Nuclear Chemical Engineering Report

1. Configuration of PUREX process

PUREX which is the abbreviation of Plutonium, Uranium, Reduction, Extraction, or
Plutonium and Uranium Recovery by Extraction process, is a method developed as a solvent
extraction technology for reprocessing the spent nuclear fuel using TBP (tri-n-butyl-phosphate) in
late 1940. The PUREX extraction cycle consists of five fractions: U product, Pu product, high
intermediate/low-level, aqueous waste and off-gas waste. Figure below shows a schematic of the
reprocessing process and the explanation of each process.

a. Storage
The spent fuel containing 93.2% of uranium 238, 1.0% of uranium 235, 1.1% of plutonium,
0.6% of uranium 236 induced, and 4.7% of fission product are stored and cooled. When they are
ready to be reprocessed, they will be delivered to the shearing and dissolving part.

b. Shearing and Dissolving

In this section, spent fuels are sheared become metal chips etc. Then are dissolved into
the boiling concentrated nitric acid (8~11 M). Nevertheless, around 1% of the iodine in the
solution is distributed into TBP and retained up to the solvent regeneration step, and it may
accumulate it the recycled solvent. Therefore, iodine should be eliminated immensely as much
as possible. On the other hand, the metal chips which are not dissolved, are sealed into containers
and stored safely. While the remaining spent fuels (uranium, plutonium, and fission products) are
delivered to a separation process.

c. Separation
There are two processes in this part: co-decontamination and partitioning (where the
uranium and plutonium are separated from each other). In the co-decontamination process, the
first scrub is used for the recovery of Zr, second scrub is used for the recovery of Tc and Ru. Pu(IV)
in the organic phase is decreased to unextractable Pu(III) in the partitioning process to be back-
extracted selectively into the aqueous phase. The organic phase contains TBP, and the aqueous
phase contains uranium and plutonium.
Diluted nitric acid back-extracted the remains U(VI) in the organic phase. An organic phase
with ligands such as CMPO and TBP get contacted with an U(VI) aqueous phase. Then U(VI) in the
aqueous phase are moved to the organic phase by the complex formation of these ligands and
U(VI). Both Pu and U solution are then delivered to the purification section, while fission product
is vitrified and stored safely.

d. Purification of Uranium and Plutonium

There are two containers in this part: uranium purification and plutonium purification.
This step is important to remove the remaining fission product. When the targeted purity of the
products cannot be achieved in the specified extraction cycle, it becomes necessary to perform
re-extraction of U and Pu for further purification.

e. Denitration
After uranium and plutonium are purified, they are sent to denitration to produce
uranium oxide and MOX fuel. Thermal denitration reaction that is first-order endothermic will
transform UNH to uranium trioxide (UO3) at the temperature above 3000C.

2. Difference between PUREX and Advanced Reprocessing

 Issues in PUREX process
 The distribution of Np between product stream requires additional decontamination,
especially the U product.
 Pu is separated in high purity, converted to an oxide and back blended with U to prepare
MOX.
 Separating a combined U and Pu product would simplify the overall process, decrease the
number of unit operations, and alleviate proliferation concerns.

Below are some advanced reprocessing methods to overcome those issues.

a. COEX (Co-Extraction
In this process, uranium, plutonium, and neptunium are co-extracted and co-precipitated.
Pu stream is also eliminated in this method. In addition, this method only uses a single route for
the Np to eliminate the uranium purification cycle. Therefore, due to that single route, the process
is simplified, and this is one of the improvement to address PUREX’s issue. Besides that, no
plutonium separation at any point of this process is one of the advantages of COEX to solve the
proliferation problem.

b. UREX (Uranium Extraction)

The advantage of UREX is that it has a possibility to dispose of U as low-level waste without
the need for U purification cycle(s) would require decontamination of the U from Pu and Np.
Basically, UREX is similar to PUREX, but 95% of LWR spent fuel is removed by UREX process which
includes U and Tc extraction, Tc recovery, and U recovery. Then, 5% of the remaining solution
which is the minor actinides are treated in the next step. In the UREX method, Pu is not isolated
but is mixed with Np, therefore it means that the UREX method can alleviate the proliferation
issue.
 c. NPEX Process
In this process, Np and Pu are transferred to the aqueous phase and recovered, which can
address to an improvement of PUREX regarding producing MOX. Besides that, Pu isolation is
impossible in this process. Accordingly, a proliferation issue can be decreased.

d. DIAMEX-SANEX
This method focuses on the selective separation of long-lived americium (Am) and curium
(Cm) from short-lived nuclides. The DIAMEX solvent has four elements: oxygen, carbon,
hydrogen, and nitrogen. While the SANEX solvent has only one element: nitrogen. DIAMEX-SANEX
method can recover Np more than 99.9% and Am+Cm 99%.