorganic and hazardous components in the melt,
molten salts are a class of ionic liquids (ILs).
molten salt oxidation can be used as either
Molten salts have a variety of uses. Molten
hazardous waste treatment or energy harvesting
chloride salt mixtures are commonly used as
similar to coal and wood gasification [5, 6].
baths for various alloy heat treatments, such as
annealing and mar tempering of steel. Cyanide 2．Properties of molten salts
and chloride salt mixtures are used for surface
Ionic substances with melting points close to
modification of alloys such as carburizing and
room temperature are referred to as ionic liquids.
nitro carburizing of steel. Cryolite is used as a
They have unique properties, e.g.,
solvent for aluminum oxide in the production of
environmentally benign, nonvolatile,
aluminum.
nonflammable and are good solvents for a wide
Fluoride, chloride, and hydroxide salts can
range of both organic and inorganic materials, so
be used as solvents. A eutectic mixture of
they are widely used in different chemical
choline chloride/urea is liquid at ambient
processes such as heterogeneous catalysis,
temperature and can be used as a non-volatile
synthesis, electrochemistry, sensors, battery
reaction medium for the synthesis and [7,8]
applications and analytical chemistry .
crystallization of a coordination polymer [1].
Molten salts are extensively studied in view
Molten salts can also be used as heat
[2]
of their unique physical and chemical properties,
transfer fluids as well as for thermal storage .
such as high chemical and thermal stability,
New electrolytes for lithium battery consisting
broad electrochemical window, negligibly low
of room temperature molten salts have been
vapor pressure, and ability to dissolve various
tested. Easy to prepare, their chemical and
solutes, and of their possible applications as
physical properties make them serious
solvents in organic synthesis and in batteries [9].
contenders to conventional organic liquid
 Molten salt technology is a catch-all phrase 3.1. Catalyzers
that includes some very diverse technologies:
Ionic liquids are becoming widely used in
electro-chemistry, heat transfer, chemical
synthetic organic chemistry and the intrinsic
oxidation/reduction baths, and nuclear reactors.
reactivity of these molten salts is ought to be
All of these technologies are linked by the
studied. Clues to the non-innocent nature of
general characteristics of molten salts:
many ionic liquids are contained in the reports of
1) Can function as solvents
altered reactivity of dissolved substrates,
2) Have good heat transfer characteristics (heat
unexpected catalytic activity and unforeseen
capacity)
by-product formation [13, 14].
3) Function like a fluid (like water)
Large increases in reactivity and selectivity
4) Can attain very high temperatures
have been achieved using this medium for
5) Can conduct electricity [15]
homogeneously catalyzed reactions , and in
6) Some molten salts have chemical catalytic
some cases, reactions have been demonstrated to
properties
only work in the ionic environment and not in the
Some simple physical properties of the
molecular solvents.
ionic liquids that make them important as
While similar remarks can also be attributed
potential solvents for synthesis are the following:
[10, 11] to heterogeneously catalyzed reactions, the depth
of study has not yet been achieved for trends to
1) Unusual combinations of reagents that
be easily identified. However, it is clear that there
can be brought into the same phase.
is a large potential using the combination of ILs
2) Composed of poorly coordinating ions
and solid catalysts in both liquid-phase and
and have the potential to be highly polar yet non
gas-phase reactions. The latter shows the
coordinating solvents.
versatility of ILs in stabilizing homogeneous
3) Immiscible with a number of organic
using thin films of the IL. Much more research
solvents and provide a non aqueous, polar
needs to be performed in this area to explore the
alternative for two-phase systems.
scope of IL-solid interactions in terms of
4) Nonvolatile and can be used in
chemical reactivity and selectivity [16].
high-vacuum systems and eliminate many
containment problems. 3.2. Solvents
One of the important features of molten
Efforts have been made to eliminate the
salts is their ability to conduct electricity [12]. For
consumption of volatile organic compounds
example, solid sodium chloride does not conduct
(VOCs) as reaction media that contribute to
electricity; it is an insulator. If NaCl is placed
the major source of environmental pollution.
into water, the mutual attraction both sodium and
Non-volatile ionic liquids, or near ambient
chlorine have for water molecules cause their
temperature organic molten salts, have been
bonds to break and form ions within the water.
recently utilized as potential substitution of
These electrically charged ions can conduct
traditional organic solvents for catalytic
electricity if there is a voltage potential. Molten
synthesis, separation and electrochemical
salts conduct electricity the same way they do
process.
when they are dissolved in water; some of the
Inorganic eutectic mixtures, such as
salt molecules are dissociated into ions, which
halides and hydroxides, are known to decrease
allows the ions to conduct electricity.
significantly the freezing points of molten
3．Applications of molten salt salts and have been used as inert or reactive
‘‘low-temperature’’ solvents for solid-state
 synthesis.
