Uranium Conversion

Uranium Conversion
After the yellowcake is produced at the mill, the next step is conversion into pure uranium
hexafluoride (UF6) gas suitable for use in enrichment operations. During this conversion,
impurities are removed and the uranium is combined with fluorine to create the UF6 gas. The
UF6 is then pressurized and cooled to a liquid. In its liquid state it is drained into 14-ton
cylinders where it solidifies after cooling for approximately five days. The UF6 cylinder, in the
solid form, is then shipped to an enrichment plant. UF6 is the only uranium compound that exists
as a gas at a suitable temperature.
As with mining and milling, the primary risks associated with conversion are chemical and
radiological. Strong acids and alkalis are used in the conversion process, which involves
converting the yellowcake (uranium oxide) powder to very soluble forms, leading to possible
inhalation of uranium. In addition, conversion produces extremely corrosive chemicals that could
cause fire and explosion hazards.
Conversion and Deconversion

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:
UO2 + 4HF ===> UF4 + 2H2O deltaH = -176 kJ/mole
The tetrafluoride is then fed into a fluidized bed reactor or flame tower with gaseous fluorine to
produce uranium hexafluoride, UF6. Hexafluoride ("hex") is condensed and stored.
UF4 + F2 ===> UF6
Removal of impurities takes place at each step.
The UF6, particularly if moist, is highly corrosive. When warm it is a gas, suitable for use in the
enrichment process. At lower temperature and under moderate pressure, the UF6 can be
liquefied. The liquid is run into specially designed steel shipping cylinders which are thick
walled and weigh over 15 tons when full. As it cools, the liquid UF6 within the cylinder becomes
a white crystalline solid and is shipped in this form.
The siting, environmental and security management of a conversion plant is subject to the
regulations that are in effect for any chemical processing plant involving fluorine-based
chemicals.
Secondary sources of conversion supply
Secondary supply of equivalent conversion services includes UF6 material from commercial and
government inventories, enricher underfeeding, and DU tails recovery. Uranium and plutonium
recycle effectively adds to this. All these were estimated at 26,000 tU in 2013 but with the end of
the Russian HEU supply to USA, they will be much less from 2014 and are projected to be less
than 16,000 tU to 2022.
Depleted uranium and deconversion
Depleted uranium (DU) is stored long-term as UF6 or preferably, after deconversion, as U3O8,
allowing HF to be recycled. It may also be deconverted to UF4, which is more stable, with much
higher temperature of volatilization. To early 2007, about one-quarter of the world's 1.5 million
tons of DU had been deconverted. World deconversion capacity was about 60,000 t/yr at end of
2010.
The main deconversion plant is the 20,000 t/yr one run by Areva NC at Tricastin, France, and
over 300,000 tonnes has been processed here. The technology has been sold to Russia. Two
plants have been built by Uranium Disposition Services (UDS) at Portsmouth and Paducah,
USA, with capacities of 13,500 and 18,000 t/yr respectively. A 6500 t/yr plant is being built at
New Mexico in the USA by International Isotopes (INIS). In the UK, Urenco ChemPlants is
building a plant and expects 2016 start-up.
Russias W-ECP deconversion plant is at Zelenogorsk Electrochemical Plant (ECP) in Siberia.
The 10,000 t/yr deconversion (defluorination) plant was built by Tenex under a technology
transfer agreement with Areva NC, so that depleted uranium can be stored long-term as uranium
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.

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Conversion and Deconversion

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