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Conversion
Conversion
Uranium leaves the mine as the concentrate of a stable oxide known as U3O8 or as a peroxide. It
still contains some impurities and prior to enrichment has to be further refined before being
converted to uranium hexafluoride (UF6), commonly referred to as 'hex'.
Conversion of uranium oxide to UF6 is achieved by a dry fluoride volatility process in the USA,
while all other converters use a wet process.
After initial refining of U3O8 (or peroxide), which may involve the production of uranyl nitrate,
uranium trioxide is reduced in a kiln by hydrogen to uranium dioxide. This is then reacted in
another kiln with hydrogen fluoride (HF) to form uranium tetrafluoride (HF4). The tetrafluoride
is then fed into a fluidized bed reactor with gaseous fluorine to produce UF6. The alternative wet
process involves making the tetrafluoride from uranium oxide by a wet process, using aqueous
HF.
Some secondary supplies, from downblended high-enriched uranium or re-enriched tails may be
supplied or already exist in the form of UF6. Recycled uranium from reprocessing plants needs
to be converted so that it can be enriched.
Chemistry of Conversion
In the dry process, uranium oxide concentrates are first calcined (heated strongly) to drive off
some impurities, then agglomerated and crushed.
For the wet process, the concentrate is dissolved in nitric acid. The resulting solution of uranyl
nitrate UO2(NO3)2.6H2O is fed into a countercurrent solvent extraction process, using tributyl
phosphate dissolved in kerosene or dodecane. The uranium is collected by the organic extractant,
from which it can be washed out by dilute nitric acid solution and then concentrated by
evaporation. The solution is then calcined in a fluidized bed reactor to produce UO3 (or UO2 if
heated sufficiently).
Purified U3O8 from the dry process and purified uranium oxide UO3 from the wet process are
then reduced in a kiln by hydrogen to UO2:
U3O8 + 2H2 ===> 3UO2 + 2H2O deltaH = -109 kJ/mole
or UO3 + H2 ===> UO2 + H2O deltaH = -109 kJ/mole
This reduced oxide is then reacted in another kiln with gaseous hydrogen fluoride (HF) to form
uranium tetrafluoride (UF4), though in some places this is made with aqueous HF by a wet
process:
oxide, and HF is produced as a by-product. The W-ECP plant is similar to Arevas W2 plant at
Pierrelatte in France and has mainly west European equipment. It was commissioned in
December 2009.
Russia is also building a plant at Angarsk to deconvert UF6 to UF4, recovering some HF in the
process. Capacity of 2000 t/yr was planned for 2012, with subsequent increase to 6000 t/yr.
These use essentially a dry process, with no liquid effluent. It is the same as that used for the
enriched portion, albeit at a scale of 20,000 tonnes per year in the one plant.
The UF6 is first vapourised in autoclaves with steam, then the uranyl fluoride (UO2F2) is reacted
with hydrogen at 700C to yield an HF product for sale to converters and U3O8 powder which is
packed into 10-tonne containers for storage.
UF6 + 2H2O == UO2F2 + 4HF
3UO2F2 + 2H2O + H2 ===> U3O8 + 6HF
The INIS plant in Idaho uses a slightly different deconversion followed by fluorine extraction
process (FEP), on a toll basis. The deconversion plant had been used to produce DU metal for
the military and was purchased by INIS. In this, the depleted UF6 is first vapourised in
autoclaves and hydrogen is added to give depleted UO2 and anhydrous UF4 which is the main
product for sale. The FEP then involves reacting some UF4 with silica to give silicon fluoride
(SiF4) as a commercial co-product.
Ownership title is normally transferred to the enricher as part of the commercial deal. It is
sometimes considered as a waste, though only for legal or regulatory reasons and in the USA, but
usually it is understood as a long-term strategic resource which can be used in a future generation
of fast neutron reactors. Any much more efficient enrichment process would also make it into an
immediately usable resource to supply more U-235. Enrichment companies with ownership of
large amounts of depleted uranium are quite clear that their stocks are a significant asset.