Room-temperature ionic liquids (ILs) are
gaining wide recognition as novel solvents in
chemistry. Their application in analytical
chemistry, especially in separating analytes, is
merited because ILs have some unique
properties, such as negligible vapor pressure,
good thermal stability, tunable viscosity and
miscibility with water and organic solvents, as
well as good extractability for various organic
[17]
compounds and metal ions . disadvantage is these molten salts corrode metal
3.3. Heat transfer medium
Molten salts have been used in many
industries as a high temperature heat transfer
medium. It uses a Sodium Nitrite/Nitrate mixture
to absorb and store the sun's heat from the focus
of many mirrors in the desert upon a central
tower. The heat from the salt is then transferred
via a heat exchanger to produce steam to drive a
conventional steam turbine and generator to
[18]
produce electricity from the sun
3.4. Pyroprocessings
Molten salts are also used to produce most
non-ferrous metals (non-iron like metals; e.g.,
aluminum, titanium, etc.). The most notable and
oldest use was the production of aluminum via
electrolytic decomposition of alumina.
A non-electrical method of using molten
salts to produce metals is used to produce
titanium. Titanium oxide from various ores is
reacted with chlorine and carbon to form
titanium tetrachloride, which is a salt of titanium.
[19]
This salt is melted and boiled off so as to
distill and purify the TiCl4. It can then be
contacted with sodium or magnesium metal in
the Hunter or Kroll process to produce titanium
sponge and sodium chloride or magnesium
chloride. The titanium sponge is a raw material in
the fabrication of finished titanium metal
[20]
products . The most common use of synthesis gas
3.5. Electrolytes
Molten salts are also used in Fuel Cells.
While there are many different type currently
being researched, the usual characteristics is to
employ a mixture of various salt carbonates (e.g.,
Na2CO3, sodium carbonate & other carbonates
of lithium, potassium, etc.) as the electrolyte of a
battery called a fuel cell. The advantage of this
type of fuel cell is its ability to use carbon
containing fuels (methanol, gasoline, etc.)
directly in the production of electricity. The
very easily. Lifetime of the electrodes is still a
problem area [21].
Molten salts are currently used
commercially to strip metal clean of impurities.
This simple process utilizes the high temperature
and catalytic and oxidative properties of Sodium
Nitrite/Nitrate (NaNO2/NaNO3) salts. A molten
salt bath of sodium nitrite/nitrate salts can be
used to clean the paint off of its appliances that
failed quality control checks. The molten salt
completely cleans the metal of all paints by
thermally decomposing and oxidizing the paint
into carbon dioxide and water vapors. The
stripped metal appliance can then be repainted.
Molten salt batteries are a class of primary
cell and secondary cell high temperature electric
[22]
battery that use molten salts as an electrolyte .
They offer both a higher energy density through
the proper selection of reactant pairs as well as a
higher power density by means of a high
conductivity molten salt electrolyte. These
features make rechargeable molten salt batteries a
promising technology for powering electric
vehicles.
3.6. Molten salt oxidation
Molten salts have also been studied since
the early 1900s to gasify coal in a process called
Molten Salt Oxidation (MSO). The molten salt
used is usually sodium carbonate heated above its
melting point of 851℃ to around 900℃- 1000℃.
however, is to produce Methanol (methyl
alcohol-CH3OH) which can also be used as a fuel,
and is used in race cars, but is usually a raw
material for the production of various organics
such as octane boosters, gasoline additives,
plastics, chemicals and drugs[23].
MSO will play a significant role in the
production of hydrogen fuel for the Hydrogen
Economy via the "water shift" reaction where the
Synthesis gas is converted into nearly pure H2
gas [24].
Molten salt oxidation is a non-flame,
thermal process that destroys all organic
materials while simultaneously
inorganic and hazardous components in the melt.
It is used as either hazardous waste treatment or
energy harvesting similar to coal and wood
[25]
gasification .
It has been used for safe biological and
chemical weapons destruction, and processing
waste such as scrap tires where
incineration/effluent treatment is difficult. The
major downside of the process compared to
direct incineration is the eventual saturation of
the melt by contaminants, and
reprocessing/replacement.
In the mid-1950s, Rockwell, Inc. conducted
extensive tests of molten salts for the purpose of
destroying chemical weapons. Similar to the
advantages of using molten sodium carbonate to
gasify coal, MSO has the additional advantage of
having large amounts of sodium in close
proximity to the decomposing chemical weapons
molecules [26].
This is significant because
weapons usually contain large amounts of
fluorine, sulfur and/or chlorine, all of which can
form radicals which may cause the production of
carcinogens such as dioxins [27].
The long residence times of the chemical
weapons in a molten salt bath, as compared to
incineration, combined with the presence of large
amounts of sodium allows the chlorine, sulfur,
and fluorine radicals plenty of time to form stable,
and safe, sodium compounds such as sodium
sulfate, sodium chloride, and sodium fluoride [28,
29]
.
4. Conclusion
In this paper, the general situations of
molten salt systems were reviewed. The
development of molten salt oxidation was
emphasized. Applications of molten salts to the
areas of catalyzers, solvents, heat transfer
medium, pyroprocessings, electrolytes, and
molten salt oxidation have good prospect. In
order to continually develop the molten salt
retaining system, it is necessary further to know the
properties of molten salts and relevant theories,
as well as exploiting the new methods and novel
systems of synthesizing molten salts.
5. Acknowledgment
This work was financially supported by
direct Chinese National 863 High Technology (Grant
No. 2009AA064001).
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