Separation of zirconium and uranium

Zirconium is selectively precipitated from aqueous solutions containing zirconium and uranium by treatment with a precipitant consisting of tartaric acid or a tartrate.

This invention relates to separation and recovery of zirconium from aqueous 
solutions containing zirconium and uranium. Such solutions are typically 
those formed by the processes disclosed in U.S. Pat. Nos. 3,658,466 and 
4,231,994. Those processes involve initial sulfuric acid leaching of 
zircon sands to extract zirconium, along with hafnium and uranium which 
are commonly present in the sands. Recovery of zirconium, with substantial 
separation from hafnium, is then accomplished by solvent extraction with 
an organic amine, followed by stripping with sodium chloride solution to 
remove the zirconium from the organic phase. 
Separation of zirconium from uranium is, however, difficult since the 
uranium tends to accompany the zirconium in the solvent extraction and 
stripping steps. It is therefor desirable, and an object of the invention, 
to provide a simple and economical way of removing a major portion of the 
zirconium from the zirconium and uranium-containing strip solutions, with 
minimal removal of uranium. This is particularly desirable for production 
of nucleargrade zirconium, in which the uranium content must be reduced to 
3 ppm or less in the final product. 
It has now been found, according to the present invention, that such a 
removal of zirconium may be accomplished by means of a process involving 
precipitation of zirconium from such zirconium and uranium-containing feed 
solutions by means of tartaric acid or a tartrate. Tartaric acid or 
ammonium tartrate are the preferred precipitants, but other tartrates such 
as sodium tartrate may be used. 
Precipitation of zirconium from the feed solution is accomplished by 
addition of precipitant in an amount, usually approximately 
stoichiometric, sufficient for maximum precipitation of zirconium, with 
minimal precipitation of uranium. When the feed solution consists of a 
strip solution of the type discussed above, the amount of precipitant will 
usually range from about 0.05 to 0.3 mole. The precipitant is added with 
agitation, such as stirring, of the solution, and ambient conditions of 
temperature and pressure are usually satisfactory. The pH of the feed is 
not critical, but will usually range from about 0.2 to 1.0. Addition of 
about 20 to 30 volume percent of methanol with, or following addition of, 
the precipitant is also usually desirable for the purpose of speeding 
settling and facilitating filtering of the flocculant precipitate. 
Subsequent treatment of the zirconium tartrate precipitate will ordinarily 
consist of conversion to ZrO.sub.2 by conventional means such as roasting, 
with the ZrO.sub.2 ultimately being used as a feed material to make 
zirconium sponge. 
The invention will be more specifically illustrated by the following 
examples.

EXAMPLE 1 
A feed solution from a solvent extraction process for recovery of zirconium 
from zircon sands was treated according to the process of the invention. 
The feed consisted of a strip liquor obtained from use of a 1.5 molar NaCl 
strip solution to strip zirconium from a zirconium-loaded amine 
extractant. The strip liquor contained 23 g/l zirconium, 12 ppm uranium 
relative to zirconium, 3.8 g/l chloride, 120 g/l sulfate, and was 0.44 
normal with respect to hydrogen ion. 
Ammonium tartrate in the amount of 10.6 grams was dissolved in 200 ml of 
the feed, and a 25 ml portion of methanol was added with stirring. A white 
precipitate was formed. After 20 minutes of standing, another 25 ml 
portion of methanol was added. After 45 minutes of additional stirring, 
the precipitate was permitted to settle for one and one-half hours, and 
the resulting amorphous precipitate was filtered, washed with two 25 ml 
portions of methanol and dried at 125.degree. C. 
X-ray diffraction studies identified the major component of the precipitate 
as a zirconium tartrate compound containing approximately 27.5 to 27.7 
percent zirconium. Eighty percent of the zirconium in the feed solution 
was thus recovered as precipitate, and the dried precipitate contained 
2.78 ppm uranium relative to zirconium. 
EXAMPLE 2 
A feed solution from a solvent extraction process for recovery of zirconium 
from zircon sands was treated according to the process of the invention. 
The feed consisted of a strip liquor obtained from use of a 1.5 molar NaCl 
strip solution to strip zirconium from a zirconium-loaded amine 
extractant. The strip liquor contained 13 g/l zirconium, 10 ppm uranium 
relative to zirconium, 25 g/l chloride, 70 g/l sulfate, and was 0.20 
normal with respect to hydrogen ion. 
Tartaric acid in the amount of 2.58 grams was dissolved in 200 ml of the 
feed, and a 25 ml portion of methanol was added with stirring. A white 
precipitate was formed. After 20 minutes of standing, another 25 ml 
portion of methanol was added. The solution is stirred intermittently. 
After aging overnight, the resulting amorphous precipitate was filtered, 
washed with two 25 ml portions of methanol and dried at 125.degree. C. 
X-ray diffraction studies identified the major component of the precipitate 
as a zirconium tartrate compound containing approximately 27.5 to 27.7 
percent zirconium. Sixty-three percent of the zirconium in the feed 
solution was thus recovered as precipitate, and the dried precipitate 
contained &lt;1.9 ppm uranium relative to zirconium.