Lesson 5 5.4 The PUREX Reprocessing Process

Organic solvent extraction (OSE) is the selective transfer of components between two immiscible liquids. The organic solvent is 30% TBP diluted in odourless kerosene (OK). The aqueous feed from the dissolver, typically containing about 250 g U/L, is contacted with the solvent in a counter-current pulsed column.

How it works:

  1. The aqueous feed (containing dissolved U, Pu, fission products, and minor actinides in nitric acid) is pumped into the pulsed column roughly halfway up.
  2. The TBP/OK solvent is fed in at the bottom and rises through the column.
  3. As the two phases mix, uranium and plutonium are selectively extracted into the organic (solvent) phase via the following reactions:

UO22++2NO3+2TBPUO2(NO3)2(TBP)2\text{UO}_2^{2+} + 2\text{NO}_3^{-} + 2\text{TBP} \rightarrow \text{UO}_2(\text{NO}_3)_2 \cdot (\text{TBP})_2

Pu4++4NO3+2TBPPu(NO3)4(TBP)2\text{Pu}^{4+} + 4\text{NO}_3^{-} + 2\text{TBP} \rightarrow \text{Pu}(\text{NO}_3)_4 \cdot (\text{TBP})_2

  1. The fission products remain in the aqueous phase (containing >99% of the total activity).
  2. Fresh aqueous nitric acid is fed in at the top of the column to scrub any remaining fission products from the rising loaded solvent.

Why TBP works so well:

  • TBP is highly selective for uranium and plutonium over fission products (distribution factors are orders of magnitude higher).
  • TBP has reasonable resistance to radiation and nitric acid damage.
  • It has low volatility and flammability.
  • The kerosene diluent is cheap and readily obtainable.
  • No salting agents are required (unlike earlier processes), which reduces waste volumes.

THORP uses three stages of pulsed column contactors in the highly active (HA) cycle to separate the uranium/plutonium from the waste stream, followed by further columns for purification.

Types of Contactor Equipment

The choice of contactor equipment in a PUREX plant significantly affects throughput, separation efficiency, and criticality safety:

Contactor TypePrincipleAdvantagesDisadvantagesWhere Used
Pulsed columnTwo liquid phases flow counter-currently through a tall column; a pulsing mechanism creates turbulent mixing at perforated platesContinuous operation; no moving parts in contact with active liquor; good criticality geometry (tall, narrow)Large physical size; slow to reach steady state; difficult to cleanTHORP (UK), UP3 La Hague (France) — HA cycle
Mixer-settlerLiquids mixed in a stirred vessel, then separated by gravity in a settling chamber; stages connected in seriesFlexible; easy to operate and maintain; high stage efficiency; well-understood technologyLarge floor area; high liquid inventory (criticality concern); moving parts in active environmentUranium purification cycles at THORP; La Hague plutonium purification
Centrifugal contactorLiquids mixed and separated by centrifugal force in a rapidly spinning rotorVery short contact time (seconds); very small liquid inventory (excellent for criticality safety); compactComplex mechanical design; moving parts require maintenanceSavannah River (USA); some modern facilities

In general, pulsed columns are preferred for the highly active first cycle (where the liquid inventory is most radioactive and criticality control by geometry is paramount), while mixer-settlers are used for the lower-activity purification cycles where their flexibility and high efficiency are advantageous.

Key Point: The aqueous phase containing fission products and other actinides is the highly active raffinate — this is high-level waste (HLW). It is stored in water-cooled, double-walled stainless steel tanks prior to vitrification.