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Solvent Extraction process

The nuclear energy industry was the prime user of the solvent extraction technique
for metals separation and recovery up to the time of base metals recovery in
the late 1960s when the first large copper plants came into production.
The recovery of uranium from ores by using solvent extraction began in 1955 with
the use of di-ethylhexyl phosphoric acid (DEHPA) (the DAPEX process), and
since 1957 secondary or particularly the tertiary amines (the AMEX process) have
been the most popular extractants.
The tertiary amines are selective for uranium in the presence of impurities such as
iron, thorium, phosphate and rare earths. Molybdenum as well as zirconium, if
present, will also be extracted.
The DAPEX process using DEHPA is not selective, and will also extract many
other metals, such as iron, vanadium and rare earths. The general solvent extraction
flow sheet is shown schematically in Fig.
The metal bearing process solution is usually fed as a countercurrent to a flow of
an organic solvent fed into a mixing device or contactor to mix the two phases.
This contact, or extraction process, results in the transfer of the metal species from
the aqueous phase into the organic phase.
Generally, more than a single stage of contact will be required in order to obtain
maximum recovery of the metal. Following mixing, the phases are allowed to
separate or coalesce. The aqueous phase, or raffinate, is separated from the organic
phase and may be treated for the recovery of other values, recycled to some point
upstream or downstream of the solvent extraction process, or discharged as waste.
Following extraction, the loaded solvent is usually contacted with a scrub solution
to remove undesirable impurities from the solvent prior to recovery of the metal,
in this case uranium. In uranium circuits the common impurities in the solvent,
which are usually caused by absorption, will be the entrained leach feed liquor
which will contain iron, silica, aluminium and other impurities. Removal of these,
usually by washing in water, will result in minimum emulsion and crud formation
as well as a better final uranium product.
After scrubbing, the solvent passes to the stripping circuit where the uranium
is recovered in an aqueous solution by contact of the solvent with a suitable
aqueous solution. The resultant strip solution is treated in a precipitation circuit to
produce a uranium 'yellow cake' product. The stripped solvent is returned to the
extraction circuit. If necessary it may be treated (equilibrated) with sulphuric acid
prior to extraction to obtain maximum stage efficiency.
Several contactors may be required in each of the extraction, scrubbing and
stripping circuits depending upon the particular feed solution concentration and
impurities present. In addition, different contactors may be used in each circuit to
provide for optimum operation and economy, as well as to minimize the potential
environmental impact of the process wastes.

The most common lixiviant for uranium ores has been sulphuric acid, although
at least one plant has used nitric acid with a tri-n-butyl phosphate (TBP) extraction
and a few plants have used alkaline leaching followed by direct precipitation of the
yellow cake. Several plants use a combination of ion exchange and solvent
extraction in treating sulphuric acid leach solutions containing uranium. The
possible use of chloride leaching has been thoroughly investigated and should be
carefully considered for future uranium plants.
For the most part, mixer settlers have been the contactors used in the processing of
uranium bearing liquors, with many modifications and designs having been
presented since the early gravity mixer settlers. More recently there has been an
interest in the possible application of differential column contactors, and now there
are plants using a compact sieve plate pulse column design.

Although both the alkyl phosphoric acids and amines are possible extractants, the
alkyl phosphoric acids never did become popular, mainly because of their non-
discriminating nature compared with me relatively discriminating amines. Thus the
tertiary amines continue to be the most widely used for treating process solutions
resulting from sulphuric acid leaching of uranium bearing materials. As noted
earlier, there is also the possibility of leaching ores in nitric acid, and therefore the
neutral alkyl phosphate (TBP) can be used with success.
1. Acidic extractants
The extraction of metals as cations from acidic solutions is very much dependent
on pH, and therefore the degree of extraction is somewhat parallel to the order
of the hydrolysis constants. Because of this sensitivity to pH there must be close
control of the acidity in order to reduce the amounts of metal contaminants that are
also extracted. The common extractant in the so called DAPEX process has been
di-2-ethylhexyl phosphoric acid, which is often abbreviated to DEHPA, EHPA or
2(RH)2 + U02S04 * U02R4H2 + H2S04
As noted above and earlier, control of the pH value is important in this system, and
unwanted metals can be extracted and be a problem. One such co-extracted metal
is iron. This contaminant not only occupies sites on the extractant, but is also
extremely difficult to strip.
The degree of co-extraction can be minimized by maintaining the iron species
in the reduced state of oxidation during the extraction stages. In addition, because
the extraction of metals by DEHPA is usually very fast, the kinetic differences
between uranium and iron, the latter being extracted very slowly, can enhance the
discrimination and reject the iron. Recently, other alkyl phosphorus acid
extractants have been produced that could offer possibilities in the extraction of
uranium: these are phosphonic acid (Albright and Wilson) and the phosphinic acid
(Cyanamid Chemicals).
2. Basic extractants
Tertiary amines, Alamine 336 have been the most widely used anion extractants
for the recovery of uranium from sulphuric acid leach liquors. While these
extractants are relatively selective for uranium, there are nevertheless a few other
metals that extract much more preferentially.
In uranium circuits the major impurity that is extracted preferentially to uranium is
molybdenum. It can be removed by carbonate stripping after first selectively
stripping the uranium with a chloride solution. Several plants have operated
successfully with such a process. In addition, oxidized vanadium, if present, will
be extracted and stripped together with the molybdenum. Another impurity to the
uranium circuit could be that of zirconium. If extracted, even in small quantities, it
can present a problem in the stripping circuit in the form of a crud.
Zirconium co-extraction can be suppressed by the addition of phosphate. Although
iron is not extracted it can be absorbed onto the organic phase. This impurity can
be removed prior to uranium stripping by scrubbing in water. If arsenic is present it
will be removed in a scrub stage.
The extraction of uranium with a tertiary amine from a sulphate solution can
be represented as follows:
2(R3NH)2S04 + U0 2S0 4 * (R3NH)4U02(S04)3
The effectiveness of amines for the extraction from either sulphate or chloride
media is in the following order:
quaternary > tertiary > secondary > primary
Amines can be used in sulphate or chloride media without a problem of amine
degradation. However, the amines are degraded very quickly in the presence of
nitrates or nitric acid, or at high oxidation potential in the leaching solutions. This
problem of oxidation degradation has occurred in several mills when excessive
amounts of sodium chlorate oxidant have been added in the leach, resulting in an
electromotive force (EMF) of much greater than 600 mV, and thus in amine
degradation. Obviously, good EMF control is necessary to prevent oxidation and
excessive losses of the reagent.
3. Neutral extractants
Tri-n-butyl phosphate has been used very extensively in the nuclear field, but
primarily for the refining of die mill grade uranium product to high purity uranium
compounds such as UO3, U02 and UF4. Only one mill has used the TBP-HNO3
process. The TBP-HNO3 system has also been used successfully for the
production of a refined zirconium metal for nuclear fuel cladding.
Uranium extraction technology, International atomic energy agency, vienna, 1993,
Technical reports series no.359.

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